摘要:

l 2 2 Ethyl bromide .............. Propyl ................ Butyl ................ Iso-propyl bromide. ......... Amy1 bromide.. ............ ABSTRACTS OH CHEMICAL PAPERS. 0 *8 1 '0 3'6 8.8 4 '5 Organic Chemistry. 81.2 65.2 25.2 15 7 33-45 Methods for Determining the Relative Stability of the Alkyl Bromides. By I. REMSEN and H. W. HILLTER (Anrer. C7~ern. J., 8, 251-262) .-The bromides in molecular proportion were treated in alcoholic solution with the several reagents, and the hydrobromic acid formed estimated by silver nitrate solution with ferric thiocyanate as indicator. The relative results are embodied in the following table, Column I showing the action of zinc arid dilute sulphuric acid; 11, the action of cobalt-zinc couples and acetic acid ; I11 and IV, the action of alcoholic soda under certain conditions; T, the action of cobalt-zinc couples in presence of soda, but after deducting the action of the soda itself; VI, that of ammonia; and VII, that of silver nitrate o r acetate.The action of sodium amalgam is unsatisfactory, owing to the cnnstant variation of the alkalinity of the solution, and the authors believe that the best results are to be obtained by the action of cauqtic soda or ammonia, or of silver salts. 1 . 0 - - 1.11 27 3 2.6 0'58 - - 0 53 4.3 21.7 0.83 -- - ------- I 11. 1 -3 3 *3 6 '0 11 *1 9 . 5 111. 28 -4 9.1 4 '3 3 . 4 4 -5 IV. 1 v. 1 TI. 1 VII. H. B. Derivatives of Diethylene Bisulphide. By W. MANSFIELD (Ber., 19, 2658-2668) .--In continuation of former work (Abstr., 1886, 525), other derivatives of diethylene bisulphide, C4H8S, (compare Masson, Trans., 1886, 234), are described.The metlhiodide, C4HBS2,MeI, is converted by silver chloride into the corresponding chlorine compound, a crystalline substance me1 ting at 225" ; it yields crystalline precipitat,es with platinic, mercuric, and auric chlorides. With moist silver oxide, the methiodide yields the corresponding hydroxide, C4H8S2Me*OH, the solution of which possesses w ell-marked basic propei-ties, absorbs carbonic anhydride, and precipitates solutions of the heavy metals. The salts obtained by its neutralisation with acids are exceedingly deliquescent ; the most stable is the picrate, which chrystallises in golden needles meltiiig at 192-193'. The dimethiodide, C4H8S2,2MeI, nielts a t 207-208", and yields a corresponding chloro-derivative, which gives precipitates with the chlorides of the platinum-group of metals.In the course of the preparation of the dimethiodide, a periodide' of the composition C4H8SaMeI,12 is obtained, which melts at 92-93", and crystallises in the monoclinic system (a : b : c = 0.89 : 1 : 0.67). Experiments made with a, view of obtaining the hydroxides byORQANIC CHEMISTRY. 128 evaporation of their aqueous solutions were unsuccessful ; an oil of composition C,H,,S, was formed (to this substance Masson ascribes the formula C,,H,S,, ibid., 247). The author considers that this compound is derived from dithioglycocine by the displacement of both sulphydryl hydrogen-atoms by the methyl and vinyl groupings respectively, thus, SMe*C,H,*S*CH : CH, ; and in accordance with this view it is shown that the compound takes up four atoms of bromine. Diethylene bisulphide combities readily with benzyl halogen com- pounds ; thus with the bromide it forms a substance, ClH8S2,C,H7Br, which melts at 146", and crystallises in the rhombic system.The corresponding iodine compound crystallises in pale yellow needles, de- composing when heated a t 145", and the chlorine compound in colour- less needles melting. a t 143". On heating the above bromine compound with alkalis, an oifof the composition Gl1H,S, is produced. V. H. V. Disulphones. By R. ESCALES and E. BAUMANN (Ber., 19, 2814- 28 17) .-Ethylidenediethylsulp hone, CHMe ( S0,E t),, is prepared by the action of potassium permanganate on a-dithioethylpropionic acid (from pyruvic acid and mercaptan). It forms plates rather soluble in water, more soluble in alcohol and ether.It melts a t 60°, and distils without decomposition. The bromo-derivative, CBrMe( SO,Et),, crystallises in small prisms melting at 115" ; it is sparingly soluble. Ethylitlenedipheny ZsuZp hone, CHMe (SO,Et),, is prepared by gradu- ally treating a very dilute solution of potassium dithiophenylpropio- nate (Abstr., 1886, 878) with 1 per cent. permanganate solution. It is insoluble in water, alkalis, and, acids, sparingly soluble in alcohol and ether, more readily in benzene. It melts at 101-102". It is isomeric with Blomstrand and E werloeff 's etbylenediphenylsulphone (Ber., 4, 726; compare also Otto and Damkohler, J. Pherm. Chern., 30, 171 and 321). Disulphcnes.Br E. BAUMANN ( B e y . , 19, 2806-2814) .-Diethyl- sul~honedimetliylmetha?1e, CMe2( S02Et),, is prepared by shaking dithioethyldimethylmethane with 5 per cent. permanganate solution, and occasionally adding a few drops of acetic or sulphuric acid. When no more permanganate is decolorised, the liquid is heated and filtered, and the filtrate evaporated to half its bulk. The greater part of the disulphone separates on cooling. It crystallises in thick prisms, melts at 130-131", and boils with slight decomposition a t about 300". It is readily soluble i n warm alcohol and water, rather soluble in ether, benzene and chloroform. Sulphuric acid dissolves it very readily, and decomposes it when warmed; nitric acid and bromine both dissolve it, but are without further action.Dietli yls~lphonepr~7metliylllzethane, C MePr( SO,Et),, crystallises from water in long needles melting at 86" ; it dissolves sparingly in water, readily in alcohol, ether, and chloroform. Ethylic P-diethylsulphonebzctyrafe, CMe( SO,Et),.COOEt, is prepared by oxidising ethylic P-dithioethylbutymte. It crystallises from water in slender needles more than an inch long, melts at 63", and dissolves very sparingly in cold water, more readily iu alcohol and ether. N. H. M.124 ABSTHACTS OF CHEMICAL PAPERS. Diethyls~lphonsmethnne, CH,(SO,Et),, is obtained by oxidising ethyl orthothioformata (Gabriel, this Journal, 1877, ii, 311) with potassium permanganate in presence of sulphuric mid. It orystallises in lustrous plates melting at 104" ; and dissolves sparingly in ether, readily in benzene and alcohol.When t h e aqueous Bolution is treated with bromine-water, the dihromo-deriz?ative, CBr,( SO,Et),, is formed. This crystallises from boiling water in lustrous needles melting at 131". The disulphone is probably formed by the oxidatioh of the sulphide CH,(SEt), present in the thio-ether. N. H. M. Reagent for the Hydroxyl-group. By H. A. LANDWEHR (Ber., 19, 2726).-The substance to be tested is added in excess to 10 to 20 C.C. of a solution of ferric chloride (prepared by adding two drops of a, 10 per cent. solution of ferric chloride to 60 C.C. of water) con- tained in a white dish. The production of a sulphur colour denotes the presence of hydroxyl. All bydroxy-acids and all alcohols and carbo- hydrates which dissolve in water give the reaction.Ether, alkyl salts, formic, propionic, butyric, oxalic, fumsric, and maloaic acids give negstiv e results . N. H. M. Non-acid Constituents of Beeswax. By B. SCHWALB (Annalm, 235, 106--149).-Repeated boiling with alcohol extracts about 5 per cent. of cerotic acid from beeswax. The residue is saponified with alcoholic soda, and after the alcohol has been removed by distillation and by boiling with wpter, the soap is separated by the addition of common salt. To remove any free alkali, the soap is pressed in a cloth, redissolved in hot water, and again salted out. This operation is repented several times. The soap is thoroughly dried at 110-120", and the non-acid constituents are separated by fractional solution in, and recry stallisation from, light petroleum.The most soluble portion of the extract, melting between 55" and 6 5 O , contains two hydrocarbons; one melting at GO.5" appears to be identical with Krafft's normal heptacosane, C27H,s (Abstr., 1882, 1273), and the other which melts at 67", is probably identical with normal hentriacontane, CYIHM. It is probable that other hydro- carbons are also contained in the wax, The myricyl alcohol is less soluble in light petroleum than the hydrocarbons. It appears to have the formula C31H640, and is not identical with the alcohol C30H6,0, contained in carnauba wax (Abstr., 1884,1281). I t melts at 85-85.5", and resolidifies at 84". When hetlted with soda lime, it is converted into the salt of an acid, C31HB202. This acid is sparingly soluble in the usual solvents at the ordinary temperature, but i t dissolveR in hot light petroleum, and is deposited from the solution in white needle-shaped crystals, which melt at 88.5-89'.The lead salt melts at 115-116", and dissolves freely in acetic acid and in boiling toluene. The silver salt is amorphous. It melts at 180", with decomposition. The copper and magnesium salts are also amorphous. They dissolve in boiling benzene. The methyl and ethyl salts crystallise in needles. They dissolve freely in warmORGANIC CHEMISTRY. 125 ether and warm alcohol. The methyl salt melts at 71-71.5", and the ethyl salt at 69-5-70". Heated under the ordinary atmospheric pressure, the ethyl salt decomposes before boiling into ethylene and the free acid. Beeswax also contains two lower alcohols, namely, ceryl alcohol, C2sH,,0 or C2,H5,0, and an alcohol of the formula, C2rHw0 or C z a 5 2 0.Conversion of Starch into Glucose by means of Hydrochloric Acid. By S. HARVEY (AnaZyst, 11, 221-223).--Tn reference t o the process used by Heisch, heating in a boiling water-bath is as good as heating over a naked flame. In the author's experiments, when- ever the conversion of starch was complete, the results obtained were too low, owing to destruction of the glucose ; in fact, it appears impossible to limit the time of heating, so as to prevent the glucose being attacked. D. A. L. Carbohydrates. By M. HONIG and S. SCHUBERT (Monatsh. Chew,., 7, 455-484).-1n a former paper (Abstr., 1886, 44), the authors have shown that by the action of sulphuric acid on cellulose and starch, a series of sulphuric acid-derivatives are formed of the general composition Cs,H,,,O,,,( SO,),.These are decomposed in alcoholic solution with production of sparingly soluble compounds, containing a smaller proportion of sulphuric acid, which in their turn are decomposed at a higher temperature with formation of various dextrins. The different phases of these changes in the case of cellulose, starch, and grape-sugar are worked out more fully in this paper. From cellulose, a series of derivatives is obtained from a form of soluble cellulose to dextrose, according to the temperature (5-33") at which the change is effected ; these increase in specific rotatory power and solubility, the lower members of the series giving a blue coloration with iodine, the intermediate a red, and the end products no coloration, corresponding with the formation of an achroo- dextrin.These substances also differ from one another as regards their conversion by diastase ; the end members are unaltered, whilst the others are converted into dextrins. From starch, a similar series of compounds was obtained ; although in this case the specific rotatory power diminishes from that of starch t o that of a dextrin similar to the final product from cellulose, but differing from it in possessing a slight cupric oxide reducing power. w. c. w. With grape-sugar also, similar results were obtained. In conclusion, the question is discussed whether the starch mole- cule is compounded of other less complex units, differing among themselves, a view represented by the formula 15( C,2H200,,), assigned by Brown and Heron, or whether it is decomposed into these less complex molecules by a chemical change rather than by a process of disintegration.Identity of Cadaverine with Pentamethylenediarnine. By A. LADENBURG (Ber., 19, 2585-2586) .--Cadaverhe and penta- methylenediamhe show the same boiling point, solubility and odour, V. H. V. VOL. LII. E126 ABSTRACTS OF CHEMICAL PAPERS. and agree in their general reactions. The mercuriochloride of pentn- methylenediamine has the forniula C5H,,N,,2HC1,3HgCl2, whilst, according to Brieger, that of cadaverine mercuriochloride is C~HlrN~,2HC1,4HgCI2. The imine obtained from cadaverine is identical in its properties with piperidine, which the author has previously shown to be the imine of pentamethylenediamine (Abstr., 1886, 139, 269).w. P. w. Compounds of Aldehydes and Ketones with Mercaptan. Bay E. BAUMANX (Ber., 19, 2803--2806).-When furfuraldehyde and mercaptan are treated with dry hydrogen chloride, the reaction is accompanied by considerable development of heat, which causes a further deco tnposition. Fatty aldehydes and ketones and aromatic aldehydes also react with mercaptan with development of heat ; with fatty aromatic ketones, the mixture must be warmed, whilst in the ease of benzophenone the reaction only takes place in presence of zinc chloride. When dithiophenyldim ethylme thane, CMe2( SPh) (Abstr., 188-5, 749), is prepared, avoiding development of heat, a solid product is obtained instead of an oil.It forms large, clear crystals, which melt at 56", and dissolve readily in alcohol, ether, benzene, &c., and are insoluble in water. When heated at loo", it decomposes into a mix- ture of several substances, which no longer solidifies. Dithioethyl- dimethylmethane, CMe,(SEt)2 (Zoc. cit.), was also prepared at, a lower temperature, and was obtained as a mobile, strongly refractive liquid, boiling at 190-191" ; it combines directly with methyl iodide, yielding a crystalline substance. N. H. M. Linoleic Acid. By K. PETERS (Monatsh. Chem., '7, 552-555).- The formula generally ascribed to linoleic acid is C18H2602 ; it would thus be the isologue of palmitic acid, and convertible into it by hydrogenising agents. It is here shown that the analytical results of a sample of an acid, purified by means of its barium salt, are more in accordance with the formula C18H3202, and when heated with, phos- phorus and hydriodic acid, it yields not palmitic, but stearic acid.V. H. V. AcetyllEevulinic Acid. Constitution of v-Ketonic Acids. By J. BREDT (Annulen, 236, %25-232) .-Acetyllaevulinic acid is formed by the action of acetic anhydride on lavulinio acid at 100". It is deposited from an alcoholic solution in crystals, resembling those of potassium nitrate. It melts at 78-79", and boils about 14OC, under 15 mm. pressure ; under the ordinary atmospheric pressure, it splits up on boiling into acetic acid and a- and P-angelica lactones. As the compound is neither decomposed by water nor by a cold solution of sodium carbonate, the author regards it as a hydroxy- lactone-derivative, not as an anhydride.This is evidence in favour of the formula C H , < ~ ~ ~ > C M e . O H for lavulinic acid. w. c. w.ORGANIC CHEMISTRY. 127 New Reaction of Aluminium Chloride; Syntheses in the Acetic Series. By A. COMBES (Compt. rend., 103, 814-817).- When aluminium chloride is added to a solution of acetic chloride in carbon bisulphide or chloroform, there is abundant evolution of hydrogen chloride, and a white, crystalline solid of the composition C12H,406A12C18 is obtained. It remains unaltered in dry air, but is immediately decomposed by water with evolution of carbonic anhr- dride. If the water is added carefully to the solid, or if the lrhtter is thrown into water in small quantities at a time, a clear liquid is obtained, which, when extracted with ether, or better, chloroform, yields a colourless liquid boiling at, 156-137" under a pressure of 750 mm.It has the composition C6H8O2, and is lighter than water, in which it is readily soluble without undergoing any decomposition. The action of aluminium chloride on acetic chloride is represented by the equation- 6CzH30C1 + Al,Cl, = 4HC1 + (COMe*CH2*CO-CE2.CC1zO~)zAlzC14, and the solid compound is decomposed by water with formation of aluminium hydroxide and the acid COMe*CH,*CO*CH,*COOH, which immediately loses carbonic anhydride and yields acetylacetone, CsH,02. Acehjacetoize has the properties of a diketone, and combines, with development of heat, with a concentrated solution of sodium hydrogen sulphite.It is not affected by phosphorous chloride or acetic chloride, but is decomposed by potash or soda, with formation of acetone and an acetate. When treated with sodium amalgam, it yields isopropyl alcohol, pinacone, and sodium acetate. If slowly hydrogenised in an acid solution, it should yield symmetrical amylic isoglyool, CH2( CHM~OOH)~. Bromine acts energetically on acetyl- acetone, with formation of acetic bromide and penta- and tetra-brom- acetone. Phosphoric chloride removes the oxygen, and yields a tetrachloride which immediately loses 2 mols. HCl, and yields chlorides of the composition C5H6C1,, derived from an unknown valer-ylene. When the solid product of the action of aluminium chloride on acetic chloride is treated with absolute alcohol instead of water, no gas is evolved.The products will be described in a subsequent This reacicion is general, and takes place with propionic and butyric paper: chlorides, and with chloral. C. H. B. Gluconic Acids. By F. VOLPERT ( B e y . , 19, 2621 - 2623)- Ethy lic pentacetylgl ucoiiate is a white, crystalline substance, readily soluble in alcohol and water; it melts a t 103.5". Ammonium and potassium gluconate crystallise well in plates and needles. Corn para- tive experiments made with Hoenig's paragluconic acid (hbstr., 1881, 893) show that it is identical with gluconic acid. Action of Thiocarbamide on Ethyl Acetoacetate. By R. LIST (Annalen, 236, 1-32) - In the preparation of thiornethyluracil from thiocarbamide and ethyl acetoacetate, by the process previously described by the author (Abstr., 1886, 4 3 ) , it is found that the pre- N. H.M. k P128 ABSTRACTS OF CHEMICAL PAPERS. sence of ammonium thiocyanate increases the yield of the product. Thiomethyluracil, CS<NH .-,b->CH, is very sparingly soluble in NH*CVe alcohol, ether, and cold water. It crystallises in plates, and begins t o decompose at 280'. The silver and copper salts are amorphous. The mercuric salt forms anhydrous, micaroscopic needles. The potas- sium salt, C5H,NzOSK + QHzO, is insoluble in alcohol, but freely soluble in water. The sodium salt, C5H5N20SNa + 2Hz0, crys- tallises in prisms, which effloresce on exposure to the atmosphere. The methyl salt melts at 219-220", but begins to sublime at 120", forming plates or needle-shaped crystals. The addition of silver nitrate to the amrnoniacal solution of this substance precipitates the compound C6H,NzSOPhg.E thy1 t hiometh y Zuracilacetate is obtained in needle- shaped crystals by the action of ethyl monochloracetate on thiomethyluiacil. Thio- meth9luraciZacetic acid crystallises in needles or plates, and melts a t 203-204". It is very sparingly soluble in cold water, alcohol, and ether. Thiomethyluracil unites with hydrogen bromide to form an unstable crystalline additive product. Bromine acts on thiornefhylnracil sus- pended in water, eliminating the sulphur and forming dibromoxy- methyluracil. By a similar reaction, dichloroxymethyluracil is obtained in transparent plates, soluble in hot water and in warm alcohol. Thiomethyluracil is converted into methyluracil by boiling with freshly precipitated d v e r or mercuric oxide, and also by the action of ammonia, or strong hydrochloric acid at 150", and of acetic acid at 180".w. c. w. The ethyl compound melts a t 144-145". Nitro- derivatives of Methyluracil. By A. KOHLER (Annalen, 236, 32-57) .-Behrend (Armalen, 229, 32) obtained nitrouracil- carboxylic acid and a cornpound, C5H2N405, by the action of strong nitric acid on methyluracil. Nitrouracilcarboxylic acid, C5H,N30, + 2H,O, crystallises in rhombic prisms ; a : b : c = 0.323: 1 : 1.081. On boiling the aqueous solution, carbonic anhydride is evolved and nitro- uracil, CaH3N30a, is formed. Ethy I nitrourncilcarBo~ylate, prepared by saturating the alcoholic solution of the acid with hydrogen chloride, crystallises in monoclinic prisms.I t is less soluble in alcohol and water than the free acid, and it does not split up on boiling with water. The salt melts at about 250" with partial decomposition. The constitution of this substance may be represented by the formula Amido~?.a~ilcarbox~lic acid, C5H5N30,, is formed by the action of tin and hydrochloric acid on the nitro-acid, but a better yield is obtained by the reduction of the ethyl salt. The product, con- sisting of a mixture of the ethyl salts of amidouracilcarboxylic and hjdroxyuracilcarboxylic acids, is saponified by boiling with an aqueoiis solution of potassium hydroxide. Amidouracilcarboxylic acid is deposited from its aqueous solution in needles. Between 150" and 160", it splits u p into carbonic anhydride and amidouracil.The potassium salt, C5H6N,05K + HzO, crystallises in prisms ; the barium,ORGXSIC CHEMLSTRY. 7 29 copper, and mercury salts are amorphous. The sparingly soluble lead and silver salts are crystalline. The ethyl salt is insoluble in alcohol and sparingly soluble in water. It melts sat 260" with p r t i e l decom- position. A4 good yield of nitrouracil is obtained by adding 5 C.C. of strong snlphuric acid to 4 grams of methyluracil suspended in 10 C.C. of fuming nitric acid. The yield of the sparingly soluble compound, C5H2N,05, which is obtained as a bye-product by the action of nitric acid on methyluracil, is increased by warming the mixture as som as the reaction ceases. C5HN,05*NB, t &H20 crystallises in yellow glistening needles ; C5HN,05R + liE20, red needles, sparingly soluble in water ; the soiution decomposes, on boiling.The barium salt, (C5HN405)2Ba + 4H20, forms prismatic needles, freely soluble in water. On reduction with tin and hydro- chloric acid, the amido-compound, C,H,N,O, + HzO, is obtained in slender needles, sparingly soluble in water. After evaporation with hydrochloric acid, the residue yields the murexide reaction. This compound unites with bases to form salts. w. c. w. New Mode of Formation of Dibromo- and Dichloro-bar- bituric Acids. By R. B E H n E w (Annulen, 236, 57-68).-The most convenient method of preparing bromomethyluracil (Abstr., 11386, 338) is to convert methyluracil into dibromoxymethyluracil by the action of bromine-water (Annden, 229, l8), and to decompose the product by boiling in alcohol.DichloroaymsthyZuraciZ resembles the corresponding bromo-derivative in its properties and in its mode of preparation. It crystallises in triclinic plates, and is not decomposed by boiling with alcohol. It is decomposed by alcohol or water at 150", forming a sparingly soluble compound, and is converted into mono- chloromethyluracil by the action of stannous chloride and hydro- chloric acid. Chloromethyluracil is insoluble in ether, sparingly soluble in water and alcohol. It crystallises in needles. Dibromoxymethyluracil is oxi dised to dibromoburbituric acid by fuming nitric acid. This is identical with the dibromobarbituric acid described by Baeyer (ArLnaZen, 130, 130). Hot fuming nitric acid converts dichloroxymethyluracil into dichlorobarbituric acid, C4H,Cl2NzO3.This substance crystallises in rhombic prisms or plates, a : b : c = 0.7766 : 1 : 0.8929. The crystals are isomorphous with those of dibromobarbituric acid, and are much more soluble in alcohol, ether, and water. A small quantity of barbituric acid is formed in the preparation of dichlorobarbituric acid by this process. Relation of the so-called a-Thiophenic Acid to the Normal Thiophencarboxylic Acids. By V. MEYER (AnnaZen, 236, 200- 224).-1n former communications (Abstr., 1885, 1207 ; 1886, 227, 534), the author has pointed out that the derivatives of a- and P-thio- phenic acids (melting a t 118" and at 126.5" respectively), are identical in crystalline form, solubility, and melting point, but that on decom- position the a-derivatives yield the a-acid, and the &derivatives the /3-acid.The so-called a-acid is really a mixture of the p- and 7-acids, which cannot be separated by recrystallisation. It is formed on w. c. m.130 ABSTRACTS OF CHEMICAL PAPERS. oxidising a mixture of ,9- and y-thiotolens, but is not obtained by mixing together the ready-formed p- and r-acids. In the thiophen- group the tendency for the isomeric compounds to crystallise together Halogen Carriers. By C. WILLGERODT (J. pr. Chem. [el, 34, 264c292).-An accoant of experiments on the effective value of various elements and their compounds in the chlorination of benzene (compare Abstr., 1885, 1034). Two cases occur on the passage of chlorine into benzene in presence of these foreign substances, namely, either the formation of benzene hexachloride attended by a consider- able gain in weight of the benzene and practically no evolution of hydrogen chloride, or the displacement of hydrogen by chlorine with corresponding evolution of hydrogen chloride.The details of the various experiments are given in full. To the substances inducing the first reaction belong aluminium hydroxide and sulphate ; those inducing the latter reaction are again separable into thoso elements the presence of which induces the production of mono- or di-substitution- derivatives, and those forming a chloride of the formula XC1, or (XCl,),, which lead to the production of tetra- o r penta-substitution- derivatives. The function of these is conditioned by the atomic mobility of the chlorine-atoms in its compound, and in fact to the affinity of some kind or another of the inorganic chloride for the carbon compound.Adopting the periodic system of classification, the members of the first two groups are inactive, those of the second, fifkh, seventh, and eighth groups are eminently active, and those of the fourth are, with the exception of tin, inactive. The experiments of Lothar Meyer, Friedel and Crafts, and others on the chlorination of carbon compounds by means of such substances as aluminium or ferric chloride, seem to indicate that a t first a hydrogen-atom of the hydrocarbon is displaced by the grouping M,CI, with separation of hydrogen chloride, and to this compound a molecule of chlorine adds itself on and finally takes the place of the hydrogen. The compounds AlzC16,6C6H6 (or 6C7He) obtained by Gustavson, the author regards as combinations of a molecule of metallic chloride with one of the hydrocarbon, the remaining five molecules functioning in like manner to water of crystallisation. is much stronger than in any other series.w. c. w. V. H. V. Preparation of Organic Fluorides. By 0. WALLACH (Annulen, 235, 255-271) .-Fhorobenzene, C,H,Fl, can easily be prepared by pouring 20-30 C.C. of strong hydrofluoric acid into a flask containing 10 grams of benzene dinzopiperidide. The flask is connected with a receiver by means of a spiral condenser surrounded by a freezing mixture. A tube passes through the doubly perforated cork which closes the receiver, and dips into mercury. On gently warming the flask, the reaction commences and the fluorobenzene collects in the receiver.Pluoroto Zuene is prepared from toluene paradiazopiperidido. As it is much easier to condense than fluorobenzene, the apparatus may be simplified by omitting the tube dipping iinder mercury. Fluorotoluene resembles benzonitrile in odour. It is oxidised by chromic acid, yielding fluorobenzoic acid.ORGANIC CHEMISTRY. 131 ATitl.obenzeneparadia~opiperidide forms golden, needle-shaped crys- tals. It melts at 96-97', and dissolves freely in ether and warm alcohol. It is decomposed by hydrofluoric acid, yielding parajuoro- nitrobenzene. This compound is also formed by nitrating flaorobenzene. It melts at 21-22' and boils at 204-206". Acetamidobenzene rnetadiazopiperidide, C6H4(NHAc) N N2C5B is deposited from weak alcohol in thick prisms which melt at 100- 101".It is decomposed by hydrofluoric acid, yielding metujluor- aniline ; an oily liquid resembling aniline. Parqfiuornniline is formed by reducing an alcoholic solution of parafluoronitrobenxene with stannous chloride and hydrochloric acid. The nitrate, hydrochloride, and sulphate crystsllise well. Acetic anhydride converts parafluor- aniline into ncetoJuoruniZide. This compound is sparingly soluble in water, but dissolves readily in alcohol. The replacement of hydrogen by fluorine increases the RP. gr., but has very slight effect on the boiling points of the compounds. Benzene ................ Toluene. ................ Nitro benzene ............ Aniline. ................. Fluorobenzene ............ Parafluoro to1 ue ne ........ Parafluoronitrobenzene ....Parafluoraniline .......... Sp. gr. 0.899 0.882 1.2 1.036 1.024 0.992 1326 1.153 B. p. 80.5" 3 11 205 184 84 -85 116" 205-206 185-189 Fluorobenzenesulphonic acid and fluorodiphenyl, when added to an alkaline solution of piperidine, form the compounds NaS03*C6H4*N2*C5NH10 and C5NHlo*N2*C6Ha*CsH4*N2*C5NHI0 respectively. w. c. w. Reaction of Potassium Cyanide with Orthonitrobenz ylic Chloride. By E. BAMBERGER (Ber., 19, 2635--2642).-1n the reac- tion between potassium cyanide and orthonitrobenzylic chloride there are formed, besides orthonitrobenzyl cyanide, an orthodinitrocyano- dibenzyl and substances of the composition C22H14N40, and CI5HON3O3, the constitution of which is uncertain. Orthonitrobenzy l cyailide, NOz*C6H4*CH2*CN, previousIy described by Salkowski, crystallises in pale-yellow prisms which melt at 82.5" ; its solutions give a blue-violet coloration on addition of s trace of alkali ; the dye formed is, however, unstable.Orthodinif rocyanodibemyl, N0,*C6H4*C'H( CN) *CH2*C6HI*NOa, crys- tallises in snow-white prisms, melts at 110.5" and is soluble in benzene, alcohol, and acetic acid. This substance is also obtained directly from orthonitrobenxyl chloride and the corresponding cyanide. It is very stable towards acids ; when heated with alkalis and the product heated with mineral acids, a compound, CI5HBN1O3, separates out in volum~nous, yellow flocculze, which can be crystallised from alcohol i n silky leaflets melting at 235-238". The same substance, i s also a subsidiary product in the above reaction.132 ABSTRACTS OF CHEMICAL PAPERS.The compound C22RliN406, mentioned above, crystallises in thick glisteaing prisms which melt at 190.6"; it is sparingly soluble in alcohol, readily in acetic acid ; it behaves towards acids and alkalis as a, perfectly indifferent substance. V. H. V. Oxidation of Nitromesitylene, By W. H. EMERSON (Amer. C h ~ m . J., 8, 268--271).-Schmitz has pointed out that as paranitro- mesitylcnic acid is prodnced during the preparation of mononitro- mesitylene, it is probable that the first-named substance is produced by the oxidation of the last-named, and therefore here as in other cases, except with mesitylene sulphonamide, the presence of the nitro-group protects those hydrocarbon side-chains that occupy the ortho-position relatively to the negative nitro-group.This oxidation has before been attempted but without success ; by dissolving both the substance and the chromic acid in glacial acetic acid, however, the paranitromesitylenic acid was actually obtained and recognised by its properties and by those of the corresponding amido-acid. H. B. Intramolecular Changes in the Propyl-group of the Cumene Series. By 0. WIDMAN (Ber., 19, 2769-278CL).-PropyZhyd~o- curbostyril, C12H15N0, is obtained by treating a solution of orthamido- cumenylacrylic acid (Abstr., 1886, 465) in soda with an excess of sodium amalgam. Acetic acid is then added, which precipitates a, yellow substance melting at 80"; this changes in a short time to propylhydrocarbostyril melting at 134".The latter crystallises in well-formed rhonibic prisms, a : 7, : c : = 0,87978 : 1 : 1.64451; p = 1.620435, and is very readily soluble in alcohol and benzene. The compound is also obtained by reducing orthamidoparapropylcinnamic acid (Abstr., 1886, 464). In the latter reaction, the isopi*opyl-group must have undergone an intermolecular change ; prop91 tiydrocarbo- stvril is therefore a normal comDound of the formula, Cumenylpropionic acid (Perkin, this Journal, 1877, i, 400) is best prepared by boiling pure cumenylacrylic acid for 45 minutes with 20 times its weight of hydriodic acid (sp. gr. 1.7) and an equal weight of red phosphorus. The product is filtered, washed with water, and dissolved in ammonia ; it is precipitated with acid, pressed, and dried.It melts sharply at 75.5" (not 70"). When gradually treated with fuming nitric acid (10 parts) at -5" to O", and the product poured into water, a white crystalline nitro-acid is precipi- tated; it crystallises from 50 per cent. acetic acid in well-formed plates melting at 99". When reduced, it yields propylhydrocar- bostyril. When cumenylpropionic acid is oxidised by potassium permanganate, it is converted into orthonitrohydroxyisopropylbenzoic acid (Abstr., 1886, 466). The above experiments show that a conversion of isopropyl into normal propyl occurs in the successive conversion of cumenylacry lic acid into cumenylpropionic acid, orthonitrocumenylpropionic acid, and propylhydrocarbostyril. The same molecular change dso takes place when cumenylacrylic acid is converted successively intoORGANIC CHEMISTRY.133 orthonitrocumenylacrylic acid, orthamidocumenylacrylic acid, and propylhydrocarbostyril. The author considers that the so-called '' cumenylpropionic acid " contains normal propyl, and that it is paraprop y lhydrocinnamic acid. The propionic radicle, therefore, as well as the methyl and acrylic acid radicles, influences a propyl-group in the para-position, causing the formation of normal propyl. N. H. M. Reciprocal Transformations of Cymene- and Cumene- derivatives. By 0. WIDMAN (Ber., 19, 2781-2785).-With regard t o the change of cumene- into cymene-derivatives, the author objects to Fileti's suggested law (this vol., p. 36) on the ground that the nature of the group has not been determined in any of the compounds containing these elements or groups (Cl, Br, Cy, COOH, &c.), and mentions experiments previously described by him (Abstr., 1886, 464) which show Fileti's view to be quite incorrect.By F. AHRENS (Ber., 19, 2717--2725).-0ctyI- benzene (v. Schweinitz, Abstr., 1886, 540) boils at 262-264" (uncorr.), sp. gr. 0.852 at 14". It solidifies at -7' to a crystalline mass, is insoluble in water, miscible with alcohol, ether, and ben- zene. Chloroctylbenzene, CsH,C1*CeH17, is prepared by the action of chlorine in presence of iodine on the hydrocarbon. It is a yellow- ish oil, almost without odour, readily soluble in alcohol and ether ; it boils at 270-275'. Bromnctylbenzene, C6'&Br*C8&, boils at 285-287". The moniodo-derivative is prepared by the action of iodine and mercury oxide on octylbenzene diluted with light petro- leum. I t is a yellow oil, insoluble in water, soluble in alcohol and ether.It solidifies at -4", and does not distil without decomposition. I t is very susceptible towards light and heat. Netanitro-octylbenzene, NOz*CsH&&, is formed by the action of fuming nitric acid on octylbenzene in the cold. It crystallises in long needles insoluble in water and ether ; sparingly soluble in alcohol and chloroform ; it melts at 123-124", and sublimes unchanged at a high temperature. When oxidised with potassium permanganate, it yields metanitro- benzoic acid. Orthonitro-octylbenxene is obtained, together with the para-derivative, by heating the mother-liquor from the preparation of the meta-compound. The heavy oil so formed is washed with hot water.It begins to decompose at loo", and cannot be distilled ; at 130" it sud- deiily carbonises. Paranitro-octyl bemene is obtained by first nitrating octylbenzene in the cold, separating the liquid from the crystals of metanitro-octylbenzene, and heating for 12 hours. It is then filtered and again heated, and this is repeated until all the hydrocarbon has dissolved. The crystalline Rubstance is gently heated to sublime any metanitro-derivative present, and then strongly heated, when the para-coapouiid sublimes. It forms small, yellowish, lustrous needles, having a slight odour of benzaldeliyde ; it melts at 204", is insoluble in water, soluble in alcohol and ether. was formed when crystals of metranitro-octylbenzene containing N.H. M. Octylbenzene. It is a thick, yellow oil with a peculiar aromatic odour. Diuitro-octy Zbenxene, c6H,(N02)2GH17,134 ABSTRACTS OF CHEMICAL PAPERS. fuming nitric acid were washed with ether. Water was poured on to stop the violent reaction which at once took place. It melts at 22ti0, and sublimes below this temperature in transparent cr,ystals with a vitreous lustre, soluble in ether and alcohol, insoluble in water ; its constitution was not determined. Orfhamido-octylbenzeize hydrodtlo- ride, NH,*C6H4*C8H,,,HCl, is prepared by reducing the ni tro-compound with tin and hydrochloric acid ; i t forms small, lustrous, white plates ; when heated, it becomes red. N. H. M. A Fourth Monobromophenol, and a Second Monobromg- benzene. By I?. FITTICA (Ber., 19, 2632--2634).-1n this communi- cation, the author still maintains the existence of the fourtb mono- bromophenol described by him in a former work, the conclusions from which were subsequently shown by Hand to be erroneous (Abstr., 1886, 101 7).The preparation of a second monobromoben- zene is also described, but it was not obtained of constant boiling point (60-66"), and the analytical results are far from satisfactory. V. H. V. Constitution of Nitranilic Acid. By R. NIETZKI (Ber., 19, 2727) .-When dinmidotetrahydroxybenzene (obtained by redncing nitranilic acid) is distilled with zinc-dust, paraphenylenediamine is formed. This is fresh evidence that nitranilic acid is paradinitro- dihydroxyquinone (compare Hantzch, Abstr., 1886, 1021). N. H. M. Aniline and its Homologues. By L.LEWY (Bey., 19, 2728- 2729 ; compare Abstr., 1886, 872).-When paratoluidine is boiled with water, splendid crystals of the hydrate separate on cooling ; when exposed to air they effloresce. The xylidinefl and cumidines behave towards phosphoric acid as orthotoluidine does, and yield only primary phosphates. As paratoluidine forms a secondary phosphate, and orthotoluidine a primary phosphate, the para-compound behaves like an element having the atomic weight 214, whilst, the ortho-compound behaves like an element having the atomic weight 107. In estimating the phosphoric acid in a misture of the two phosphates, the relative amoiints of paratoluidine and orthotoluidine can therefore be deter- mined. N. H. M. Alkyl-derivatives of Aniline. By A.CLAUS and H. EIRZEL (Ber., 19, 2785-2791).-MethylpropylaniZine, NPhMePr, is prepared by heating methylaniline and propyl iodide for eight hours in a water- bath. The product is dissolved in water, extracted with ether, and treated with alkali. It is a yellowish oil, boiling at 212" (uncorr.). The hydrochZoride melts at 106" (uncorr.) ; it is very hygroscopic. The ethiodide, NPhMePr,EtI, is a viscous substance readily soluble in water. When boiled with concentrated aqueous potash, methyl- ethylaniline is formed. EthyZpropy Znniline, NPhEtPr, is obtained by the action of propyl- aniline (Claus and Roques, Ber., 16, 909) on ethyl bromide, or from ethylaniline and propyl bromide. It is a bright yellow oil boiling atORGAXIC CHEMISTRY. 3 35 216" (uncorr.). The hydrochloride is a crystalline substance, and mclts at, 131" (uncorr.).The msthiodide is a syrup having all the properties of methylpropylaniline ethiodide. Methylethylaniline was prepared by the method of Clans and Howitz (Abstr., 1884, 1005) ; i t was obtained in the crystalline stale. The hydrochloride melts a t 114". The propiodide is identical with the iodide mentioned above. When the aqueous solution of the iodide is heated, or kept in contact with ether, decomposition takes place, with formation of props1 alcohol and methylethylaniline hydriodide. N. H. 31. Action of Ethyl Imidocarbonate on Aromatic Ortho-corn- pounds. By T. SANDMEYER (Ber., 19, 2650-2657).-1n continuation of former experiments on the reactions bet ween ethyl imidocarbonate and the amines of the aroniatic series (Abstr., 1886, G l l ) , the prepa- tion and properties of various derivatives of phenylene and toluylene diamines are described.Ethox ymetheny ltolujy lenediamina, C7H, <- N>C OE t, prepared from tolnylenediamine hydrochloride and ethyl imidocarbonnte, crystallises in golden needles which melt at 163", insoluble in cold, sparingly soluble in hot water, moderately soluble in alcohol. Its aqueous solu- tion gives a voluminous, white precipitate with mercuric chloride. With acids, it forms very soluble salts. When heated with hydrochloric acid, it yields hydroxymetheny I- NH ---- N H toluylenediamine, C7H6<- N>C*OH. This substance crystallises iu small needles, melts at 290", and is sparingly soluble in boiling alcohol, readily in water.Prom its formation, i t would seem to contain the hydroxyl-group, but it is also identical with a compound obtained directly from carbamide and toluylenediamine, which would contain the carbonyl-group ; the atomic transformation of the -N-COH- group into -NH-C 0 is however of frequent occurrence. Et hoxymetheny7pheny lenediainine, CsHa<- N>C *OE t, prepared in like manner from phenylenediamine, crystallises in reddish glisten- ing leaflets which melt a t 160". In its solubility and physical pro- perties, it resembles its homologne. With hydrochloric acid, it yields NK hydroxymethenylphenylenediamine, C6H4<- NH ,>C*OH, which crys- tallises in leaflets, and is identical with phenylenecarbamide obtained directly from or thoni trophenylure thane.Ethoxymethenylanzidophenol, C,H,<N>C*OEt, 0 hydroxymethenylamidophenol, CsH4<N>C*OH, 0 prepared from amido- phenol and ethyl imidocarbonate, is a colourless oil, boiling at 225- 230", of peculiar odour. It is converted by hydrochloric acid into crystallising in red prisms, which lose their colour on exposure or when separating slowly from solution. The reaction of the amido-acids on ethyl imidocarbonate differs136 ABSTRACTS OF CHEMICAL PAPERS. from those of the amines and the amidophenols ; thus with anthraniIic acid an amidine of the composition COOH*CsH,*NH*C(OEt) N*C,H4*COOH is formed. This crystallises in white needles, melts at 223", and is spariogly soluble in boiling water, soluble in hot alcohol. It would appear from its formation that this substance should be a bibasic acid, yet its silver salt contains only one atom of the metal in the molecule.V. H. V. Decomposition of Diazo-compounds by Alcohol : Paradiazo- tolueneorthosulphonic Acid. By I. REMSEN and A. G. PALMER (Amer. Chem. J., 8, 243--251).-The authors expected to be able to prepare benzoic sulphinide by the oxidation of orthotoluenesulphon- amide, itself prepared from the orthotoluenesulphonic acid obtained by boiling the diazo-compound of paramidotolueneorthosulphonic acid with alcohol. This method seemed all the more promising, as Jensen and Ascher have described the actual elimination of the diazo-group in the above compound. The authors find no difficulty in the conversion of paranitrotoluene in to paradiazotolueneorthosulphonic acid ; but this, when boiled with alcohol under pressure, yields, contrary t o the statements of Jensen and Ascher, not tolueneorthosulphonic acid as the principal produce, but ethoxytolueneorthosnlphonic acid.The reaction will not proceed without the application of pressure ; it commences at 90 mm., and the two compounds are then formed in equal quantities, but the yield is very bad, the reaction slow, and the product is black with tarry matters. At 150 mm. thrice as much of the ethoxy-compound as of the toluenesulphoiiic acid is formed, and at 500 mm. the ethoxy-com- pound is formed almost alone ; the reaction takes only a few minutes, and the product is far purer. The acid product of the reaction cannot be puritied by means of the barium salts, but has to be converted into the acid amide, and it is to be noted that ethoxytoluenesulphamide, OEt*CsH,Me*S02NH2 [4 : 1 : 21, melts at 143-144", and not at 136", as described by Heffter.It is at present assumed by all writers that the normal reaction of the diazo-com- pounds when boiled with alcohol is that which results in the displace- ment of the diazo-group by hydrogen ; it is, however, certain that the reaction frequently takes place i n such a way as to form phenetoils: thus the sulphate or nitrate of diazobenzene yields benzene in extremely small quantity, but pheneto'il in very considsrable quantity, and it appears probable that the normal reaction is the one that gives the phenetoll. The action in the above case is therefore represented not by the equation generally given, but by This action has not been satisfactorily explained.A list of 15 similar cases is cited in illlistration. C6H3Me<!g:> + EtOH = OEt.C6H3Me*X03H + Nz. H. B.ORCtANlC CHEMISTRY. 137 Diazo- and Diazoamido-compounds. By 0. WAL LACH (Annulen, 235, 233-255) .-Some of the diazo-compounds of the monacetic derivatives of the diamines (Abstr., 1883, 584) are quite stable in the dry state, and their hydrobromides can be obtained in a pure state owing to their relatively slight solubility in water and alcohol. Acetic anhydride decomposes the dry diazo-compounds, yielding the acetic derivative of a phenol, thus acetoparatoluidine orthodiazobromide yields diacetamidocresol, OAc*C6H3Me*NHAc. The diazo-com- pounds unite w i t h nitro-ethane to form the mixed azo-compounds discovered by V.Meyer (this Journal, 1875, 1202, and 1876, ii, 93), and they also combine with secondary amines, forming diazoamido- compounds. The latter substances are decomposed by boiling with strong hydrochloric, hydrobromic, and hydriodic acids according to the equation RN : N*NR" + 2HCI = RC1 + Nz + KHR",HCl. Phenols are the chief products of the action of dilute sulphuric acid ou the mixed diazoamido-compounds. Benzene diaxopiperidide, C5NHlo*Nz*Ph, first described by Baeyer and Jaeger (this Journal, 1876, i, 273), can be readily prepared by pouring a dilute ice-cold solution of diazobenzene chloride (from 100 parts of aniline) into a dilute cold aqueous solution of piperidine, 100 pwts by weight mixed with 60 of potassium hydroxide.Every precaution must be taken to prevent the temperature of the mixture rising above 0". It is decomposed by warm hydrochloric, hydrobromic, and hydriodic acids, yielding chloro-, bromo-, or iodo-benzene respectively, and piperidine. Toluene paradiazopiperidide, C6H4Me*Nz*C,NH,,,, crydallises in colonrless prisms. It is soluble in alcohol, light petroleum, and ether, and melts at 41". It unites with 2 mols. HC1 to form an unstable cchnpound. Toluene orthodiuzopiperidide and orthonitrotoluene para- diazoFiperidide are oily liquids. Puraiiitrotoluene orthodiazopiperidide melts at 50-51", and is decomposed by hydrobromic acid, yielding bromonitrotoluene, C6H3MeRr*N0, [ 1 : 2 : 41. Nitrobenzene rrtetadiaxo- piperidide and benzene diazoconine and toluene paradiazoconine are oily liquids. By the action of sodium nitrite on a soliition of acetotoluylenedi- amine in hydrobromic acid, the diazobromide, The piperidide melts a t 43".NHAc*C6H,Me*NzBr [Me : N,Br : NHAc = 1 : 2 : 41 is obtained as ft yellow precipitate. In the dry state, this diazobromide is remarkably stable. It acts on an alcoholic solation of nitroethane and sodium ethoxide, yielding a red precipitate of acetoparatoluidine orthodinzonitroethane, NHAc*CsH,Me*Xa*CHMe*NOz [Me : NzCzHaNOz : NHAc = 1 : 2 : 41. The precipitate dissolves in alkalis, and is reprecipitated by acids. It is deposited from an ethereal alcoholic solution in red needles melting a t 143". Acetoparntolu,idine orthodiazodiethylamide, NHAc.C6H3Me*N,*NEtZ, is deposited in colourless prisms when acetoparatoluidine orthodiazo- bromide is added to a cold solution of diethylamine.It melts at 108".138 ABS'l'RACTS OF CHEMICAL PAPERS. Acetoparatoluidine orthodi(izo~iperidide melts at 154", and dissolves in alcohol and in ether. When hydrogen chloride is passed into the alcoholic solution, the diazochloride, NHAc*CsH,Me*N2C1, is pre- cipitated in a state of purity. In a dry state, the diazochloride is stable. It explodes when heated, and is decomposed by boiling with water or weak alcohol, yielding acetamidocresol. The diazopiperidide is de- composed by warm hydrochloric or hydrobromic acid, yielding ortho- chloro- or orthobromo-acetoparatoluidine and monochloro- or mono- bromotoluidine. w. c. w. Hydrazines. By E. FISCRER (Annalen, 236,198-199).--PhenyZ- hydrazine distils without decomposition under 35 mm.pressure. It boils at 241-242" under a pressure of 750 mm. (column of mercury surrounded by vapour). At 22*7" the sp. gr. of the base is 1*097", compared with water at 4". In the preparation of methylphenylhgdmzine, the author finds that the reduction of the nitrosamine (Abstr., 1878, 312) may be carried out in aqueous instead of in alcoholic solution. The base boils a t 131" under 35 mm. pressure, and a t 227" under 745 mm. W. C. W. Phenylhydrazine- compounds. By C. B ij LOW (Annul en, 23 6, 194-197) .-Malic, tart ark, and muck acids unite with phenylhydr- azine at 130", forming diphenylhydrazides. The malic compound, OHC2H,(CO*N2H2Ph)2, melts a t 218", the tartaric compound, C2H2(OH)2( CO*N2H2Ph)2, melts a t 226", and the mncic compound at 238-240'. Pkenylucetic phenylhydrazide, CH2Ph*CO*N2H2Ph, melts at 168-169", and dissolves freely in alcohol and acetic acid.Ethyl oealate pheny1hydi.azide crystellises in plates and melts a t 119". Benzil phenylhydrazine, COPh*CPh :N,HPh, is formed by warming equal molecular weights of benzil and phenylhydrazine. I t melts a t 158-129". w. c. w. Dicyanphenylhydrazine-compounds. By J. A. BLADIN (Bw., 19, 2598-2604). - The anhydro - compound, NPh<N=CMe C(CN) : N>' . I previoiisly obtained by the action of acetic anhydride on dicyanphenyl- hydraziue (Abstr., 1885, 979) can be prepared by adding the calcu- lated quantity of pyruvic acid to an alcoholic solution of the cyano- compound and warming gently. The author regards this compound as a derivative of the hypothetical triazole, NH<C= : N> ; i t will therefore be pheny lmet hy 1 cyantriaxol e.The salts of the corresponding pheizylmethy ltriazolecarboxy lie acid, C2N,MePh.COOH, are described. The copper salt with 1& mols. H20, is obtained in the form of microscopic needles; the siZver salt with If mols. H20 does not crystallise well ; and the lead salt with 2& mols. H20 forms small, white needles ; all these salts are sparingly soluble, whilst those of barium and the alkalis are easily soluble in water. The ethyl salt, C2N,MePh.COOEt, is a thick, bright-yellow oil, insoluble in water, but readily soluble in alcohol, ether and benzene. With hydro- N'CHORGANIC: CHEMISTRY. 139 cLloric acid, a hydrochZoride, C2N7MePh*COOH,HC1, is obtained in small, colourless tables, which are decomposed by water.The ttmide, which can be obtained by the action of hydrogen peroxide on dicyan- phenylhydrazine, crystallises in small, colonrless prisms, soluble in water and alcohol, less soiuble in ether, and melting a t 170". The anxidoxime is sparingly soluble in water, but more so in alcohol, and crystallises in colonrless leaflets melting at 208-210". Acids and alkalis, with the exception of ammonia, dissolve it, whilst with acetic anhydride a compound crystallising in needles and melting a t 148" is obtained. PhenylmethyltriazoZe, C2N3HMePh, obtained by heating the acid a t 180", is an oil which does not solidify at -15". It forms a platino- chloride, (C,N,HMePh),,H,PtCl, + H20, which crystallises from alcohol in lemon-yellow tables melting a t 122-124"; it is decomposed by water.To the compound CN,Ph.CN obtained by the action of nitrous acid on dicyanphenylhydr~zine (Abstr., 1886, l46), the author gives the name phersylcya~tetraxolp, regarding it as a derivative of the CH-NH hypothetical tetrazole, NqNrN>. - w. P. w. Phenazine-derivatives. By A. BERNTHSENaTld H. SCHWEITZER (Ber., 19, 2604-2607).-011 diazotising Witt's toluylene-red, Cl5HlbN,HC1 (Trans., 1879, 356), a compound, dimethami~omethylppher~axine, NMe2*CsH,( I \C6H,Me, is obtained, which forms beautiful dark-red needles or flat prisms having a greenish lustre. It dissolves in dilute acids with A TTiolet, and in concentrated sulphnric acid with a reddish-brown coloration. Alcohol dissolves it to a red, and ether to a yellowish-red solution exhibiting golden-yellow fluorescence.It shows considerable analogy to eurhodine, and, like that base, sublimes without decomposition. When, instead of nitrosodimethylaniline, 1 : 4 phenylenediamine acts on metatoluylenediamine in the presence of oxidising agents, 8 " simple " toluylene-blue, and subsequently a " simple " toluylene- red are produced. On diazotising, the latter yields methylphen- azine; this class of dyes must therefore be regarded as derived from phenazine. The formation of toluylene-blue is represented by the equation NMe2*C6H4*NH2 + NH2*C6H3Me*NH2 - 4H = .N-. N 'N' N toluylene - red, NMe2*C H ' I \C6H2Me*NH2. The constitutional 3\N/ formula of the leuco-toluylene-red, NH<-c6H3(NMe)->NH, shows R remarkable similarity to that of leucomethylene-blue.C6HZMe( NH2) W. P. W. Constitution of the Safranines. By A. BERNTHSEN (Ber., 19, 2690-2693 ; comp. preceding Abstract).-The fact that an indamine140 ABSTRACTS OF CHEMICIAL PAPERS. is formed as an intermediate product in the preparation of pheno- safranines makes it probable that the phenyl-group in the latter is combined with the same nitrogen-atom which connects the two other benzene nuclei. The constitution of leucophenosafranine (formed by oxidising equal mols. of paradiamidodiphenylamine and aniline) would thus be N P h < ~ ~ ~ $ ~ ~ ] > N H . This reaction, and the form- ation of safranines by the oxidation of a paradiamine (1 mol.) with a monamine (2 mols.), explains why the para-position to the amido- nitrogen cannot be taken up, and shows that 2 atoms of nitrogen are present in safranine as amido-groups.The following constitutional formula are suggested for pheno- safranine hydrochloride :- The first formula is in accordance with the analogy of the dye with the thionine-group, and the fact that rosaniline yields a triazo-derira- tive, although its salts contain one imido- and two amido-groups. On the other hand, the presence of two intact amido-groups in the safranine dye, and the fact that toluylene-red can also be diazotised, are in favour of the second formula (comp. also Abstr., 1885, 10%). N. H. M. Metanitromethylsalicylaldehyde and its Derivatives. By A. SCHNELL (Chew,. &ntr., 1886, 469--470).-A11 attempts to prepare a, hydroxymethoxybenzaldehyde by the amidation and diazotation of the above compound (first prepared by Voswinckel, Abstr., 1882, 189) were unsuccessful.An amide was formed, but was so unstable that it could not be isolated. When metanitromethylsalicylaldehyde is heated with sodium acetate and acetic anhydride, nzetanitro-orthomethox ycinnnamic acid, N0,*C6HJ(OMe)*CH:CH*COOH [CH : OMe : NO, = 1 : 2 : 51, is formed. It melts at 238", and when reduced with ammoniaand ferrous sulphate yields metamido-orthomethozycirtlzanaic acid, which forms yellow needles melting a t 189". Sodium nitrite and concen- trated hydrochloric acid convert this acid into orthometlzoxycinnamic acid diazochloride, C6H4( OMe) ( C3H302)*N : NC1, which is very unstable. The corresponding nitrate is much more stable ; it explodes at 151- 152".When either of these salts is heated with water, nzetah?ydrory- orthornefl~ox~~cin~amic acid is formed, and yields yellow crystals melting at 179-180'. When this acid is fused with potash, it is almost completely decomposed ; when methylated, it yields met12 yZ wetortho- dimethoxycinnamate (diwefhylgentisate), a thick, red-brown oil, which yields the acid on saponification. The acid melts at 143": Tiemann and Muller (Abstr., 1882, 53) give the melting point as 76". ThisORGANIC CHEMISTRY. 141 acid when oxidised with alkaline permanganate yields dimethyl- gentisaldehyde. These results prove the nitro-group to be present in the meta- position. L. T. T. New Chlorine-derivatives of Acetophenone. By H. GAUTIE R (Compt. rend,, 103, 812-8 14).- Trichloracetophenone, COPh*CClp- 60 grams of trichloracetic chloride is mixed with 100 grams of benzene, heated to the boiling point of the latter, and aluminium chloride added in emall quantities. After treatment with water, the dried product is fractionated under reduced pressure, and the portion boiling a t 135-155" under a pressure of 25 mm. is re-fractionated. About 20 to 25 grams of trichloracetophenone is thus obtained as a colourless liquid with a pungent odour and extremely burning taste. It remains liquid at, -21", and boils without decomposition at 145" under a pressure of 25 mm., and with slight decomposition a t 249' under atmospheric pressure; sp. gr. at 16" = 1.427. It is very slowly oxidised by alkaline potassium permanganate, yielding benzoic acid ; when subjected to prolonged boiling with water, or when treated with very dilute alcoholic potash, the product is like- wise benzoic acid.Dichlorcrcetophercone, COPh*CHC12, is obtained in the same manner from 50 grams of dichloracetic chloride and 100 grams of benzene; the yield being about 20 grams. It is a colourless liquid, with an odour and taste resembling those of the tri-derivative. It boils unchanged a t 143" under a pressure of 25 mm., and with slight decomposition at 247-248' under atmospheric pressure ; sp. gr. a t 1.5" = 1.338. It is as difficult to oxidise as the tri-derivative, and is not sensibly affected by boiling water. When subjected to prolonged treatment with an alcoholic solution of po tassium acetate, the whole of the chlorine is removed with formation of potassium chloride and a product which has not yet been examined.These derivatives afford further illustration of the stability of chlorine in combination with the carbongl-group. It is attacked with difficulty by reagents which readily remove the chlorine from the side-chains of benzene hydrocarbons, whilst energetic reagents act on the ketonic group, and give rise to simpler substitution derivatives of benzene. C. H. B. Action of Sulphuric Acid on Aromatic Ketones, By K. KREKELER (Ber., 19,2623-2628 ; comp. Abstr., 1886, 538) .-Benzyl- ?neb72 yZketoneszclpho?iic acid, SO3€€.C6H4*CH2*COMe, is prepared by heating benzyl methyl ketone with sulphuric acid on a water-bath. Acefophenonesulphonic acid, S03H*CsH4*COMe, is obtained by gradually adding pyrosulphuric acid (4 grams) to acetophenone (1 gram) kept well cooled ; the intensely red liquid is then heated for half a n hour on a water-bath.The lead salt dissolves very readily in water. The sulphonic acid reacts with phenylhydrazine, and yields the cornpouiid K H P h : CMe*C6H4*S03H(N,HPh) ; this crystallises in lustrous plates, readily soluble in alcohol. Isobzctyrothienonesul~honic acid, CHMez*CO*C4SH,.SO3H, is obtained VOL. LII. I142 ABSTRACTS OF CHEMICAL PAPERS. by acting on the thisnone with pyrosulphuric acid in the cold. The lead and barium salts are very readily soluble in watw, and can be crystallised from dilute alcohol. The phenyZh;lldraxine-derivaSive, NzHPh : CPr@*C4SHz*S0,H-(N,HPh), crystallises in lustrous plates, readily soluble in alcohol, very sparingly in cold water.N. H. M. Plochl's Phenylglycidic Acid. By E. ERLENMEYER, Jun. (Bw., 19, 2576--2577).-The phenylglycidic acid prepared by Plijchl's method (Abstr., 1884, 604) yields well characterised hydroxylamine- and phenylhydrazine-deri vatives, and also gives the Laubenheimer- Victor Meyer thiophen reaction. From these facts, the author draws suggested by the conclusion that the formula Plochl cannot be sustained, and advances the view that the compound w. P. w. By A. LIPP (Ber., 19, 2643-2650) .--Paranitro~hen,yloxynci.ylic acid, first ob- tained by Erlenmeyer, is readily prepared by heating paranitrophenyl- a-chlorolactiu acid with alkalis ; it crystallises in glistening leaflets, which melt at 186-188" with complete decomposition ; when heated with sulphuric acid it yielda paranitrophenyIglyceric acid, which crystallises from water in small interlaced leaflets, melting at 167- 168".In order to determine whether the constitution of this acid is CHPhGH-COOH \O/ is probably phenylpyruvic acid. Para- and Ortho-nitrophenyloxyacrylic Acid. N02*CsH4* C H *C H*CO OH , or of a p-hydroxy-acid, its 'O/ that of a glycide, reaction with hydrochloric acid was studied ; nitrophenyl-P-chloro- lactic acid was formed, thus confirming the former view. This /3-lactic acid resembles the corresponding a-acid in appearance and behaviour towards solvents ; it forms small, glistening crystals which melt a t 167-168'. When boiled with water, it is completely decom- posed into hydrochloric acid, carbonic anhydride, and a red resin ; its barium salt when heated yields paranitropbenethylaldehyde and car- bonic anhydride.Since the paranitrophenyl-a- and -P-chlorolactic acids yield the same nitrophenylacrylic acid, which in ita turn is reconverted into the p-lactic acid, the constitution of the oxyacrylic acid is analogous to that of glycidic acid, according to the formula written above. The orthonitrophenylacrylic acid, obtained by Baeyer, behaves like the above in combining directly with hydrochloric and hydrobromic acids ; its constitution therefore is analogous. By R. STEPHAN (Chew. Centr., 1886, 470-471). -Tiemann, Friedlander, and Priest (Abstr., 1882, 50 and 56) have shown that the cyanhydrins of aromatic aldehydes form an easy source for the preparation of substituted amido-acids.The author finds that the same holds good in the case of aldehydes of the fatty series. Acetaldehyde cyanhydrin, when heated on the water-bath with aniline, yields a-unilidopropionitrile, NHPh*CHMe*CN, melting a t 92". V. H. V. Amido-acids.ORGANIC CHEMISTRY. 143 The hydrochloride forms crystals melting at 8 6 O , and giving up hydro- gen chloride very easily. The nitrile dissolves in boiling water with partial decomposition into its components. Neither hydrochloric acid nor potash causes hydrolysis, but when heated with these reagents the nitrile undergoes decomposition. When the nitrile is dowly added to concentrated sulphuric acid, ~-annilidop~opionaml:de is formed ; this melts at 140-141", and is decomposed when heated with strong potash.Wit-h hydrochloric acid, it yields a-anilidopropionic acid, which melts at 163" and sublimes unchanged. Ortho- and para-toluidine form compounds similar to the above. a-Paratoluidopropionitrile melts at 82' ; the amide, CTH,*NH-C HMe-C 0 NH2, melts at 145", and is more unstaoble than the anilido-amide ; the free acid forms colourless, hygroscopic scales melting at 152". a- Orthotoluidopropioi2.itrile melts at 72-73', the antide at 125", and the acid at 116" when separated from alcoholic, but at 123" from aqueous solutions. The hg drochlorides of these nit riles yield unstable, crystalline platinochlorides. Bromine forms tribromo- subs ti tut ion products. a- Tribrom ad1 ido- propionitrile, C,H,Br,-NH*CHMeGN, forms yellow needles melting a t ISO" ; a-orthotoluidodibromopropionitrile melts at 105", and a-para- toluidodibromopropionitrile at 11 7".L. T. T. Derivatives of Methyl Carbanilate. By W. HENTSCHEL (J. p r . Ghem. [2] , 34, 423427).-1n a former communication (Abstr., 1885, 792), the author has described the formation of methyl amido- sulphobenzoate from methyl carbanilate by the action of sulphuric acid. When the substance is decomposed with excess of bromine- water, and the solution allowed to remain for some days, a substance of the formula C,H,O2NBr2 separates, which crystallises in needles, and melts at 96 5". This substance, in which two atoms of bromine have taken the place of the sulphonic group, when warmed with sulphuric acid yields dibromsniline sulphate, which on decomposition with sodium hydroxide gives ordinary dibromaniline (1 : 2 : 4).When treated with nitric acid of sp. gr. 1.45, the brominated substance gives a nitro-compound, crystallising in silky needles, melting at 152O, and having the constitution OMe~CO*NH*C6H2Br2*NO2 [NH : Br, : NO2 = 1 : 2 : 4 : 61. When heated with aqueous ammonia in a sealed tube, the nitro- compound yields dibromonitraniline (m. p. 127-5"). The acid liquid containing methyl amidosulphobenzoate yields a nitrocarbanilide when treabed with strong nitric acid. This forms colourless plates or prisms, melts at 189", and when heated with strong hydrochloric acid in sealed tubes, yields a dinitraniline which agrees in all respects with uusyinmetrical metadinitraniline. G. H. M.144 ABSTRACTS OF CHEMICAL PAPERS.Ethyl Phthalylacetoacetate. By C. B~~LOW (Awualerc, 236, 184 -194).-Ethyl phthalylacetoacetate, prepared by the method de- scribed by Fischer and Koch (Abstr., 1883, SOS), is decomposed by the action of sulphuric acid at 65" for half an hour, yielding alcohol and acetic and phthalylacetic acids. It is also decomposed by prolonged boiling witb water o r with alkalis, but with a cold alcoholic solution of potassium hydroxide it yields a deliquescent crystalline compound, C11H12K20s + C2H60, which is very soluble in water. At the ordinary temperature, ammonia converts ethyl phthalylacetoacetate into phthalyldiamide, but at a temperature of 100" phthalimide is formed. Et h y 1 pheny 1 hy drazinep ht ha1 y laceton cetate, Cz,H,,N,04, forms thick plates, soluble in alcohol, in stroiig acetic and sulphuric acids, and in alkalis.It melts at 236-238", and on reduction with zinc- dust and acetic acid yields the ethylic salt of benzylacetoacetic- orthocarboxylic acid. This compound melts at 92", and dissolves freely in hot water, alcohol, ether, chloroform, and acetic acid. It is decomposed by boiling with baryta-water, yielding b e m y Zacetoneort hocarbox y lic acid, C OOH*C6'E14*C H2*CH2*COMe. This acid dissolves freely in the usual solvents, and melts at 114'. The phenylh ydraxine compound of eth y 1 benzy lacetoaceticorthocarboxylate, COOH*C6H4*CH,*CH(C00Et)~c~~e : NzHPh, forms pale - yellow, needle-shaped crystals. It melts with decomposition at 235", and dissolves freely in alcohol, ether, chloroform and carbon bisulphide.At the ordinary temperature, and more rapidly at loo", the com- pound splits UP into alcohol, water, and a new substance, C18H16N2O3, which melts at 228-229". w. c. w. Benzoic Sulphinide. By I. REMSEN and A. G. PALMEB (Amer. Chem. J., 8, 223--227).-Benzoic sulpliinide may be sublimed; it is decomposed by simple evaporation with strong hydrochloric acid or by boiling with strong baryta-water, yielding orthosulphobenzoic acid. The following salts are described :-C7H,S03XK + HzO, very soluble cryst,als ; C7H4S03NAg, sparingly soluble in boiling water, and separating in long needles ; (C,H4S03N),Ba + l+HzO, easily soluble in water and difficult to crjstallise; the methyl salt has also been prepared, but not completely examined. H. B. Parethoxybenzoic Sulphinide. By I.REMSEN and A. G. PALMER (Amer. Chew. J., 8,227-229).--Etboxytoluenesulphonamide (this vol., p. 136) was oxidised in warm dilute aqueous solution with potassium permanganate ; from the filtered and concentrated solution, hydrochloric acid precipitated parethoxybenzoic sulphinide, Eto*c6Ha<~~>NH. The substance forms needle-shaped crystals, melting at 257-258" ; it has not a sweet taste. The potassium and silver ealts, C,H,S04NK and C9H8S04NAg, are described. H. B,ORGANIC CHEMISTRY. 11-3 Parabromobenzoic Sulphinide. By I. REMSEN and W. S. BATLEY (Amer. Chern. J., 8, 229-235) .-Parabromotoluenesulphon- amide (Hubner and Post, this Journal, 1874, 57) was oxidised with potassium permanganate in considerable excess, when besides the sulphinide, there is also formed a considerable quantity of para- bromosulphobenzoic acid ; this substance is not formed if potash is also added during the oxidation.Parabromobenzoic sulphinide is sparingly soluble in cold water, volatilises at about 200°, melts at 217", and is characterised by an extremely sweet taste, followed by an after-taste of extreme bitterness. The following salts are de- scribed :-(C7H303SNBr),Ba + 7+Hz0 ; (C7H303SNBr)2Ca + 7iH20 ; C7H,0,SNBrAg + 2+H20. When treated witlh phosphorus penta- chloride, and then with alcohol, the ethyl salt, C7H303SNBrEt, is obtained as a substance which after recrystallisation f rom hot alcohol melts at 199-199.5". Attempts to prepare the ethyl salt from the silver salt and ethyl iodide were unsuccessful, a mixture of at least two substances being obtained.Benzoyltoluenesulphonamide and some of its Derivatives. By I. REMSEN and C. S. PALMER (Amer. Chern. J., 8, 235-243).- Somewhat similar t o the sulphiuides is the class of substances repre- sented by benzoylbeozenesulphonnmide, Ph*C@*NH-SQ,*Ph, and benzoyltoluenesulphonamide, Ph*CO-NH*S02*CsH,Me, obtained by the action of benzoic chloride on the corresponding amides. But the constitution of these substances has not been definitely proved, and Wolkow has shown that benzamide when treated with benzenesulphochloride yields not benzoylbenzenesulphonamide, but toluenesulplionic acid and phenyl cyanide, and it is, therefore, possible that the above two substances are represented, not by R*S02*NH*COR, but by R-SO2*N : C(0H)R. On the first of these suppositions, two ethyl salts should be obtained, one, R*SO,*N Et*COR, from the silver or lead, salts and ethyl iodide, and the other, R*SO,*N : CR*OEt, by acting on the sulphonamide with phosphorus pentachloride and alcohol ; on the second supposition, only one ethyl Balt can be prepared by either method, namely, R*S02*N CR*OEt.It has already been shown, and is confirmed by the authors, that ethereal salts of benzoyltoluene-sulphonamide cannot be obtained by the action of phosphorus pentachloride and alcohol. Neither can they be obtained by the action of ethyl iodide on the lead or silver salts of the sulphonamide ; similar n gative results have been recorded by other writers. But although the ethereal salts of the sulphonamides cannot be obtained from the sulpbonamides, they may nevertheless be prepared indirectly.Benzoylnzethyltolue.nesuZ~honamide, C7H50*NMe*C7137S(32, crystallises with difficulty; i t melts at 58", and is prepared by the action of benzoic chloride on methylparatolzceneszrIrphonamic~e, NHMe*S0,*C7H7. On adding water to its alcoholic solution, the latter crystallises in plates melting at 75", is very stable, and is obtained by treating paratol uenesnlphochlorid e with methy lamine. BenzoylethyZtolzLenesulphonamide was prepared, but not analysed ; it is obtained from benzoic chloride and ethy7,parutoluenesulphonamide, H. B.146 ABSTRACTS OF CHEMICAL PAPERS. NHEt.SO2*C,H7, melting at 58", and prepsred like the above methyl- compound. Benzoylphenyltolzcenssulphonamide crystallises readily from alcohol ; the crystals melt at 149" ; when boiled with alcoholic potash, it yields benzoic acid and toluene-sulphanilide.It is prepared from phenyl- paratol.uenes.ulphonamic~e, NHPh*S02*C7H7, melting at 103", and already prepared by Miiller. Separation of the Two Isomeric Toluidinesulphonic Acids. By E. A. SCHNEIDER (Amer. Chem. J., 8, 274).-The potassium and sodium salts of paratoluidinemetasulphonic acid are very soluble in water, but insoluble in cold aqueous potash, whilst the potassium and sodium salts of paratoluidineorthosulphonic acid are very easily soluble in the same liquid at ordinary temperature. Action of Concentrated Sulphuric Acid on Hydraxine- toluenesulphonic Acids. By E. A. SCHNEIDER (Amer. Chem. J., 8, 271-273).-1t was hoped that condensation might be effected between the hydrazine- and sulphonic-groups.Parahydrazinetoluene- orthosulphonic acid apparently underwent no change. Parahydrazine- toluenemetasulphonic acid react's violently with sulphuric acid at 80" ; the product poured into water gives a bright red precipitate, not further examined, and the filtrate, with excess of soda, gives a yellow precipitate which resembles in all its properties the basic substance obtained by Gallinek and Richter (Abstr., 1886, 236) by heating paratolylhydrazine with snlphuric acid, and is probably identical with it. H. B. H. B. H. B. Oxidation by Means of Potassium Permanganate. By I. REMSEN and W. H. ENERSON (Awer. (>hem. J., 8, 262--268).-1t has been stated " that acid oxidising agents tend to transform para- groups (hydrocarbon-chains) and leave ortho-groups unchanged, and that alkaline oxidising agents tend to transform ortho-groaps and leave para-groups unchanged," and R.Meyer and Baur (Abstr., 1881, 46) have adduced in favour of this the case of cymenesulphonic acid [Me : S03H : P r = 1 : 2 : 41, which with permanganate yields hydr- oxypropylsulphobenzoic acid [COOH : S03H : C3H70 = 1 : 2 : 41, but with nitric acid yields sulphoparatoluic acid [CH, : S0,H: COOH = 1 : 2 : 41. On the other hand, Jacobsen has shown that metaxylene- sulphonamide [SO,H : Me : Me = 1 : 2 : 41 yields the same product of oxidation [ SO,H : Me : COOH = 1 : 2 : 41 with either chromic acid or potassium permanganate. Jacobsen's work is fully confirmed, and i t is also shown that paraxylenesulphonic acid and paraxylenesulphonamide yield the same oxidation products with permanganate, namely, sulphoterephthalic acid and a sulpho- or sulphamido-paratoluic acid. By fusing the last-named compounds with potash, they are both converted into one and the same hydroxytoluic acid, a-orthohomometahydroxybenzoic acid [Me : OH : COOH = 1 : 2 : 41, and hence the methyl-group first oxidised is not that which is in the ortho-position relatively to the s u 1 phonic group.ORGANIC CHE3lISTKT.147 The work of Meyer and Baur was then repeated and fully con- firmed, and finally the behaviour of cymene itself with alkaline permanganate was examined. It was found that the products of the oxidation were almost equal quantities of terephthalic acid and of hydroxypropylbenzoic acid, COOHgC6H~*C3H70, which was recognized by converting it into propenylbenzoic acid and isopropenyl benzoic acid.Cymene treated with chromic acid yields as the first product toluic acid, and hence the C~USB of the different behaviour of cymene- sulphonic acid towards alkaline permangarlate solution, and towards acid oxidising agents (nitric acid) is not to be soughb for in the influence of the sulphonic group on the hydrocarbon side-chains @eyer), but in the difference between the side-chains themselves, the isopropyl- group yielding most easily to acid oxidising agents, the methyl-group yielding most easily to alkaline oxidising agents. (Compare Abstr., 1886, 541.) H. B. Action of Bromine and Water on a-Metaisocymenesul- phonic Acid : Constitution of a- and p-Metaisoeymenesul- phonic Acids.By W. KELBE and N. v. CZARNOMSKI (Annalen, 235, 272-299).-1n addition to the results which have previously ap- peared in this Journal (Abstr., 188%, 619 ; 188%, 1355 ; and 1886, 355), the authors describe the following compounds :- Lead p- bromotnetisocyme.nesulphonate, P b ( CIOH,2BrS03)2 + H,O, crystallises in ueedles, and is soluble in alcohol and in hot water. The barium salt forms colourless plates ; the copper salt glistening green plates containing 4 mols. H20; and the potassium salt, C,,H,,Br*S(n3K + H20, silky needles. The sulphonamide, CloHrzBr*S02*NH2, melts a t 162" and dissolves in strong alcohol, from which solvent it is deposited in transparent needles. After drying over sulphuric acid, it melts a t 126".Its salts are much more soluble than those of the /3-acid. The barium and copper salts crystallise with 7 mols. H20. The potassium salt crystallises in needles containing 1 mol. H20. It dissolves readily in water or alcohol. The sodium salt contains 2 mols. H20. The sulphonamide forms long, wliite, needle-shaped crystals. It melts at 170.5", and dis- bolves in hot water and alcohol. Pure a-bromisocymenc, CIOH13Br, boils a t 225' instead of 235" as previously stated (Abstr., 1882, 618). Dibromocyrnene is prepared by the action of bromine on an aqueous solution of a-bromocymenesulphonic acid. It is an oily liquid boiling a t 272-273". Pare broniocymene is obtained as a strongly refractive liquid when potassium p-bromometaisocymenesulphonate is decom- posed by superheated steam.I t boils a t 224", one degree lower than the a-compound, and is slowly oxidised by nitric acid, yielding bromo- nletatoluic acid (m. p. 152"), C6H3~eBr*COOH [1 : 4 : 3-j: Geizeral Conclusions.-when metaisocymene dissolves 1n sulphuric acid, the SOaH group displaces the H atoms at 4 or 6. Bromine cc-Bronzisocynzei2.esulpponnic acid is very hygroscopic.148 ABSTRACTS OF CHEMICAL PAPERS. displaces the H atom at 4 in a-cymenesulphonic acid, and at 6 in the /%-acid. When bromocymenes are dissolved in sulphuric acid, the sulphonic group takes the position 4 in the a-compound, and 6 in the p-corn- pound. The constitution of these compounds is shown in the following table t- a. 8. Bromotoluic acids, Me : COOH : Br .... Bromocymene, Me : Pr : Br ............Cgmenesulphonic acid, Me : Pr : S0,H . Bromocymenesulphonic acid, Me:Pr:SOaH: Br.. ................ Dibromocymene, Me : Pr : Br : Br ...... Bromoisophthalic acid, COOH: COOH: Br Synthesis of Indole-derivatives. By E. FISCHER (Annulen, 236, 116--126).-Many of the results contained in this paper have already been published (Abstr., 1884, 52, 1180 ; and 1886,835).--The fsxalodour of indole is most marked in skatole, and in the mono- and di-methyl compounds with the exception of ihose substances in which the methyl-group is united to the N-atom. The odour and volatility of the compounds is destroyed by the introduction of the phenyl- group. All indole-derivatives form crystalline picrates, and all the indoles with the exception of the carboxylic acids are reduced by zinc and hydrochloric acid to hydro-bases.The pine-wood reaction is not exhibited by the carboxylic acids, nor by those derivatives in which both the 2' and 3's hydrogen-atoms are replaced by methyl, ethyl, &c. Nitrous acid converts indole and 1' methylindole into nitroso- compounds. It forms complicated products with 2' methyl or phenyl indole, and converts 3' or 2', 3' substituted indoles into nitrosamines. 1 : 3 : 6 1 : 3 : 4 1 : 3 : 6 1 : 3 : 4 1 : 3 : 6 1 : 3 : 4 1 : 3 : 4 : 6 1 : 3 : 6 : 4 1 : 3 : 6 1 : 3 : 4 w. c. w. 1 : 3 : 4 : 6 The following is a list of indoles derived from the hydrazines. Melting Boiling point. point. 1'. ......... liquid 240" Monomethyl 2'. ......... 60" 2 72 3'.. ........ 95 265-26c (2' : 3' ...... 106 285 1 ' : 2 ' ......56 ? ? 13 : 1' 9, ? (1 :1' 9 , ? { Dimethyl.. 4 1 : 3' ...... liquid ...... ...... * Note.-In the notation of the indole series, 1,2, 3, 4 refer to the positions in the benzene-ring, and l', 2', 3' to the corresponding positions in the basic ring con- taining the nitrogen, where N = l', as shown in the annexed symbol :- 1' 1 N 4 3' -EDITOBS.ORGANIC CHEMIST RT. 149 Melting Boiling point. point. Trimethyl., 1' : 2' 3' .... liquid ? picrate melts at 150". Ethyl ..... l'.. ........ 9 , 2' : 3 ' . ..... ,, 291-293" ...... Methyl ethyl { : 1t 9 , Monophenyl { g: Diphenyl. .. 2' : 3 ' . ..... 123 Benzyl .... l ' . . ........ 44.5" Naphthindole 2'. ......... liquid 222" under 18 mm. pressure. Methyl naphthindole, 2' . . 2 , ' ' ......... 18%" w. c. w. Indoles from Phenylhydrazine.By E. FISCHER (Annulen, 236: 126--151).-Most of the compounds mentioned in this paper ham already been described by the author (Abstr., 1886, 805). 2', 3' Di- methylindole, CeNH5Me2, prepared from the phenylhydrazine com- pound of methyl ethyl ketone, melts at 106" and boils at 285". The nitrosamine, C8NH4Dlle2*N0 [NO = 1'3, melts at 61-62", and decom- poses at a higher temperature. 2' 3' kfelhylethylindole, C8NH5MeEt, prepared frpn the phenylhydrazine of methyl prop91 ketone, is an oily liquid boiling at 291-293". The picrate crjstallises in dark red needles. Phenylhydrazillelaevulinic acid, PhNzH : CMe*CH2*CH2*COOH, melts at 108", and at a higher teniperature splits up into water and the anyhdride, C11H,,N20. This substance crystallises in colourless plates.It melts at 106-107O and boils between 340" and 350" with partial decomposition. Ethyl phenylhydrazinelmdinate melts a t 110". Methylindoleacetic acid, prepared from this ethyl salt, melts between 195" and 200", and splits up into carbonic anhydride and Indoles from Methylphenylhydrazine. By J. DEGEN ( A n n u l e n , 236, 151-164) .-The preparation of l', 2' dimethylindole, l', 2' methylphenylindole, and l', 2', 3' dimethylindolecarboxylic acid from the compounds of methylphenylhydrazine with acetone, acetophenone, and ethyl acetoace tate, respectively, has already been described (Abst- ., 1886, 805). Dimethylindolecarboxylic acid crys- tslllises in six-sided plates. It melts at 185" with partial decomposition into carbonic anhydride and l', 2' dimethylindole. l', 2', 3' DI- methylindoleacetic acid (Zoc.cit.) melts at 188" and decomposes a t 200", yielding l', 2', 3' trimethylindole, an oily liquid which boils about 280° without decomposition. The picrate melts at 150". Trimethylindole is obtained i n a less pure state by the action of zinc chloride on the compound of methy lphenylhydrazine with methyl ethyl ketone. l', 3' Dimethylindole is obtained in an impure state by acting on propylidenemethylphenylhydrazine with zinc chloride. 2', 3' dimethylindole. w. c. w. w. c. w. Indoles from Metahydrazinebenzoic Acid. By A. RODER (Annalen, 236, 164-173). - Metahydraziiiebenzoic acid is con-150 ABSTRACTS OF CHEMICAL PAPERS. vqniently prepared by adding the theoretical quantity of sodium nitrite to 100 grams of metamidobenzoic acid suspended in a mixture of 400 grams of water and 190 grams of strong hydrochloric acid.The liqiiid is poured into an ice-cold solution of sodium sulphite (4 mols. Na2S03 to 1 mol. amido-acid). As soon as the mixture turns yellow, strong hydrochloric acid is added to precipitate the hydro- chloride of metahydrazinebenzoic acid. The free acid is obtained by adding sodium acetate to a solution of the hydrochloride. The acetone compound is formed when acetone and sodium acetate or potassium hydroxide are added to a solution of the hydrochloride. This sub- stance forms colourless needles melting a t 150". It is freely soluble in alcohol and acetic acid, and is easily decomposed by warm mineral acids into acetone and hydrazinebenzoic acid.The ethylic salt CIOH11N2C)2Et, melts R t 90-91" and dissolves freely in alcohol, ether and acetic acid. Hydrazinebenxopjruvic acid, CloHloN204 + H20, melts a t 306-208" with decomposition, and is freely soluble in am- monia and fixed alkalis. The barium and sodium salts are crystalline. The ethyl salt, C,oH8N,04Et,, melts a t 101-102". It dissolves freely in alcohol, ether, and in warm benzene. By the action of zinc chloride on this componnd, the ethyl salt of indoledicarboxylic acid is formed, together with indole and a small quantity of another substance. Monethy 1 indoledicarboxylate crystallises in needles and melts a t 250" with decomposition. The free acid melts a t 250" with decomposition, It dissolves freely in hot alcohol and in acetic acid. It has the constitution [(COOH), = 4 : 2' or 3 : 2'3.Hydrazinebenzoic acid unites with benzaldehyde, forming benxylideii e- hydrazinebetuoic acid. This acid cry stallises in plates, melts a t 170-172", and is freely soluble in alcohol and acetic acid. Phenyl- glucosaxonecarboxylic acid melts at 206-208" with decomposition. Metahydrazinebenzoic acid unites with phenyl isothiocyanate, forming diphenylthiosemicarbaxidecarboxylic acid, Cl4Hl,N30,. This substance crystallises in colourless needles and melts at 204-205" with decom- It is freely soluble in alcohol. position. w. c. w. Aluminium Chloride Reaction. By R. ANSCH~~TZ (Annalen, 235, 150-229 aud 299-341). The experimental results of the author's research on the aluminium chloride reactions have already been published (Abstr., 1883, 807, 809, 1132 ; 1884, 326, 753, 754, 1034 ; 1885, 269, 768, 769).The following conclusions me deduced from these results. Dibenzyl and unsymmetrical dipheiiylethane (obtained by tho action of aluminium chloride and benzene on the isomeric dibrom- ethylenes) correspond with the dibromethylenes in constitution. The synthesis of anthracene from a1 uminium chloride, benzene, and acetylene tetrabromide, indicates that the mesocarbon-atoms in anthra- cene are probably linked together. The formation of dimethyl- anthracene from toluene, acetylene tetrabromide, and aluminium chloride, shows that the methyl-groups in dimethylanthracene, melting at 225", are divided between the two benzene nuclei. Aluminium chloride not only removes but also transfers the side-chains of methyl-ORGANIC CHEMISTRY. 151 and ethyl-benzenes from one molecule to another.Only the symme- trical tetraphenylethane is known. In many aluminium chloride reactions, theoretical yields are obtained when carbon bisulphide is used as a diluent. Symmetrical mesodimethylanthracene hydride is formed, together with ethylbenzene and unsymmetrical diphenylethane, by the action of benzene and aluminium chloride on ethylidene bromide or chloride, or on vinyl bromide. Ethyltoluene, unsymmetrical ditolylethane, and tetramethylanthracene hydride are formed by the action of aluminium chloride on ethylidene chloride and toluene. A new dimethyl- anthracene is formed by heating the tetramethylanthracene hydride with zinc-dust. w. c. w. By E. LIPPMANN (Monatsh.Chem., 7, 521-528) .-Benzoic peroxide can react as a dehydrogenising agent, removing two hydrogen-atoms from two molecules of an aromatic hydrocarbon. Thus from toluene a hydrocarbon, ClaHl,, is formed ; the hydrocarbon boils a t 258-262", is strongly refractive, and of aromatic odour, sp. gr. 1.0032; it is isomeric with stilbene and diphenylethylene, and as, on oxidation, it yields benzoic acid only, its constitution is probably expressed by the Dehydrogenation by Means of Benzoic Peroxide. ,-. -7 formula <z:> CH2, that of a benzylidenetolylene. 6 4 Similarly from xylene, a bydrocarbon, Cl6HI6, is obtained as a refractive liquid, boiling at 260-270", sp. gr. 998 ; as being isomeric with ditolylethylene and dimethjlstillene, it is named dixylylene. Formation of Substituted Stilbenes.By K. ELBS (J. pr. Chem. [2], 34, 340--342).-0n endeavouring to extend Strakosch's method of synthesis of stilbene-derivatives by the action of potash on benzyl- derivatives, the reaction wit.h orthonitrobeiizyl chloride was successful, but in the case of parabromo benzyl bromide the corresponding alcohol was obtained together with ethyl parabromobenzoate ; the latter substance, the derivation of which in the above reaction is not satisfactorily explained, is a colourless viscid liquid, boiling at 236" under a pressure of 713 mm., of odour resembling pears, soluble in most menstrua with the exception of water, saponified only with difficulty. Substituted Stilbenes. By K. ELBS and F. BAUER (J. p r . Chem. [2], 34, 343--347).-Paradinitrostilbene is not altered by potassium permanganate ; on oxidation with chromic acid i n acetic acid solution, it is readily converted into paranitrobenzoic acid.With bromine, it forms paradinitrosLiZbene bromide, NOa.CGHb*CHRr*CHBr*CGH4.N02, a white, crystalline powder melting above 300", but dedomposing even at 110" with evolution of hydrobromic acid and the formation of para- dinitrotolane ; it is sparingly soluble in most menstrua. When an acetic acid solution of paradinitrostilbene bromide is boiled with potassium acetate, ethyl paradinitrohydrobeneoin acetate, is formed ; this crystallises in small, yellow crystals, melting at 340", moderately soluble in alcohol, ether, and acetic acid. V. H. V. V. H. V. NOz*O6Hk*CH (OAc)*CH ( OAC) *C6H4*NO2,152 ABSTRACTS OF CHEMICAL PAPERS.Paradinitrotolane, NO-,*C6H4*C i C*C6H4*NO2, obtained as dewribed above, and best purified by sublimation, crystallifies in needles melting at 288" ; it usually separates from solvents in the amorphous form. V. H. V. Euxanthone-group. By C. GRAFBE and A. FEER (Ber., 19, 2607-2614).-Spiegler (Abstr., 1854, 1182) ascribed to benzo- phenone oxide the constitution < g:z:E<>, as it reacts neither with hydroxylamine nor with phenylhydrazine. The authors suggest for this compound the constitution CsB4-G-L6H4 ; this would account for the negative result with hydroxylamine, as well as for the fact that i t yields dihydroxybenzophenone when fused with potash (Richter, Abstr., 1884,324). Orthodihydroxybenzophenone (Richter, loc. cit.) boils at 330-334" with partial decomposition into water and benzophenone oxide.The potassium salt has the formula CO(C,H,*OK),. The phen ylhydrnaine and hydron: ylainine-cowpounds melt at 152" and 99" respectively. The methyl salt was found to melt at 104" (not 98") ; it undergoes no change when heated with alcoholic potash at 150" ; the hydroxylamine- deyivative melts at 188". The ethyl salt crystallises from alcohol in colourless needles me1 ting at 109" ; the pheir ylhydraaine-cmpound melts at 114". When paracresol salicylate is subjected to the same treatment as the phenjl salt in the preparation of benzophenone oxide (Siefert, Abstr., 1885, 0 0 A/\- The acetyl-derivative melts at 96" (not 83"). loss), the compound C6H,<-O->C6H3Me CO is formed; this is very readily soluble in hot alcohol and melts at 106".&-Naphthol salicylate yielded a-naphthopheitorte oxide, C1,H1002 ; i t melts at 155", and dissolves very readily in hot toluene. The picrate is yellowish-red. t3-Xaphthophenone o&de crystallises in needles melting at 140". When euxanthonic acid is fused with potash, it is converted into quinol ; it has therefore the constitution CsH,(OH)2*CO*C6H,(OH), [CO : OH : OH = 6 : 1 : 41. An ethyl salt was obtained which reacts with hydroxylamine. N. H. M. Preparation of Dinitronaphthylamine : Metanitrophenyl- azodirnethylamidobenxene. By R. MELDOLA (Ber., 19, 2683- 2684) .--a-Naphthylamine is boiled for several hours with acetic acid ; the theoretical amount of nitric acid (sp. gr. 1.5) diluted with glacial acetic acid is then gradually added to the warm solution of the aceto- naphthalide and the whole warmed until the reaction is finished.The product is then poared into cold water, filtered, and washed well with cold water. The precipitate whilst still moist, is mixed in small quantities with strong sulphuric acid and warmed ; it is then poured intq cold water, and the orange-red precipitate washed with water ; it may be purified by recrystallisation from alcohol. The yield of crude substance is almost theoretical.OROANIC CHEMISTRY. 153 Metanitrophenylazodimethylamidobenzene (Staedel and Bauer, Abstr., 1886, 944) has already been fully described by the author (Trans., 1884,120). N. H. M. Eurhodines and Laurent's Naphthase. By 0. N. WITT (Ber., 19,2791-2796).-The eurhodo2, C14H8 <i>CloH5*OH, is obtained by N fusing sodium diphenylenenap h thaquinoxalinesulphonate (Abstr., 1886, 889) with potash until the yellow colour suddenly changes to a pure cinnabar-red.When the product is diluted withwater and treated with hidrochloric acid in excess, the hydrochloride separates as a cinnabar-red, insoluble powder. If acetic acid is used in the place of hydrochloric acid, the free eurhodol separates in orange-yellow crystalline flakes. It is insoluble in all solvents and can only be purified by recrystallising the hydrochloride from boiling phenol. When heated, it sublimes with partial decomposition. Sulphuric acid dissolves it with a pure deep blue colour whicL changes immediately on addition of very little water to a splendid carmine-red ; when the blue solution is heated to a certain point i t becomes successively violet, red, and yellow.N a-/3-NaphthapzcinoxaZine, CloH6/ I \CIOH6, is prepared by the action of P-naphthaquinone on orthonaphthylenediamine in acetic acid solution ; it is purified by crystallisation from naphthalene. It forms yellow needles melting sharply at 275". It dissolves in sulphuric acid, yielding a pure violet solution which becomes orange-yellow when diluted ; when further diluted, the free base is precipitated. I t sublimes readily in long, yellow needles, and when quickly heated distils as a yellow oil which soon solidifies. It is identical with Laurent's naphthase (Annalm, 9, 384 ; compare also Nietzki and Goll, Abstr., 1885, 545). By A. SCHLIEPER (Anna- Zen, 236, 17P-l84).-The P-naphthylhydrazine described by E.Fischer (Abstr., 1886, 555) unites with acetone, forming the com- pound CloH,*NzH : CILIe,. This substance crystallises in prisms of a pale-yellow colour. It melts at 65.5", and is freely soluble in alcohol, ether, benzene, acetone, and in (hot) light petroleum. E'thylidene p-naphthy lhydrazine, CloH7*N,H : CHMe, forms three-cornered plates, soluble in hot alcohol, benzene, and chloroform. It melts at 228-129'. ~-NaphthyIhydrazinepyrz~vic acid, C,,H7-N2H CMe-COOH, forms yel- low needles. This acid melts at lW", and decomposes with evolution of carbonic anhydride. It dissolves in hot alcohol and acetic acid. The ethyl salt melts at 131", and is freely soluble in alcohol, ether, benzene, and acetic acid. On fusion with zinc chloride, /3-naphthindole is prodnced ; ,8-naphthindolecarbox~lic acid is formed as an inter- mediate product.After purification by conversion into the picrate, ,kI-naphthindole, CIoH6< CH>CH, boils at 222" under 18 mm. pres- The dry eurhodol is electric. 'N' N. H. M. Indoles from p-Naphthylhydrszine. NH154 ABSTRACTS OF CHEMICAL PAPERS. sure, and above 360" under the ordinary atmospheric pressure. It dissolves in alcohol, ether, benzene, and acetic acid with fluorescence. Strong hydrochloric acid forms a crystalline compound with it. P-Naphthindolecarboxylic acid, c~o~6<,,>c*coo~, crystallises in colourless plates, soluble in alcohol and acetic acid. It melts at 226" with evolution of carbonic anhydride. The sodium and barium salts are sparingly soluble in cold water.The ammonium and potassium salts are much more soluble. NH NH Methylnaphthindole, c,OH6< CH>CMe, f porn acetone-p-naphthyl- hydrazine, boils between 37 4' and 320" under a pressure of 223 mm. It is freely soluble in alcohol, ether, and benzene. The picrate melts at 1 76". On reduction with nascent hydrogen, hydrornethyZ-P-na~hth- i d o l e is obtained as an oily liquid, boiling between 190 and 200" under 20 mm. pressure. It is a strong base, and with mineral acids, forms salts which are very soluble in water. w. c. w. Action of Monamines on Citric Acid. By H. HECHT (Bw., 19, 2614--:!618).-0CitrotrinzethyZamide, C6H,0,(NHMe)3, is prepared by adding a strong solution of methylamine to a concentrated solution of inethyl citrate in absolute alcohol, and keeping the product over sulpburic acid for some time.It separates in prisms melting a t 124' ; i t is very readily soluble in cold water, and is not acted on by alkali or hydrochloric acid. Citrodinaphtlzy lamine, CloH,*N : C6H504*NH*C,oH,, is formed when a mixture of citric acid (1 mol.) and P-naphthylamine (3 mols.) is heated at 140-150" for several hours. It crystallises in six-sided platew melting at 233". It is insoluble in water or hydrochloric acid, sparingly soluble i n alcohol. The trinaphthylamide, C6H,04(NH*C,oH,),, is obtained by heating the dinaphthylamide with naphthylamine (eq. mols.) a t 150-160" ; it forms microscopic, prismatic crystals readily soluble i n alcohol, in- soluble in water ; it melts a t 215", and is very stable.Citrodinctphth ylamic acid, OH*C6H504(NH*C,oH,),, is prepared by heating the djnaphthylamide with an excess of concentrated ammonia for six hours a t 170". It crystallises from alcohol in slender, microscopic needles melting a t 172" ; i t is readily soluble in alkali, insoluble in water. Monobasic ncrphth yzamine cif rate, C6H5O8,NCloH,, separates as a rose- coloured Pubstance when a hot, concentrated alcoholic, solution of citric acid (1 rriol.) is mixed with p-naphthylamine (1 mol.) and cooled. It melts at 89", dissolves readily i n alcohol, ether, nitrobenzene, and water. Compounds isomeric with the above were prepared from a-naphthyl- amine in a similar manner. Citrodiiiaphth~lamide is purified by precipi- tating the solution in glacial acetic acid with water; it crystallises from benzene in six-sided plates melting at 194"; i t is insoluble in hydrochloric acid.3, crystal- lises in microscopic, rhombic prisms vhich melt at 129". Boiling alkali solution and acids do not act on it. CitrodinaplLt7~yZarninio acid The silver salt was prepared. Citrotrin aph t hy lomide, C6H504( NHCORGANIC CHEMlSTRY. 155 cryshllises in small groups of needles melting a t 149" ; the alcoholic solution reacts slightly acid. The silver salt is sparingly soluble in water. N. H. M. Action of Ammonia on Ethyl Acetonedicarboxylate : Syn- thesis of Pyridine-derivatives. By H. N. STOKES and H. v. PECH- MANN (Bey., 19,2694-27 1'7) .--Ethyl p-hydroxamidoglutamate (Abstr., 1885, 1202) is readily soluble in hot water and in alcohol ; the aqueous solution decomposes gradually,.giving off ammonia. It gives a deep red coloration with ferric chloride. The compound obtained by the action of alkalis on ethyl P-hydrox- nmidoglutamate and described as glutazine (loc. cit.), is shown to be a, pyridine-derivative, probably having the constitution It melts at ahout 300" with evolution of ammonia, is moderately soluble in hot water, almost insoluble in hot alcohol, and insoluble in other solvents. The neutral solution acquires a deep-red colour on addition of ferric chloride ; on warming, the solution turns dark- green without becoming turbid. The liydrochloride (with 1 mol. H,O) q s t a l l i s e s in prisms readily soluble in alcohol ; water decomposes it. The sulphate was prepared. The sodium, amm,oniutn, and barium salts are very soluble.Pentabromacetylacet,amide (Zoc. cit.) melts at 148" ; a t a higher temperature, it gives off bromine and hydrogen bromide. It is in- soluble in water, readily soluble i n alcohol, ether and glacial acetic acid, moderately in chloroform. When heated with water, it is con- verted into dibromacetsmide, bromoform, and carbonic anhydride. Eoiling alcoholic ammonia converts it into dibrornomalonamide (melt- ing a t 200*5°) arid bromoform. AcetyZgZutazine, NH<Co.CH,>C CO*CH, : NAc, is obtained by heating glutazine with acetic chloride at 100-120". It crjstallises from water in small lustrous plates, which darken at 230" and melt a t 285-290'. When warmed with ferric chloride. i t acquires a brilliant violet colour. The arnnwizium (with 1 mol.H20), silver, and barium salts were pre- pared. 2, 4, 6 Trihydroxypyridine itl prepared by boiling glutazine for 3 4 minutes with an excess of strong hydrochloric acid and then evaporating the solution in clock glasses as quickly as possible on a water-bath. The dry residue is extracted with cold alcohol and the solution quickly evaporated ; the thick syrup so formed is mixed with a little water and a solution of caustic soda (0.3 gram to 1 gram glutazine) in twice its weight of water added, the whole being kept cool. The crystalline product is washed with a little water and dried. It forms yellow, microscopic needles which swell up when heated at 220-230" and give off water. It dissolves readily in hot water, but is insoluble i n other solvents.When treated with ferric chloride, i t gives a deep- red coloration. Bromine-water converts it into pentabromacetylacet- amidc. It reacts strongly acid and decomposes carbonates. The salts156 ABSTHAUTS OF CHEMICAL PAPERY. of the alkalis and alkaline earths are very readily soluble in water. When distilled with zinc-dust, it yields a small quantity of pyridine. Hydroxylamine h yd rochl oride reacts with trih y dox ypyridine, yielding a monoxime, C,NH,O, N*OH + H20. The latter is a heavy, sandy powder consistiiig of hexagonal plates ; it melts a t 196196O with evolution of gas. It is rather soluble in hot water, less so in alcohol. When treated with strong soda solution, it becomes blue; with ammonia, it gives a yellowish-red colour which chanqes t o intense purple when warmed.It is also formed by acting on glutazine with hvdroxylamine. The phenylhydr- mine-compound (obtained from both trihydroxypyridine and glutazine) forms plates readily soluble in hotl alcohol ; it melts a t 230". When trihydroxypyridine is heated with ammonium acetate at 120-140", it is converted quaiititntivelv into glutazine, Trihydrozypyridin e anhiidride, C10H805N2, is formed as the chief product in the decomposition of glutazine by boiling dilute sulphuric acid. It crystallises in flesh-colonred, microscopic prisms ; it is very stable, and melts only at a high temperature. It is insoluble in all neutral solvents except water, which dissolves i t slowly. It dissolves readily in an excess of alkali. The oxime forms salts with acids.The hydrogen barium salt, ( CloH705N2)zBa + 4H20, forms yellow prisms insoluble in water and alcohol. The normal alkali and alkaline earth salts are readily soluble in water ; they are not decomposed by carbonic anhydride. .The hydrochloride crystal- lises in needles readily soluble in alcohol ; it is decomposed by water. The sulphate crystallises from water in prisms. The anhydride can be converted into trihydroxypyridine by evaporating its aqueous solution. The way in which glutazine is formed shows that the nitrogen of the pyridine-ring has the para-position to the side-chain con- taining nitrogen, and the ortho-position to both the oxygen-atoms. Hence the three oxygen-atoms in trihydroxypyridine must be sym- metrical to one another and to the nitrogen, and trihydroxypyridine is therefore analogous to phloroglucinol.The analogy of the two com- pounds is seen in their yielding anhydrides and in their behaviour towards ammonia and hydroxylamine (compare Baeyer, Abstr., 1886, 350). It is probable that the yyridine-derivative exists in two forms, a,~ shown in the following formulee:- 3, 5 Dichloro-2, 6-dihydroxy-4-amidopyridine (Zoc. cit.) forms short flat needles melting a t 241.5" ; it dissolves sparingly in hot water and alcohol, readily in alkali and dilute hydrochloric acid. 2, 4, 6 Trichloro-4-~midopyridine forms long colourless needles melting a t 157.5"; it is very readily soluble in alcohol, readily in dilute hydrochloric acid, and insoluble in alkali; it sublimes un- changed. 2, 3, 5 Trichloro-6-hydroxy-4-amidopyrid ine, melting at 282", is vei-y readily soluble in hot weter, moderately in hot alcohol, sparingly inORGANIC CIHEIIISTRY.157 ether and benzene. It is a monobasic acid, and decomposes carbo- nates. The sodium saZt is rather soluble in water, sparingly in alc7hol. 2, 3, -5, 6 Tetrachloro-4-amidopyridine melts a t 212O, and sublimes unchanged. It is insoluble in water, soluble in alcohol and benzene. It can be boiled with strong sulphuric acid without decomposition. When heated with fuming hydriodic acid a t 200°, black crystals of an iodiize-dprivative melting below 80" are formed. This, by solution in dilute sulphuric acid and precipitation with alkali, is converted into what is probably dichloramidop~rii7ilte; it melts at 158". When the t etrachloro-compound is boiled wihh sodium ethoxide and alcohol, 2, 3, 5 f~ichloro-6-ethoxy-4-amido~yridine is formed ; this crystallises in needles which melt a t 83".It distils wilh steam, is insoluble in water, alkali, and dilute acids, very readily soluble in alcohol, ether, henzene, &c. Dilute hydrochloric acid converts it (at rather above 100") into trichlorhydroxynmidopyridine (m.p. 282O) and ethyl chloride. Dick loro-d ipth oxy- 3-arnidopyridine, C,N,H,Cl, (OE t ) 2, and dichloro- 2- ~~ydroxyetho~y-4-amidopyridine, C,?5i2H,Cl,(OH)*OEt, are formed by heating tetrachloramidopyridine with excess of sodium ethoxide and alcohol a t 190". The former crystallises in long needles melting a t 98" ; it is very readily soluble in alcohol and ether, insoluble in water, alkalis, and dilute acids, and distils with steam.The latter crjg- tallises from very dilute alcohol in flat needles which melt a t 161.5'. It dissolves readily in alcohol, ether and alkalis, and is insoluble in dilute acids. The two compounds are also formed from trichlor- hydroxy*imidopyridine and from the diethoxy-compound b y the action of sodium ethoxide and alcohol a t 190". N. H. 31. Correction. By A. LADENBURG and C. F. ROTH (Ber., 19, 2586 ; compare Abstr., 1885, 994).-The authors state that in the mixture of bases of high boiling point from animal oil examined by them, aniline was present and accumulated in the fraction 174-176', from which they separated the supposed new lutidine. A repetition of the experiments has not yet been possible owing to a difficulty in obtain- ing the material.w. P. w. Derivatives of Picolinic and Nicotinic Acids. By E. SEYF- FERTH ( J . p ~ . Chem. [2], 34, 241--263).-At the outset, unsuccessful experiments are described, made with a view of obtaining hexahydm- picolinic acid from the acid itself by the action of various hyclro- genising agents. But in each case either the acid was not acted on or was decomposed with formation of picoline and its hydro-derivatives. Chlomyicolinic acid, C,NH&l*COOH, is obtained by boiling chloro- picoline trichloride, C,NH,Cl*CCI, (from picolinic acid and phos- phoric chloride), with 80 per cent. sulphuric acid, and pouring the product into water. It cr.ystallises in needles and prisms, often showing twinning. It melts a t 180", is sparingly soluble in cold water, readily soluble in hot water, alcohol and chloroform. It has strongly acid properties and does not form salts with dilute mineral acids. I t s culcium salt crystallises with 1H,O in transparent prisms, and its harz'um salt in nodular aggregates.Both salts are sparingly VOL. L11. m158 ABSTRACTS OF CHEMTCAL PAPERS. soluble in cold, but readily in hot water ; its silver salt is a voluniinous, flocculent precipitate. With reducing agents, it yields picoline and picolinic acid. ChZorohydroxypico7inic acid, OH*C5NH&1*COOH, formed simul- taneously with the above, crptallises in clusters of needles, melts above 315", is sparingly soluble in cold, readily in hot water, alcohol, and ether. Like the above acid, it does not combine with mineral acids. These acids are not identical with those obtained by Ost (Abstr., 1883, 794). With phosphoric chloride, nicotinic acid yields an oil containing chlorine, and this, when boiled with sulphuric acid, is converted into chlorhydroxy- and dichloro-nicotinic acids, together with trichloropyridine.The first of these acids crystallises in mono- clinic prisms and needles, melting at 302", sparingly soluble in cold, readily in hot water and alcohol. The aqueous solution gives with silver nitrate a white, flocculent precipitate, soluble in ammonia, and with ferric chloride a dirt.y red precipitate. Its barium salt crys- tallises in transparent rhomhic prisms. Tricklorop y ridine, C5NH zC13, crystallises in colourl ess needles, me1 ting a t 64", insoluble in water, soluble in alcohol, ether and benzene.Dirhloronicotinic acid crystallises in small, white, grouped needles, m2lting a t 138"; its e t h y l salt forms colourless needles, melting a t 50", sparingly soluble in water, but soluble in alcohol, ether, and chloroform. V. H. V. Bromoquinoline. By A. CLAUS and F. COLLISCHONN (Ber., 19, 2763-2769).-It was previously mentioned (this vol., p. 60) that when quinolinepropiobromide dibromide is heated, the hydrobromide of a new monobroruoquinoline is formed. The bromo-compound is heated a t 170" for some time, and then at 190" ; a crystalline residue is thus obtained without carbonisation. The bromoquinoline is sepa- rated from the quinoline that may be present by distilling with steam : the hydrobromide of the bromo-compound is decomposed, the free base going over with the steam, whilst the quinoline salt remains bebind. It is a slightly yellow oil, having an odour resembling that of quinoline ; it boils a t 273-274" (uncorr.).The hjjdrobronde forms characteristic envelope-shaped crystals, which dissolve sparingly in cold water with partial decomposition, more readily in alcohol, and is almost insnluble in chloroform. When carefully heated a t about, 190", it sublimes without having melted. The hydrochloride sublimes readily without me1 ting. The PZatinochZoride, (C9NH6Br)2,H2PtC16, crystallises from dilute hydrochloric acid in slender, orange-coloured needles. The nitrate and su7phate melt respectively atp 180" and 182-183" (uncorr.). The dichroinate crptallises in flat, short prisms, which melt a t 144- 145" with decomposition.The compound ( C9NHBr)2,AgN03 melts at 172-173", and detonates at a high temperature with evolution of red vapour. The same brornoquinoline is obtained when an etlhered solution of bromine is added to a solution of quinoline in ordinary ether (containing alcohol) ; a yellow precipitate is formed. The latter crystallises from chloroform in lustrous, garnet-coloured crystals, melt- ing a t 88" (uncorr.). Analysis points to the formula C,NH,,HBr,Br,. When exposed to air it gives off bromine. The hydrochloride,ORGANIC CHEMISTRY. 159 C,H,,HCl,Br,, forms small, orange-coloured crystals melting a t 100- 105". When the hydrobromide of the quinoline dibromide is heated at NO", it is converted with evolution of hydrobromic acid into bromoquinoline hydrobromide. When bromoquinoline is oxidised with potassium permanganate, Friedlander and 0 s termayer's oxalylanthranilic acid (Abstr., 1882, 732), melting a t 210" (not 200°), and bromopyridinedicarboxylic acid, C5NH2Br(COOH)2, are obtained.The latter forms yellowish crystals, readily soluble in water, alcohol, ether, &c. ; it melts a t 165" with evolution of carbonic anhydride and formation of bronzonicotinic acid, melting at 183" (uncorr.). The bromoauinoline described above is identical with that obtained by La Coste'(Abstr., 1881, 741) by brorninating yuinoline hydro- chloride. N. H. M. Synthetical Experiments with Ethyl Acetoacetate. By L. KNORR (Annalen, 236, 69-1 151.-The action of ethyl ncetoacetate on aniline a t different temperatures has already been investigated by the author (Abstr., 1884, 334).The anilide of acetoacetic acid, previously described as /3-phenylamido-a-crotonic acid, melts a t &5O and decomposes on distillation, yjelding symmetrical diphenylcarh- amide. On the addition of bromine to a solution of the anilide in chloroform, an unstable additive product is formed, which c?ecom- poses when the mixture is warmed, yielding the a d i d e of mouo- bromacetoacetic acid, COMe*CHBr*CO*NHPh. This substance crys- tallises in plates, and melts at 138" with decomposition. Isonitruso- acetoucetic anilide, COMe-C(NOH)*CO*NHPh, crystallises in prisniq, and is freely soluble in alcohol, ether, acettic acid, arid light petroleum. It melts at 99-100". On reduction with zinc and acetic acid, a crys- talline compound, melting between 212" and 215", is obtained.The formation of hydroxylepidine (0,-m eth y karbostyril), C,NH,Me*OH [Me : OH = 4' : 2'1, by the action of dehydrating agents on acetoacetic anhydride, has been already described (Abstr., 1884, 334 and 1198), and this substance has been described under the names of hydroxymethylquinoline and hydroxyquinaldine. On distillation with zinc-dust, it, is converted into y-Zepidine, and it yields chlorolepidine when treated with phos- phoric chloride (Abstr., 1885, 274). Chlorolepidiqe, C,NH,MeCl [Me : C1 = 2' : 4'1, melts a t 59" and boils a t 296" (cow.) ; i t yields y-methylquinoline when reduced with hydriodic acid, and also when decomposed by water a t 200". Methozylepidine, C9NH5Me*OMe, formed by the action of potawium methoxide on chlorolepidine, is an oily liquid boiling a t 275-276'.It forms a crystalline platinochloride. Ethoxylrpidine melts a t 51" and boils at 250" under 342 mm pressure. Chlorolepidine reacts with aniline, forming pken yllqidinaniine, a crystalline compound melting at 129-130". The platinochloride melts at 235". Methyllepidone or dimethylpseudocarbost?/ril, C6H4<NMe'. CMe ' CH co > , has already been described by the author M dimethylpseudoquinoxyl m 2160 ABSTRACTS OF CEEhilCAL PAPERS. 270" liquid volatile stupetying anhydrous, spar- ingly soluble (Abstr., 1885, 274). It can be prepared by the action of methyl iodide on hydroxylepidine, by the condensation of methylaniline and ethyl acetoacetate, and also by heating methoxylepidine a t 280".Methyllepidoiie melts a t 130- 132", and sublimes without decomposi- tion. It is a strong base, forming salts which are not decomposed by water. The platino- chloride, (C,,HllNO),,H2PtCl~ + 3H20, decomposes a t 214-21 5". Nascent hydrogen converts methyllepidone into a sparingly soluble crystalline compound, which melts a t 258". With bromine-water, methyllepidone forms bronaometh yllepidine, CIIH,,NOBr. This com- pound crjstallises in needles and melts at 172". It is insoluble in water and alkalis, but dissolves i n dilute acids and forms a cmptalline platinochloride. On the addition of bromine to a solution o€ methyl- lepidone in chloroform, a dibromo-additive product appears to be formed. It is decomposed by warm water, forming rnonobromo- met hyllepidone.The properties of methyllepidone, methoxy lepidine, and lepidine are seen in the following table :- It boils a t 290" under 250 mm. pressure. 25 3-25 5" liquid volatile penetrating, anhydrous, spar- ingly soluble Methyllepidone. I---- Boiling point ........ Melting point. ...... I n steam.. .......... Odour .............. Ylatinochloride ...... Bromine-water ...... 290" under 250 mm. non-volatile very faint contains 3H20, ' soluble in hot Hc1 monobromide 130-132" Methoxylepidine. 1 Lepidine. I--- ----- w. c. w. Metaquinolinecarboxylic Acid. By Z. H. SKRAUP and P. BRUNNER (Montrtsh. Ckem., 7, 519--520).-1t is here shown that the seventh quinolinecarboxylic or the met aquinoliuebenzocarboxylic acid, re- cently obtained by Tortelli from a-amidophthalic acid by means of the glycerol reaction, is also formed in small quantities, fogefher with its isomeride, from meta-amidobenzoic acid, by means of the same reaction.In previous experiments, its formation was overlooked (Abstr., 1882, 71). -2583) .-Further experiments on a larger scale, and with pure materials, have confirmed the author's previous results (Abstr., 1886, 478). a-AZZyZpyridine boils a t 187*5-192*5", and is a strongly refracting liquid of sp. gr. 0.9595 a t 0", sparingly soluble iu water, and having a distinct conyrine-like odour. The platinochloride, (C3H,*C,H,N)2, H2PtC16, melts at 185-186", and crystallises in needles sparingly soluble in water. The auroohloride melts at 135-136" ; the mercuriocbloride and cadmio-iodide are also described.By the action of sodium on an alcoholic solution at the boiling point, a-allyl- V. H. V. Synthesis of Active Conine. By A. LADENBURG (Em., 19, 2578ORGANIC CHEMISTRY. 161 pyridine is reduced almost quantitatively to a-propylpiperidine. This base has a sp. gr. 0.8626 a t (I", and boils at 166-167" ; its hydro- chloride crystallises in white, silky needles, melting a t 203-205". Iu smell, solubility, Rpecific gravity, and physiological action, a-pro- pylpiperidine resembles conine, and not only are the platinochlorides, aurochlorides, and cadmio-iodides similar, but when a-propylpiperidine is converted into conyrine by Hofmann's method, a blue fluoresceiice is obtained just as with conine. This fluorescence is due to a n accompanying product, for if the fluorescent base after separation from unaltered conine be converted into the plntinochloride, the conyrine regenerated from it is no longer fluorescent. Conyrine pbtino- chloride from conine crystallises in monoclinic forms : a : b : c = 1.0614 : 1 : 1-5374; g = 87" 8'; and thecrystals from the synthetical base give practically the same values on measurement.z-Propylpiperidine, however, in addition to the lower melting point of its hydrochloride, is optically inactive, and must be regarded as a physical isomeride of conine. To effect a separation into two optically active bases, a sterilised nutritive solution containing 0.5 per cent. of the tartrate was seeded with Penicillium glaucum, but with- oyt result. The active base, however, was obtained by introducing a crystal of the salt into a very concentrated solution of a-propyl- piperidine hydrogen tartrate; a slow separation of crystals took place, which yielded a dextrorotatory base, wbose specific rotation wm [a]D = 13" 87', compared with [a]D = 13" 79' for conine.The hydro- chloride of the synthetical active base melts a t 217.5", that of conine a t 217-5-218*5". From the mother-liquor, a lmvorotatory base was obtained, but it contained a large proportion of the dextrorotatory modification, which could not be further separated by the crystallisation method. However, on converting this lsvorotatory mixture into the cadmio- iodide, i t was found that after crystallisation, the crystallised salt? yielded a base which was less laevorotatory than before, whilst fram the mother-liquor a base was obtained, which in a 50 per cent.alcoholic solution gave a rotation of -3" 30' in a decimetre tube, compared with 3" 10' for conine under the same conditions. w. P. w. Reduction of Nicotine. By A. LIEBRECHT (Ber., 19,2587-2598). -The author gives reasons for regarding nicotine as a pp.hexn- hydrodipyridyl, in which one of the pyridine nuclei has taken up two, and the other four atoms of hydrogen. The author not having succeeded in obtaining dipyridyl by the oxidation of nicotine, has examined the complete reduction prodiict obtained from its solution in absolute alcohol by the action of sodium (comp. Abstr., 1886, 161). Dip@eridyZ, CloHmN2, is a colourless, oily liquid, solidifying a t a low temperature, and having an odour like that of piperidine. It has a sp.gr. = 0.9561 at do, is laevorotatory, boils at 230-252" without decomposition, and is volatile to some extent with steam. I n water, alcohol, and ether, it is readily solnble, and on exposure to light or the air it turns slowly yellow. Contrary to expectation, dipiperidyl acts only as a feehle poison. Dipiperidyl is a bi-acid base : its simple salts art: very soluble and do not readily crystallise, although some162 ABSTRACTS OF CHEMICAL PAPERS. of the double salts crystallise well. The hydrochloride is very deliquescent ; the periodide, CloH20N2,2HI,21z, crystallises in brown needles, which lose iodine on drying in the air. The platinochloride, C,&,oN2,HzPtC16, forms small, red prisms, which on rapid crystalha- tion, separate either singly or in staurolite-like groups : it melts at 202-203".The aurochloride, C18H20N2,2HA~C14, crystallises in yellow laminae, melting at 131-132", and is sparingly soluble in water. A mercuriochloride, CloHmNz,2HC1,5HgCl,, crystallises in small sparingly soluble tables. Carbon bisulphide combines with dipiperidyl, forming a, yellow salt, easily soluble in water and alcohol, less soluble in benzene and insoluble in ether. It readily becomes resinified, and when its alcoholic solution is boiled with mercuric chloride, the odour of allylthiocarbimide is evolved. Diacetodipiperidyl, CloN2H~&2, is prepared by heating the base with acetic anhydride a t 170" for six hours. It is a yellow, oily liquid, boiling a t 400-410° with slight decomposition, and does not solidify in a freeeing mixture.The action of methyl iodide results in the formation of the hydriodides of two bases, dimethyl- and trimethyl-dipiperidyl, of which the former is readily soluble, whilst the latter is insoluble in water. Bimetli yldipiperidy2, C10N2H18Me2, is an oil boiling at 230-332", soluble in water in all proportions, and slightly volatile with steam. Its salts, with the exception of the merczcriochloride, CloH18~le2N2,2HC1,2Hg;CI,, &re readily soluble, and can scarcely be crystallised ; theplatinichZoride, Cl,H,,Me2N2,H2PtC16, forms small dark red ciystals. l'rimeth?lldipi~erid~E, C10H1,Me3N2, is obtained as a yellow oil of repulsive odour resembling that of methylamine, boiling a t 205- 212"; i t is insoluble in water, and is not volatile with steam, The salts are very easily soluble and seem to be uucrystallisable, the platinochloride, C,oH,,Me3N,,H,PtC16, is insoluble in alcohol and etber.'l'be action of methyl iodide does not appear to yield a higher methyl- Sparteine. By E. BAMBERGER (Annalen, 235, 368-376).- Sparteine was discovered by Stenhouse (this Joui-nal, 1851, 223), and its compounds were afterwards investigated by Mills (this Journal, 1862, 1). The author has re-examined these bodies, and his results in many oases differ from the observations of Mills. Sparteine boils a t 311--311*5', under a pressure of 723 mm. The sulphate, C15H29N2,H2S0~, forms large, transparent prisms, which are very soluble in water. The hydriodide, C,,H,,N,,HI, forms glistening, four- sided plates, which probably belong to the rhombic system. It i R freely soluble in alcohol and in hot water.When aqueous hydriodic acid acts on sparteine, a resinous mass is formed, from which the dihydriodide can be obtained in silky needles, by boiling the alcoholic solution with animal charcoal. The compound C,,H,,N,Et12, which Mills obtained by the action of ethyl iodide and alcohol on sparteine at loo', is decomposed by ated base than trimethyldipiperidyl. w. P. w.ORQANlC CHEMISTRY. 163 sodium hydroxide solution, forming an oily liquid, which can be separated into sparteine and sparteine ethiodide, by means of ether. Spurtsine ethiodide, CI,H,,N,,EtI, is formed by the action of ethyl iodide on sparteine. It crystallises in thick prisms, and dissolves freely in water and alcohol.Sparteine methiodide crystallises in rhonibic plates; a : b : c = 0.8989 : 1 : 1.6009. Themethylhydroxide is a deliquescent substance, with a strongly alkaline reaction. The carbonate cryetallises in needles. When sparteine is oxidised with potassium permanganate, the chief product is oxalic acid ; acetamide is also formed, together with a small quantity of a pyridine-derivative. w. c. w. Pseudomorphine. By 0. HESSE (Annulen, 235, 229-232).- When potassium hydroxide (2 mols.) and potassium ferricyanide (1 mol.) are added to a solution of pure morphine hydrochloride dissolved in 40 parts of water, pseudomorphine is deposited ; 100 parts by weight of morphine yield 88.4 parts of pseudomorphine. This result shows that the reaction takes place according to the equation 9Cl7H,,NO3 + 2KOH + 2K,FeCy6 = 2CI7H,*NO3 + 2H20 +2K,FeCyG (the yield is theoretically 99.6 per cent.); not according to the following reaction : 2C17H19N03 + ZKOH + 'LK,FeCy, = C17H17N0 3 + CI7Hl9NO3 + 2H20 + 2K,FeCg6 (the yield is only 49.65 per cent.of the morphine employed). This shows that the formula for pseudc- morphine is C17H,8N03*C17H18N03, as proposed by Polstorff (Abstr., 18g9, 405), instead of C17H17N03, as formerly proposed by the author (Abstr., 1884, 616). w. c. w. Papaverine. By G. GOLDSCHMIEUT (Monnatsh. Chern., 7, 485405). -In this paper derivatives of papaveraldine, and the most con- venient method for its preparation, are described. The nitrate, Cz0H ,,N05,HN03, crystallises in citron-yellow needles ; the picrate, in needles grouped together in voluminous aggregates ; the ozime, C20HSON206, in flat, white needles melting a t 245" ; the methiodide, in golden prisms melting a t 135" with decomposition ; and the etho- bromide, in large prisms melting a t 270".Papareraldine, if heated only for a short time with potash, yields reratric acid together with small quantities of a dimethoxyquinoline, the constitution of which is at present uncertain. With tin and dilute hydrochloric acid, papaverine yields a tetra- hydro-derivative, C,,H,,NO,, which crystallises in small, white prisms melting a t 200", soluble in benzene and acetone, sparingly soluble in ether and' petroleum. Its hydrochloride crystallises in transparent prisms of the monoclinic system, melting with violent decomposition a t 290" ; when injected internally, it causes albuminuria with inflamma- tion of the kidneys.The m i d sulyhate forms acicular, and the acid oxalate prismatic crystals ; the dichromafe, glistening prisms ; and the pic?-ate, lemon-yellow needles. The platznochloride crystallises in minute yellow needles, and the stannochloride in concentrically grouped needles. I n an additional note, the author defends the formula C,H',,NO, for papaverine, as against C21H21NO4, that proposed by Hesse, Beckett,164 ABSTRACTS OF CHEMICAL PAPERS. and Wright, and others; exception is also taken to a statement of Hesse relative to the existence of an alkaloid, pseudopapaverine. V. H. TT. Papaverine Salts. By R. JAHODA (Mortutsh. Chem., 7, 506-516). -As a further proof of the formula C20H21N04, proposed for papa- verine, a number of its salts have been prepared and analysed; the results attained afford a strong confirmation of the above view.The neutral succinate forms large tabular crystals melting at 171", soluble in hot water; the bettzoute, triclinic crystals ( a : b : c = 0.459: 1 : 0.680; 9 = 95.27"), melting at 145", soluble in alcohol, insoluble in water; the salicylate, monoclinic crystals ( u : b : c = 1.161 : 1 : 1.685; T,I = 102.39), melting at 130" ; the diodide of the hydroiodide, C2oH21NO,,HI,I2, purple crystals of the monoclinic system. The hydrochloride gives with halogen salts of the metals double crystalline salts, of which the following are described :-The cadtriio- chloride, ( C20H21N0,,H Cl),CdCI,, small crystals, of the tetragonal system ; a : a : c = 1 : 1 : 0.646, melting at 176" ; the cad,mio-brQmide and -iodide, white precipitates, melting at 150" and 180' respectively ; and the zincoiodide, crystallising in small leaflets.V. H. V. Constitution of Cinchonine. By Z. B. SKRAUP (MonatsF,. Chem., 7, 517-518).-The author criticises the view of Bisohoff and Rach that cinchonic acid is ~-~-dicarboxyl-6-valerolactone (Abstr., 1886, 1012) ; R study of the syrupy oxidation product of cinchonine and quinine has indicated the presence of an amorphous acid, C,HI3NOa, a base of the formula CgHI,N02, difficult to obtain in the free state, although its salts form well-developed crystals, as also of a base of the formula C9H7N0, probably identical with kynurine, and an amor- phous substance of the supposed composition C13H'13N02, and of doubtful origin.V. H. V. Specific Rotatory Power of Piperidine Bases. By A. LADEN- BURG (Ber., 19, 2584).--Ti'he results obtained in a previous paper (this vol., p. 160) are in accordance with Le Bel-Van't Hoffs hypo- thesis, since a-propylpiperidine contains an asymmetric carbon-atom iu its constitutional formula. As this is true of all a-alkyl-derivatives of piperidine, the author has examined a-pipecoline and a-ethyl- piperidine, and by converting them into their dextrotartrates has mcceeded in obtaining optically active modifications of each. Uextro- rotatory a-pipecoline has a specific rotatory power of 21" 8'. w. P. w. Action of Bromine on Dimethylpiperidine ; New Synthesis of Piperidine-derivatives.By G. MERLLNG (Rer., 19, 2628-2632). -The author previously obtained (Abstr., 1884, 1385) by the action of bromine on dimethylpiperidine, two compounds-bromodimethyl- piperidineammonium bromide and a hydrobromide. The latter is now shown to be dibromodimethylpiperidine hydrobromide. When the free base is warmed with alcohol, the alkaline solution becomes neutral, and characteristic crystals of monobromodimethylpiperidine-ORGANIC CHEMISTRY. 165 ammonium bromide separate. These reactions can be explained by the consti tutiond formula 5tss:gned by Ladenburg to dimethylpiperi- dine : CH,: CH*CH2*CH,*CH:,*NMe2. The constitution of di bromodi- methylpiperidine and the ammonium bromide would then be CH2Br*CHBr*CH2*CH2*CH2-NMe2 and C H 2 < ~ ~ B r ~ ~ ~ > N M e 2 B r .2- The formation of the hydrobromide of dibromodimethylpiperidine is probably due to 2 mols. of the free base reacting with one another ; this view was strengthened by the discovery of a base free from bromine in the 1:ist mother-liquor from dibromodimethylpiperidine hydrobromide. Haemin Crystals. By K. BIEFALVI ( O h m . Centr., 1886, 499)- Blood free from chlorine yields no hsmin (chlorohsmatin) crystals when heated with glacial acetic acid. The author finds, however, that if NrtC1, NaBr, KBr, NH4Br, NaI, or K I be first added to the blood, crystals resembling chlorohsmat,in are formed. N. H. M. L. T. T. Diastase, By C. J. LINTNER (J. pr. Chem. [2], 34, 378-394). - The author has examined the different metbods proposed for the pre- paration of pure diastase, and determined the diastatic activity of the substances obtained, He adopts Kjeldahl's law of proportionality (Abstr., 1880, 562), and uses the modification of Kjeldahl's method for determining diastatic activity, described in a former paper (Abstr., 1886, 386). In place of his former metlhod for preparing soluble starch, he now recommends the following :-A quantity of pure potato- starch is mixed with a sufficient quantity of 7.5 per cent.hydrochloric acid to cover i t ; it is then allowed to remain for seven days a t the ordinary temperature or for three days a t 40", when the starch lias lost the power of gelatinising. The structure of' t,he starch, however, remains unaltered. It is t'hen well washed with cold water until every trace of acid is removed, and dried in the air.So obtained it is soluble in hot water to a bright and limpid solution. A 2 per cent. solution will remain clear for some days, but 10 per cent. solutions set to a jelly-like mass on cooling. The acid used must riot exceed '7.5 per cent. as 10 per cent. acid causes the gelatinisation of the starch ; with sulphuric acid, however, i t requires at least 15 per cent, acid digested a t 40" to eft'ect the conversion into soluble starch. Lintner uses a 2 per cent. solution of this soluble starch instead of that pre- pared by the method previously given. The dinstatic activity of the precipitated diastases is expressed as 100, when 3 C.C. of a solution of 0.1 gram diastase in 250 C.C. water added to 10 C.C. of a 2 per cent. starch solution produces in one hour, a t the ordinary temperature, sufficient sugar to reduce 5 c.c, of Fehling's solution.Diastase is best prepared from green nialt or from air-dried malt. Lintner examined the preparation obtained from these malts by extraction with water and glycerol and subsequent precipitation with alcohol, both before and after heating a t 70",and obtained, in all cases, a substance with a comparatively slight diastatic activity. As the result of his experiments, he recommends the following method of preparation :-1 part of green malt or sifted air-dried malt is extracted with 2 to 4 parts of 20 per cent. alcohol for 24 hours. The filtered166 ABSTRACTS OF CHEMICAL PAPERS. extract is mixed with 2+ volumes absolute alcohol ; the precipitate quickly settles, and is washed on a filter with absolute alcohol ; it is then transferred to a mortar, well mixed with absolute alcohol, thrown on a filter, and thoroughly washed with absolute alcohol and ether.Finally, it is dried i n a vacuum over sulphuric acid. So obtained it is a light, yellowish-white powder with great diastatic activity. It is purified by repeated solution in water and precipitatiorl with alcohol, and finally by dialysis. Loea's method of purification by means of precipitation with lead acetate is not to be recommended, since diastase loses three-fourths of its activity in the process. By purification, both the percentage of nitrogen and the diastat,ic activity are increased, whilst the amount of ash, which consists entirely of normal calcium phosphate, is.diminished. A preparation obtained from green malt contained 8.3 per cent. nitrogen and diastatic activity = 96. After two precipitations the nitrogen = 9.06 per cent., and the activity = 100. This submitted to dialysis had the percentage of nitrogen raised to 9.9, and the percentage of ash diminished from 10.6 to 4-79. These and other analyses show that the diastatic activity increases with the amount of nitrogen. A purified diastase gave the following numbers on analysis, calculated on the ash-free substance. For the purpose of comparison the analyses of other soluble ferments are given :- C. H. N. 8. Diastase. . . . . . . . . . 46.66 7.35 10.42 1.12 (Lintiier). Pancreatic ferment 46.57 7.17 14.95 0.95 (Hufner). Invertase . . . . . . . . 43.9 8.4 9.5 0.6 (Barth, Donatlh).Emulsin .. . . . . . . 43.5 7.0 11.6 1.3 (Bull). Diastase gives all the reactions for the albuminoyds, but not the characteristic biuret reaction for peptones ; it gives, however, a, characteristic blue coloration with tinctme of guaiacum and hydrogen peroxide, which is soluble in ether, benzene, chloroform, and carbon bisnlphide, but not in alcohol. This reaction is given by no other soluble ferment or protein substance. Note.-Lintner appears to have overlooked the fact that O'Sullivan (this Journal, Trans., 1884, 2) described an almost identical method of preparing pure diastase. Action of Diastase and Invertin. By H. MULLER (Ann. Agronom., 12,481-482).-The autlior has studied the action of these ferments under conditions such as prevail in the plant-cell, with a view t o elucidate their physiological importance.Both ferments are active at O", but the activity increases until the neighbourhood of 50" is reached : the temperatures being 0", lo", 'LO", 30", 40" ; the energy of diastase is expressed by the numbers 7, 20, 38, 60, 98, and that of invertin by the numbers 9, 19, 36, 63, 93. Under ordinary conditions, cell-say contains much carbonic anhydride, and is exposed to a pressure of several atmospheres. Both of these circumstances accelerate the activity of the ferments. Even at the ordinary pressure, saturation of the liquid with carbonic anhydride may have the effect of tripling the energy of diastase, and in presence G. H. Ill. G. H. M.PHTSIOLOGICAL CHEMISTRY. 167 of carbonic anhydride diastase has the power of acting on starch .which has not been boiled to a paste.Between the limits of 2 and 20 per cent., concentration of a sugar solution has little effect on the action of invertin, which is a little more feeble in strong solutions than in weak ones, but the accumulation of invert sugar is strongly opposed to the continuance of the reaction. J. M. H. M.l 2 2Ethyl bromide ..............Propyl ................Butyl ................Iso-propyl bromide. .........Amy1 bromide.. ............ABSTRACTS OH CHEMICAL PAPERS.0 *81 '03'68.84 '5Organic Chemistry.81.265.225.215 733-45Methods for Determining the Relative Stability of the AlkylBromides. By I. REMSEN and H. W. HILLTER (Anrer. C7~ern. J., 8,251-262) .-The bromides in molecular proportion were treated inalcoholic solution with the several reagents, and the hydrobromic acidformed estimated by silver nitrate solution with ferric thiocyanate asindicator.The relative results are embodied in the following table,Column I showing the action of zinc arid dilute sulphuric acid;11, the action of cobalt-zinc couples and acetic acid ; I11 and IV, theaction of alcoholic soda under certain conditions; T, the action ofcobalt-zinc couples in presence of soda, but after deducting the actionof the soda itself; VI, that of ammonia; and VII, that of silvernitrate o r acetate. The action of sodium amalgam is unsatisfactory,owing to the cnnstant variation of the alkalinity of the solution, andthe authors believe that the best results are to be obtained by theaction of cauqtic soda or ammonia, or of silver salts.1 .0 - -1.11 27 3 2.60'58 - -0 53 4.3 21.70.83 -- -------- I11.1 -33 *36 '011 *19 . 5111.28 -49.14 '33 . 44 -5IV. 1 v. 1 TI. 1 VII.H. B.Derivatives of Diethylene Bisulphide. By W. MANSFIELD(Ber., 19, 2658-2668) .--In continuation of former work (Abstr.,1886, 525), other derivatives of diethylene bisulphide, C4H8S,(compare Masson, Trans., 1886, 234), are described.The metlhiodide, C4HBS2,MeI, is converted by silver chloride into thecorresponding chlorine compound, a crystalline substance me1 ting at225" ; it yields crystalline precipitat,es with platinic, mercuric, andauric chlorides. With moist silver oxide, the methiodide yields thecorresponding hydroxide, C4H8S2Me*OH, the solution of whichpossesses w ell-marked basic propei-ties, absorbs carbonic anhydride,and precipitates solutions of the heavy metals.The salts obtainedby its neutralisation with acids are exceedingly deliquescent ; themost stable is the picrate, which chrystallises in golden needles meltiiigat 192-193'. The dimethiodide, C4H8S2,2MeI, nielts a t 207-208",and yields a corresponding chloro-derivative, which gives precipitateswith the chlorides of the platinum-group of metals. In the course ofthe preparation of the dimethiodide, a periodide' of the compositionC4H8SaMeI,12 is obtained, which melts at 92-93", and crystallises inthe monoclinic system (a : b : c = 0.89 : 1 : 0.67).Experiments made with a, view of obtaining the hydroxides bORQANIC CHEMISTRY.128evaporation of their aqueous solutions were unsuccessful ; an oil ofcomposition C,H,,S, was formed (to this substance Masson ascribesthe formula C,,H,S,, ibid., 247). The author considers that thiscompound is derived from dithioglycocine by the displacement of bothsulphydryl hydrogen-atoms by the methyl and vinyl groupingsrespectively, thus, SMe*C,H,*S*CH : CH, ; and in accordance with thisview it is shown that the compound takes up four atoms of bromine.Diethylene bisulphide combities readily with benzyl halogen com-pounds ; thus with the bromide it forms a substance, ClH8S2,C,H7Br,which melts at 146", and crystallises in the rhombic system. Thecorresponding iodine compound crystallises in pale yellow needles, de-composing when heated a t 145", and the chlorine compound in colour-less needles melting.a t 143". On heating the above bromine compoundwith alkalis, an oifof the composition Gl1H,S, is produced.V. H. V.Disulphones. By R. ESCALES and E. BAUMANN (Ber., 19, 2814-28 17) .-Ethylidenediethylsulp hone, CHMe ( S0,E t),, is prepared bythe action of potassium permanganate on a-dithioethylpropionic acid(from pyruvic acid and mercaptan). It forms plates rather solublein water, more soluble in alcohol and ether. It melts a t 60°, anddistils without decomposition. The bromo-derivative, CBrMe( SO,Et),,crystallises in small prisms melting at 115" ; it is sparingly soluble.Ethylitlenedipheny ZsuZp hone, CHMe (SO,Et),, is prepared by gradu-ally treating a very dilute solution of potassium dithiophenylpropio-nate (Abstr., 1886, 878) with 1 per cent.permanganate solution. Itis insoluble in water, alkalis, and, acids, sparingly soluble in alcoholand ether, more readily in benzene. It melts at 101-102". It isisomeric with Blomstrand and E werloeff 's etbylenediphenylsulphone(Ber., 4, 726; compare also Otto and Damkohler, J. Pherm. Chern.,30, 171 and 321).Disulphcnes. Br E. BAUMANN ( B e y . , 19, 2806-2814) .-Diethyl-sul~honedimetliylmetha?1e, CMe2( S02Et),, is prepared by shakingdithioethyldimethylmethane with 5 per cent. permanganate solution,and occasionally adding a few drops of acetic or sulphuric acid.When no more permanganate is decolorised, the liquid is heated andfiltered, and the filtrate evaporated to half its bulk.The greaterpart of the disulphone separates on cooling. It crystallises in thickprisms, melts at 130-131", and boils with slight decomposition a tabout 300". It is readily soluble i n warm alcohol and water, rathersoluble in ether, benzene and chloroform. Sulphuric acid dissolvesit very readily, and decomposes it when warmed; nitric acid andbromine both dissolve it, but are without further action.Dietli yls~lphonepr~7metliylllzethane, C MePr( SO,Et),, crystallisesfrom water in long needles melting at 86" ; it dissolves sparingly inwater, readily in alcohol, ether, and chloroform.Ethylic P-diethylsulphonebzctyrafe, CMe( SO,Et),.COOEt, is preparedby oxidising ethylic P-dithioethylbutymte.It crystallises from water inslender needles more than an inch long, melts at 63", and dissolvesvery sparingly in cold water, more readily iu alcohol and ether.N. H. M124 ABSTHACTS OF CHEMICAL PAPERS.Diethyls~lphonsmethnne, CH,(SO,Et),, is obtained by oxidisingethyl orthothioformata (Gabriel, this Journal, 1877, ii, 311) withpotassium permanganate in presence of sulphuric mid. It orystallisesin lustrous plates melting at 104" ; and dissolves sparingly in ether,readily in benzene and alcohol. When t h e aqueous Bolution is treatedwith bromine-water, the dihromo-deriz?ative, CBr,( SO,Et),, is formed.This crystallises from boiling water in lustrous needles meltingat 131".The disulphone is probably formed by the oxidatioh of the sulphideCH,(SEt), present in the thio-ether. N.H. M.Reagent for the Hydroxyl-group. By H. A. LANDWEHR (Ber.,19, 2726).-The substance to be tested is added in excess to 10 to20 C.C. of a solution of ferric chloride (prepared by adding two dropsof a, 10 per cent. solution of ferric chloride to 60 C.C. of water) con-tained in a white dish. The production of a sulphur colour denotes thepresence of hydroxyl. All bydroxy-acids and all alcohols and carbo-hydrates which dissolve in water give the reaction. Ether, alkyl salts,formic, propionic, butyric, oxalic, fumsric, and maloaic acids givenegstiv e results . N. H. M.Non-acid Constituents of Beeswax. By B. SCHWALB (Annalm,235, 106--149).-Repeated boiling with alcohol extracts about5 per cent.of cerotic acid from beeswax. The residue is saponifiedwith alcoholic soda, and after the alcohol has been removed bydistillation and by boiling with wpter, the soap is separated by theaddition of common salt. To remove any free alkali, the soap ispressed in a cloth, redissolved in hot water, and again salted out.This operation is repented several times. The soap is thoroughlydried at 110-120", and the non-acid constituents are separated byfractional solution in, and recry stallisation from, light petroleum.The most soluble portion of the extract, melting between 55" and 6 5 O ,contains two hydrocarbons; one melting at GO.5" appears to beidentical with Krafft's normal heptacosane, C27H,s (Abstr., 1882,1273), and the other which melts at 67", is probably identical withnormal hentriacontane, CYIHM. It is probable that other hydro-carbons are also contained in the wax,The myricyl alcohol is less soluble in light petroleum than thehydrocarbons. It appears to have the formula C31H640, and is notidentical with the alcohol C30H6,0, contained in carnauba wax (Abstr.,1884,1281).I t melts at 85-85.5", and resolidifies at 84". When hetltedwith soda lime, it is converted into the salt of an acid, C31HB202.This acid is sparingly soluble in the usual solvents at the ordinarytemperature, but i t dissolveR in hot light petroleum, and is depositedfrom the solution in white needle-shaped crystals, which melt at88.5-89'. The lead salt melts at 115-116", and dissolves freely inacetic acid and in boiling toluene.The silver salt is amorphous. Itmelts at 180", with decomposition. The copper and magnesium saltsare also amorphous. They dissolve in boiling benzene. The methyland ethyl salts crystallise in needles. They dissolve freely in warORGANIC CHEMISTRY. 125ether and warm alcohol. The methyl salt melts at 71-71.5", and theethyl salt at 69-5-70". Heated under the ordinary atmosphericpressure, the ethyl salt decomposes before boiling into ethylene andthe free acid.Beeswax also contains two lower alcohols, namely, ceryl alcohol,C2sH,,0 or C2,H5,0, and an alcohol of the formula, C2rHw0 orC z a 5 2 0.Conversion of Starch into Glucose by means of HydrochloricAcid. By S. HARVEY (AnaZyst, 11, 221-223).--Tn reference t o theprocess used by Heisch, heating in a boiling water-bath is as goodas heating over a naked flame.In the author's experiments, when-ever the conversion of starch was complete, the results obtainedwere too low, owing to destruction of the glucose ; in fact, it appearsimpossible to limit the time of heating, so as to prevent the glucosebeing attacked. D. A. L.Carbohydrates. By M. HONIG and S. SCHUBERT (Monatsh.Chew,., 7, 455-484).-1n a former paper (Abstr., 1886, 44), theauthors have shown that by the action of sulphuric acid on celluloseand starch, a series of sulphuric acid-derivatives are formed of thegeneral composition Cs,H,,,O,,,( SO,),. These are decomposed inalcoholic solution with production of sparingly soluble compounds,containing a smaller proportion of sulphuric acid, which in their turnare decomposed at a higher temperature with formation of variousdextrins.The different phases of these changes in the case ofcellulose, starch, and grape-sugar are worked out more fully in thispaper. From cellulose, a series of derivatives is obtained from aform of soluble cellulose to dextrose, according to the temperature(5-33") at which the change is effected ; these increase in specificrotatory power and solubility, the lower members of the series givinga blue coloration with iodine, the intermediate a red, and the endproducts no coloration, corresponding with the formation of an achroo-dextrin. These substances also differ from one another as regardstheir conversion by diastase ; the end members are unaltered, whilstthe others are converted into dextrins.From starch, a similar series of compounds was obtained ; althoughin this case the specific rotatory power diminishes from that ofstarch t o that of a dextrin similar to the final product from cellulose,but differing from it in possessing a slight cupric oxide reducingpower.w.c. w.With grape-sugar also, similar results were obtained.In conclusion, the question is discussed whether the starch mole-cule is compounded of other less complex units, differing amongthemselves, a view represented by the formula 15( C,2H200,,),assigned by Brown and Heron, or whether it is decomposed intothese less complex molecules by a chemical change rather than by aprocess of disintegration.Identity of Cadaverine with Pentamethylenediarnine.ByA. LADENBURG (Ber., 19, 2585-2586) .--Cadaverhe and penta-methylenediamhe show the same boiling point, solubility and odour,V. H. V.VOL. LII. 126 ABSTRACTS OF CHEMICAL PAPERS.and agree in their general reactions. The mercuriochloride of pentn-methylenediamine has the forniula C5H,,N,,2HC1,3HgCl2, whilst,according to Brieger, that of cadaverine mercuriochloride isC~HlrN~,2HC1,4HgCI2.The imine obtained from cadaverine is identical in its propertieswith piperidine, which the author has previously shown to be theimine of pentamethylenediamine (Abstr., 1886, 139, 269). w. P. w.Compounds of Aldehydes and Ketones with Mercaptan. BayE. BAUMANX (Ber., 19, 2803--2806).-When furfuraldehyde andmercaptan are treated with dry hydrogen chloride, the reaction isaccompanied by considerable development of heat, which causes afurther deco tnposition.Fatty aldehydes and ketones and aromaticaldehydes also react with mercaptan with development of heat ; withfatty aromatic ketones, the mixture must be warmed, whilst in theease of benzophenone the reaction only takes place in presence of zincchloride.When dithiophenyldim ethylme thane, CMe2( SPh) (Abstr., 188-5,749), is prepared, avoiding development of heat, a solid product isobtained instead of an oil. It forms large, clear crystals, which meltat 56", and dissolve readily in alcohol, ether, benzene, &c., and areinsoluble in water. When heated at loo", it decomposes into a mix-ture of several substances, which no longer solidifies.Dithioethyl-dimethylmethane, CMe,(SEt)2 (Zoc. cit.), was also prepared at, a lowertemperature, and was obtained as a mobile, strongly refractive liquid,boiling at 190-191" ; it combines directly with methyl iodide,yielding a crystalline substance. N. H. M.Linoleic Acid. By K. PETERS (Monatsh. Chem., '7, 552-555).-The formula generally ascribed to linoleic acid is C18H2602 ; it wouldthus be the isologue of palmitic acid, and convertible into it byhydrogenising agents. It is here shown that the analytical results ofa sample of an acid, purified by means of its barium salt, are more inaccordance with the formula C18H3202, and when heated with, phos-phorus and hydriodic acid, it yields not palmitic, but stearic acid.V. H.V.AcetyllEevulinic Acid. Constitution of v-Ketonic Acids.By J. BREDT (Annulen, 236, %25-232) .-Acetyllaevulinic acid isformed by the action of acetic anhydride on lavulinio acid at 100".It is deposited from an alcoholic solution in crystals, resembling thoseof potassium nitrate. It melts at 78-79", and boils about 14OC,under 15 mm. pressure ; under the ordinary atmospheric pressure, itsplits up on boiling into acetic acid and a- and P-angelica lactones.As the compound is neither decomposed by water nor by a coldsolution of sodium carbonate, the author regards it as a hydroxy-lactone-derivative, not as an anhydride. This is evidence in favourof the formula C H , < ~ ~ ~ > C M e .O H for lavulinic acid.w. c. wORGANIC CHEMISTRY. 127New Reaction of Aluminium Chloride; Syntheses in theAcetic Series. By A. COMBES (Compt. rend., 103, 814-817).-When aluminium chloride is added to a solution of acetic chloride incarbon bisulphide or chloroform, there is abundant evolution ofhydrogen chloride, and a white, crystalline solid of the compositionC12H,406A12C18 is obtained. It remains unaltered in dry air, but isimmediately decomposed by water with evolution of carbonic anhr-dride. If the water is added carefully to the solid, or if the lrhtter isthrown into water in small quantities at a time, a clear liquid isobtained, which, when extracted with ether, or better, chloroform,yields a colourless liquid boiling at, 156-137" under a pressure of750 mm.It has the composition C6H8O2, and is lighter than water,in which it is readily soluble without undergoing any decomposition.The action of aluminium chloride on acetic chloride is represented bythe equation-6CzH30C1 + Al,Cl, = 4HC1 + (COMe*CH2*CO-CE2.CC1zO~)zAlzC14,and the solid compound is decomposed by water with formation ofaluminium hydroxide and the acid COMe*CH,*CO*CH,*COOH, whichimmediately loses carbonic anhydride and yields acetylacetone,CsH,02.Acehjacetoize has the properties of a diketone, and combines, withdevelopment of heat, with a concentrated solution of sodium hydrogensulphite. It is not affected by phosphorous chloride or aceticchloride, but is decomposed by potash or soda, with formation ofacetone and an acetate.When treated with sodium amalgam, ityields isopropyl alcohol, pinacone, and sodium acetate. If slowlyhydrogenised in an acid solution, it should yield symmetrical amylicisoglyool, CH2( CHM~OOH)~. Bromine acts energetically on acetyl-acetone, with formation of acetic bromide and penta- and tetra-brom-acetone. Phosphoric chloride removes the oxygen, and yields atetrachloride which immediately loses 2 mols. HCl, and yields chloridesof the composition C5H6C1,, derived from an unknown valer-ylene.When the solid product of the action of aluminium chloride onacetic chloride is treated with absolute alcohol instead of water, nogas is evolved. The products will be described in a subsequentThis reacicion is general, and takes place with propionic and butyricpaper:chlorides, and with chloral.C. H. B.Gluconic Acids. By F. VOLPERT ( B e y . , 19, 2621 - 2623)-Ethy lic pentacetylgl ucoiiate is a white, crystalline substance, readilysoluble in alcohol and water; it melts a t 103.5". Ammonium andpotassium gluconate crystallise well in plates and needles. Corn para-tive experiments made with Hoenig's paragluconic acid (hbstr.,1881, 893) show that it is identical with gluconic acid.Action of Thiocarbamide on Ethyl Acetoacetate. By R. LIST(Annalen, 236, 1-32) - In the preparation of thiornethyluracilfrom thiocarbamide and ethyl acetoacetate, by the process previouslydescribed by the author (Abstr., 1886, 4 3 ) , it is found that the pre-N. H. M.k 128 ABSTRACTS OF CHEMICAL PAPERS.sence of ammonium thiocyanate increases the yield of the product.Thiomethyluracil, CS<NH .-,b->CH, is very sparingly soluble in NH*CVealcohol, ether, and cold water.It crystallises in plates, and begins t odecompose at 280'. The silver and copper salts are amorphous.The mercuric salt forms anhydrous, micaroscopic needles. The potas-sium salt, C5H,NzOSK + QHzO, is insoluble in alcohol, but freelysoluble in water. The sodium salt, C5H5N20SNa + 2Hz0, crys-tallises in prisms, which effloresce on exposure to the atmosphere.The methyl salt melts at 219-220", but begins to sublime at 120",forming plates or needle-shaped crystals. The addition of silvernitrate to the amrnoniacal solution of this substance precipitates thecompound C6H,NzSOPhg.E thy1 t hiometh y Zuracilacetate is obtained in needle- shaped crystalsby the action of ethyl monochloracetate on thiomethyluiacil.Thio-meth9luraciZacetic acid crystallises in needles or plates, and melts a t203-204". It is very sparingly soluble in cold water, alcohol, andether.Thiomethyluracil unites with hydrogen bromide to form an unstablecrystalline additive product. Bromine acts on thiornefhylnracil sus-pended in water, eliminating the sulphur and forming dibromoxy-methyluracil. By a similar reaction, dichloroxymethyluracil isobtained in transparent plates, soluble in hot water and in warmalcohol. Thiomethyluracil is converted into methyluracil by boilingwith freshly precipitated d v e r or mercuric oxide, and also by theaction of ammonia, or strong hydrochloric acid at 150", and of aceticacid at 180".w. c. w.The ethyl compound melts a t 144-145".Nitro- derivatives of Methyluracil. By A. KOHLER (Annalen,236, 32-57) .-Behrend (Armalen, 229, 32) obtained nitrouracil-carboxylic acid and a cornpound, C5H2N405, by the action of strongnitric acid on methyluracil. Nitrouracilcarboxylic acid, C5H,N30, +2H,O, crystallises in rhombic prisms ; a : b : c = 0.323: 1 : 1.081. Onboiling the aqueous solution, carbonic anhydride is evolved and nitro-uracil, CaH3N30a, is formed. Ethy I nitrourncilcarBo~ylate, prepared bysaturating the alcoholic solution of the acid with hydrogen chloride,crystallises in monoclinic prisms. I t is less soluble in alcohol andwater than the free acid, and it does not split up on boiling withwater.The salt melts at about 250" with partial decomposition. Theconstitution of this substance may be represented by the formulaAmido~?.a~ilcarbox~lic acid, C5H5N30,, is formed by the action oftin and hydrochloric acid on the nitro-acid, but a better yield isobtained by the reduction of the ethyl salt. The product, con-sisting of a mixture of the ethyl salts of amidouracilcarboxylic andhjdroxyuracilcarboxylic acids, is saponified by boiling with an aqueoiissolution of potassium hydroxide. Amidouracilcarboxylic acid isdeposited from its aqueous solution in needles. Between 150" and160", it splits u p into carbonic anhydride and amidouracil. Thepotassium salt, C5H6N,05K + HzO, crystallises in prisms ; the bariumORGXSIC CHEMLSTRY. 7 29copper, and mercury salts are amorphous.The sparingly soluble leadand silver salts are crystalline. The ethyl salt is insoluble in alcoholand sparingly soluble in water. It melts sat 260" with p r t i e l decom-position.A4 good yield of nitrouracil is obtained by adding 5 C.C. of strongsnlphuric acid to 4 grams of methyluracil suspended in 10 C.C. offuming nitric acid. The yield of the sparingly soluble compound,C5H2N,05, which is obtained as a bye-product by the action of nitricacid on methyluracil, is increased by warming the mixture as som asthe reaction ceases.C5HN,05*NB, t&H20 crystallises in yellow glistening needles ; C5HN,05R + liE20,red needles, sparingly soluble in water ; the soiution decomposes, onboiling.The barium salt, (C5HN405)2Ba + 4H20, forms prismaticneedles, freely soluble in water. On reduction with tin and hydro-chloric acid, the amido-compound, C,H,N,O, + HzO, is obtained inslender needles, sparingly soluble in water. After evaporation withhydrochloric acid, the residue yields the murexide reaction.This compound unites with bases to form salts.w. c. w.New Mode of Formation of Dibromo- and Dichloro-bar-bituric Acids. By R. B E H n E w (Annulen, 236, 57-68).-Themost convenient method of preparing bromomethyluracil (Abstr.,11386, 338) is to convert methyluracil into dibromoxymethyluracil bythe action of bromine-water (Annden, 229, l8), and to decompose theproduct by boiling in alcohol.DichloroaymsthyZuraciZ resembles thecorresponding bromo-derivative in its properties and in its mode ofpreparation. It crystallises in triclinic plates, and is not decomposedby boiling with alcohol. It is decomposed by alcohol or water at 150",forming a sparingly soluble compound, and is converted into mono-chloromethyluracil by the action of stannous chloride and hydro-chloric acid. Chloromethyluracil is insoluble in ether, sparinglysoluble in water and alcohol. It crystallises in needles.Dibromoxymethyluracil is oxi dised to dibromoburbituric acid byfuming nitric acid. This is identical with the dibromobarbituricacid described by Baeyer (ArLnaZen, 130, 130). Hot fuming nitricacid converts dichloroxymethyluracil into dichlorobarbituric acid,C4H,Cl2NzO3.This substance crystallises in rhombic prisms or plates,a : b : c = 0.7766 : 1 : 0.8929. The crystals are isomorphous with thoseof dibromobarbituric acid, and are much more soluble in alcohol,ether, and water. A small quantity of barbituric acid is formed inthe preparation of dichlorobarbituric acid by this process.Relation of the so-called a-Thiophenic Acid to the NormalThiophencarboxylic Acids. By V. MEYER (AnnaZen, 236, 200-224).-1n former communications (Abstr., 1885, 1207 ; 1886, 227,534), the author has pointed out that the derivatives of a- and P-thio-phenic acids (melting a t 118" and at 126.5" respectively), are identicalin crystalline form, solubility, and melting point, but that on decom-position the a-derivatives yield the a-acid, and the &derivatives the/3-acid.The so-called a-acid is really a mixture of the p- and 7-acids,which cannot be separated by recrystallisation. It is formed onw. c. m130 ABSTRACTS OF CHEMICAL PAPERS.oxidising a mixture of ,9- and y-thiotolens, but is not obtained bymixing together the ready-formed p- and r-acids. In the thiophen-group the tendency for the isomeric compounds to crystallise togetherHalogen Carriers. By C. WILLGERODT (J. pr. Chem. [el, 34,264c292).-An accoant of experiments on the effective value ofvarious elements and their compounds in the chlorination of benzene(compare Abstr., 1885, 1034). Two cases occur on the passage ofchlorine into benzene in presence of these foreign substances, namely,either the formation of benzene hexachloride attended by a consider-able gain in weight of the benzene and practically no evolution ofhydrogen chloride, or the displacement of hydrogen by chlorine withcorresponding evolution of hydrogen chloride.The details of thevarious experiments are given in full. To the substances inducingthe first reaction belong aluminium hydroxide and sulphate ; thoseinducing the latter reaction are again separable into thoso elements thepresence of which induces the production of mono- or di-substitution-derivatives, and those forming a chloride of the formula XC1, or(XCl,),, which lead to the production of tetra- o r penta-substitution-derivatives. The function of these is conditioned by the atomicmobility of the chlorine-atoms in its compound, and in fact to theaffinity of some kind or another of the inorganic chloride for thecarbon compound.Adopting the periodic system of classification, themembers of the first two groups are inactive, those of the second, fifkh,seventh, and eighth groups are eminently active, and those of thefourth are, with the exception of tin, inactive.The experiments of Lothar Meyer, Friedel and Crafts, and otherson the chlorination of carbon compounds by means of such substancesas aluminium or ferric chloride, seem to indicate that a t first ahydrogen-atom of the hydrocarbon is displaced by the groupingM,CI, with separation of hydrogen chloride, and to this compound amolecule of chlorine adds itself on and finally takes the place of thehydrogen. The compounds AlzC16,6C6H6 (or 6C7He) obtained byGustavson, the author regards as combinations of a molecule of metallicchloride with one of the hydrocarbon, the remaining five moleculesfunctioning in like manner to water of crystallisation.is much stronger than in any other series.w. c. w.V. H. V.Preparation of Organic Fluorides. By 0. WALLACH (Annulen,235, 255-271) .-Fhorobenzene, C,H,Fl, can easily be prepared bypouring 20-30 C.C. of strong hydrofluoric acid into a flask containing10 grams of benzene dinzopiperidide. The flask is connected with areceiver by means of a spiral condenser surrounded by a freezingmixture. A tube passes through the doubly perforated cork whichcloses the receiver, and dips into mercury. On gently warming theflask, the reaction commences and the fluorobenzene collects in thereceiver.Pluoroto Zuene is prepared from toluene paradiazopiperidido.As it is much easier to condense than fluorobenzene, the apparatusmay be simplified by omitting the tube dipping iinder mercury.Fluorotoluene resembles benzonitrile in odour. It is oxidised bychromic acid, yielding fluorobenzoic acidORGANIC CHEMISTRY. 131ATitl.obenzeneparadia~opiperidide forms golden, needle-shaped crys-tals. It melts at 96-97', and dissolves freely in ether and warmalcohol. It is decomposed by hydrofluoric acid, yielding parajuoro-nitrobenzene. This compound is also formed by nitrating flaorobenzene.It melts at 21-22' and boils at 204-206".Acetamidobenzene rnetadiazopiperidide, C6H4(NHAc) N N2C5B isdeposited from weak alcohol in thick prisms which melt at 100-101".It is decomposed by hydrofluoric acid, yielding metujluor-aniline ; an oily liquid resembling aniline. Parqfiuornniline is formedby reducing an alcoholic solution of parafluoronitrobenxene withstannous chloride and hydrochloric acid. The nitrate, hydrochloride,and sulphate crystsllise well. Acetic anhydride converts parafluor-aniline into ncetoJuoruniZide. This compound is sparingly soluble inwater, but dissolves readily in alcohol.The replacement of hydrogen by fluorine increases the RP. gr., buthas very slight effect on the boiling points of the compounds.Benzene ................Toluene. ................Nitro benzene ............Aniline..................Fluorobenzene ............Parafluoro to1 ue ne ........Parafluoronitrobenzene ....Parafluoraniline ..........Sp. gr.0.8990.8821.21.0361.0240.99213261.153B. p.80.5"3 1120518484 -85116"205-206185-189Fluorobenzenesulphonic acid and fluorodiphenyl, when added to analkaline solution of piperidine, form the compoundsNaS03*C6H4*N2*C5NH10and C5NHlo*N2*C6Ha*CsH4*N2*C5NHI0 respectively. w. c. w.Reaction of Potassium Cyanide with Orthonitrobenz ylicChloride. By E. BAMBERGER (Ber., 19, 2635--2642).-1n the reac-tion between potassium cyanide and orthonitrobenzylic chloride thereare formed, besides orthonitrobenzyl cyanide, an orthodinitrocyano-dibenzyl and substances of the composition C22H14N40, andCI5HON3O3, the constitution of which is uncertain.Orthonitrobenzy l cyailide, NOz*C6H4*CH2*CN, previousIy described bySalkowski, crystallises in pale-yellow prisms which melt at 82.5" ; itssolutions give a blue-violet coloration on addition of s trace of alkali ;the dye formed is, however, unstable.Orthodinif rocyanodibemyl, N0,*C6H4*C'H( CN) *CH2*C6HI*NOa, crys-tallises in snow-white prisms, melts at 110.5" and is soluble inbenzene, alcohol, and acetic acid.This substance is also obtaineddirectly from orthonitrobenxyl chloride and the correspondingcyanide. It is very stable towards acids ; when heated with alkalisand the product heated with mineral acids, a compound, CI5HBN1O3,separates out in volum~nous, yellow flocculze, which can be crystallisedfrom alcohol i n silky leaflets melting at 235-238".The samesubstance, i s also a subsidiary product in the above reaction132 ABSTRACTS OF CHEMICAL PAPERS.The compound C22RliN406, mentioned above, crystallises in thickglisteaing prisms which melt at 190.6"; it is sparingly soluble inalcohol, readily in acetic acid ; it behaves towards acids and alkalisas a, perfectly indifferent substance. V. H. V.Oxidation of Nitromesitylene, By W. H. EMERSON (Amer.C h ~ m . J., 8, 268--271).-Schmitz has pointed out that as paranitro-mesitylcnic acid is prodnced during the preparation of mononitro-mesitylene, it is probable that the first-named substance is producedby the oxidation of the last-named, and therefore here as in other cases,except with mesitylene sulphonamide, the presence of the nitro-groupprotects those hydrocarbon side-chains that occupy the ortho-positionrelatively to the negative nitro-group.This oxidation has before beenattempted but without success ; by dissolving both the substance andthe chromic acid in glacial acetic acid, however, the paranitromesitylenicacid was actually obtained and recognised by its properties and bythose of the corresponding amido-acid. H. B.Intramolecular Changes in the Propyl-group of the CumeneSeries. By 0. WIDMAN (Ber., 19, 2769-278CL).-PropyZhyd~o-curbostyril, C12H15N0, is obtained by treating a solution of orthamido-cumenylacrylic acid (Abstr., 1886, 465) in soda with an excess ofsodium amalgam. Acetic acid is then added, which precipitates a,yellow substance melting at 80"; this changes in a short time topropylhydrocarbostyril melting at 134".The latter crystallises inwell-formed rhonibic prisms, a : 7, : c : = 0,87978 : 1 : 1.64451; p =1.620435, and is very readily soluble in alcohol and benzene. Thecompound is also obtained by reducing orthamidoparapropylcinnamicacid (Abstr., 1886, 464). In the latter reaction, the isopi*opyl-groupmust have undergone an intermolecular change ; prop91 tiydrocarbo-stvril is therefore a normal comDound of the formula,Cumenylpropionic acid (Perkin, this Journal, 1877, i, 400) is bestprepared by boiling pure cumenylacrylic acid for 45 minutes with20 times its weight of hydriodic acid (sp. gr. 1.7) and an equalweight of red phosphorus.The product is filtered, washed withwater, and dissolved in ammonia ; it is precipitated with acid, pressed,and dried. It melts sharply at 75.5" (not 70"). When graduallytreated with fuming nitric acid (10 parts) at -5" to O", and theproduct poured into water, a white crystalline nitro-acid is precipi-tated; it crystallises from 50 per cent. acetic acid in well-formedplates melting at 99". When reduced, it yields propylhydrocar-bostyril. When cumenylpropionic acid is oxidised by potassiumpermanganate, it is converted into orthonitrohydroxyisopropylbenzoicacid (Abstr., 1886, 466).The above experiments show that a conversion of isopropyl intonormal propyl occurs in the successive conversion of cumenylacry licacid into cumenylpropionic acid, orthonitrocumenylpropionic acid, andpropylhydrocarbostyril.The same molecular change dso takesplace when cumenylacrylic acid is converted successively intORGANIC CHEMISTRY. 133orthonitrocumenylacrylic acid, orthamidocumenylacrylic acid, andpropylhydrocarbostyril. The author considers that the so-called'' cumenylpropionic acid " contains normal propyl, and that it isparaprop y lhydrocinnamic acid. The propionic radicle, therefore, as wellas the methyl and acrylic acid radicles, influences a propyl-group inthe para-position, causing the formation of normal propyl.N. H. M.Reciprocal Transformations of Cymene- and Cumene-derivatives. By 0. WIDMAN (Ber., 19, 2781-2785).-With regardt o the change of cumene- into cymene-derivatives, the author objectsto Fileti's suggested law (this vol., p.36) on the ground that thenature of the group has not been determined in any of the compoundscontaining these elements or groups (Cl, Br, Cy, COOH, &c.), andmentions experiments previously described by him (Abstr., 1886,464) which show Fileti's view to be quite incorrect.By F. AHRENS (Ber., 19, 2717--2725).-0ctyI-benzene (v. Schweinitz, Abstr., 1886, 540) boils at 262-264"(uncorr.), sp. gr. 0.852 at 14". It solidifies at -7' to a crystallinemass, is insoluble in water, miscible with alcohol, ether, and ben-zene. Chloroctylbenzene, CsH,C1*CeH17, is prepared by the action ofchlorine in presence of iodine on the hydrocarbon. It is a yellow-ish oil, almost without odour, readily soluble in alcohol and ether ;it boils at 270-275'.Bromnctylbenzene, C6'&Br*C8&, boils at285-287". The moniodo-derivative is prepared by the action ofiodine and mercury oxide on octylbenzene diluted with light petro-leum. I t is a yellow oil, insoluble in water, soluble in alcohol andether. It solidifies at -4", and does not distil without decomposition.I t is very susceptible towards light and heat. Netanitro-octylbenzene,NOz*CsH&&, is formed by the action of fuming nitric acid onoctylbenzene in the cold. It crystallises in long needles insoluble inwater and ether ; sparingly soluble in alcohol and chloroform ; itmelts at 123-124", and sublimes unchanged at a high temperature.When oxidised with potassium permanganate, it yields metanitro-benzoic acid.Orthonitro-octylbenxene is obtained, together with thepara-derivative, by heating the mother-liquor from the preparation ofthe meta-compound. The heavy oil so formed is washed with hotwater. Itbegins to decompose at loo", and cannot be distilled ; at 130" it sud-deiily carbonises. Paranitro-octyl bemene is obtained by first nitratingoctylbenzene in the cold, separating the liquid from the crystals ofmetanitro-octylbenzene, and heating for 12 hours. It is then filteredand again heated, and this is repeated until all the hydrocarbon hasdissolved. The crystalline Rubstance is gently heated to sublime anymetanitro-derivative present, and then strongly heated, when thepara-coapouiid sublimes. It forms small, yellowish, lustrous needles,having a slight odour of benzaldeliyde ; it melts at 204", is insolublein water, soluble in alcohol and ether.was formed when crystals of metranitro-octylbenzene containingN.H. M.Octylbenzene.It is a thick, yellow oil with a peculiar aromatic odour.Diuitro-octy Zbenxene,c6H,(N02)2GH17134 ABSTRACTS OF CHEMICAL PAPERS.fuming nitric acid were washed with ether. Water was poured on tostop the violent reaction which at once took place. It melts at 22ti0,and sublimes below this temperature in transparent cr,ystals with avitreous lustre, soluble in ether and alcohol, insoluble in water ; itsconstitution was not determined. Orfhamido-octylbenzeize hydrodtlo-ride, NH,*C6H4*C8H,,,HCl, is prepared by reducing the ni tro-compoundwith tin and hydrochloric acid ; i t forms small, lustrous, white plates ;when heated, it becomes red.N. H. M.A Fourth Monobromophenol, and a Second Monobromg-benzene. By I?. FITTICA (Ber., 19, 2632--2634).-1n this communi-cation, the author still maintains the existence of the fourtb mono-bromophenol described by him in a former work, the conclusionsfrom which were subsequently shown by Hand to be erroneous(Abstr., 1886, 101 7). The preparation of a second monobromoben-zene is also described, but it was not obtained of constant boilingpoint (60-66"), and the analytical results are far from satisfactory.V. H. V.Constitution of Nitranilic Acid. By R. NIETZKI (Ber., 19,2727) .-When dinmidotetrahydroxybenzene (obtained by redncingnitranilic acid) is distilled with zinc-dust, paraphenylenediamine isformed.This is fresh evidence that nitranilic acid is paradinitro-dihydroxyquinone (compare Hantzch, Abstr., 1886, 1021).N. H. M.Aniline and its Homologues. By L. LEWY (Bey., 19, 2728-2729 ; compare Abstr., 1886, 872).-When paratoluidine is boiled withwater, splendid crystals of the hydrate separate on cooling ; whenexposed to air they effloresce.The xylidinefl and cumidines behave towards phosphoric acidas orthotoluidine does, and yield only primary phosphates.As paratoluidine forms a secondary phosphate, and orthotoluidinea primary phosphate, the para-compound behaves like an elementhaving the atomic weight 214, whilst, the ortho-compound behaveslike an element having the atomic weight 107.In estimating thephosphoric acid in a misture of the two phosphates, the relativeamoiints of paratoluidine and orthotoluidine can therefore be deter-mined. N. H. M.Alkyl-derivatives of Aniline. By A. CLAUS and H. EIRZEL(Ber., 19, 2785-2791).-MethylpropylaniZine, NPhMePr, is preparedby heating methylaniline and propyl iodide for eight hours in a water-bath. The product is dissolved in water, extracted with ether, andtreated with alkali. It is a yellowish oil, boiling at 212" (uncorr.).The hydrochZoride melts at 106" (uncorr.) ; it is very hygroscopic.The ethiodide, NPhMePr,EtI, is a viscous substance readily solublein water. When boiled with concentrated aqueous potash, methyl-ethylaniline is formed.EthyZpropy Znniline, NPhEtPr, is obtained by the action of propyl-aniline (Claus and Roques, Ber., 16, 909) on ethyl bromide, or fromethylaniline and propyl bromide.It is a bright yellow oil boiling aORGAXIC CHEMISTRY. 3 35216" (uncorr.). The hydrochloride is a crystalline substance, and mcltsat, 131" (uncorr.). The msthiodide is a syrup having all the propertiesof methylpropylaniline ethiodide.Methylethylaniline was prepared by the method of Clans andHowitz (Abstr., 1884, 1005) ; i t was obtained in the crystalline stale.The hydrochloride melts a t 114". The propiodide is identical withthe iodide mentioned above. When the aqueous solution of the iodideis heated, or kept in contact with ether, decomposition takes place,with formation of props1 alcohol and methylethylaniline hydriodide.N.H. 31.Action of Ethyl Imidocarbonate on Aromatic Ortho-corn-pounds. By T. SANDMEYER (Ber., 19, 2650-2657).-1n continuationof former experiments on the reactions bet ween ethyl imidocarbonateand the amines of the aroniatic series (Abstr., 1886, G l l ) , the prepa-tion and properties of various derivatives of phenylene and toluylenediamines are described.Ethox ymetheny ltolujy lenediamina, C7H, <- N>C OE t, prepared fromtolnylenediamine hydrochloride and ethyl imidocarbonnte, crystallisesin golden needles which melt at 163", insoluble in cold, sparinglysoluble in hot water, moderately soluble in alcohol. Its aqueous solu-tion gives a voluminous, white precipitate with mercuric chloride.With acids, it forms very soluble salts.When heated with hydrochloric acid, it yields hydroxymetheny I-NH---- N H toluylenediamine, C7H6<- N>C*OH.This substance crystallises iusmall needles, melts at 290", and is sparingly soluble in boiling alcohol,readily in water. Prom its formation, i t would seem to contain thehydroxyl-group, but it is also identical with a compound obtaineddirectly from carbamide and toluylenediamine, which would containthe carbonyl-group ; the atomic transformation of the -N-COH-group into -NH-C 0 is however of frequent occurrence.Et hoxymetheny7pheny lenediainine, CsHa<- N>C *OE t, prepared inlike manner from phenylenediamine, crystallises in reddish glisten-ing leaflets which melt a t 160". In its solubility and physical pro-perties, it resembles its homologne.With hydrochloric acid, it yieldsNKhydroxymethenylphenylenediamine, C6H4<- NH ,>C*OH, which crys-tallises in leaflets, and is identical with phenylenecarbamide obtaineddirectly from or thoni trophenylure thane.Ethoxymethenylanzidophenol, C,H,<N>C*OEt, 0hydroxymethenylamidophenol, CsH4<N>C*OH, 0prepared from amido-phenol and ethyl imidocarbonate, is a colourless oil, boiling at 225-230", of peculiar odour. It is converted by hydrochloric acid intocrystallising in redprisms, which lose their colour on exposure or when separating slowlyfrom solution.The reaction of the amido-acids on ethyl imidocarbonate differ136 ABSTRACTS OF CHEMICAL PAPERS.from those of the amines and the amidophenols ; thus with anthraniIicacid an amidine of the compositionCOOH*CsH,*NH*C(OEt) N*C,H4*COOHis formed.This crystallises in white needles, melts at 223", and isspariogly soluble in boiling water, soluble in hot alcohol. It wouldappear from its formation that this substance should be a bibasicacid, yet its silver salt contains only one atom of the metal in themolecule. V. H. V.Decomposition of Diazo-compounds by Alcohol : Paradiazo-tolueneorthosulphonic Acid. By I. REMSEN and A. G. PALMER(Amer. Chem. J., 8, 243--251).-The authors expected to be able toprepare benzoic sulphinide by the oxidation of orthotoluenesulphon-amide, itself prepared from the orthotoluenesulphonic acid obtainedby boiling the diazo-compound of paramidotolueneorthosulphonic acidwith alcohol.This method seemed all the more promising, as Jensenand Ascher have described the actual elimination of the diazo-groupin the above compound.The authors find no difficulty in the conversion of paranitrotoluenein to paradiazotolueneorthosulphonic acid ; but this, when boiled withalcohol under pressure, yields, contrary t o the statements of Jensenand Ascher, not tolueneorthosulphonic acid as the principal produce,but ethoxytolueneorthosnlphonic acid. The reaction will not proceedwithout the application of pressure ; it commences at 90 mm., andthe two compounds are then formed in equal quantities, but the yieldis very bad, the reaction slow, and the product is black with tarrymatters. At 150 mm. thrice as much of the ethoxy-compound as ofthe toluenesulphoiiic acid is formed, and at 500 mm.the ethoxy-com-pound is formed almost alone ; the reaction takes only a few minutes,and the product is far purer. The acid product of the reaction cannotbe puritied by means of the barium salts, but has to be converted intothe acid amide, and it is to be noted that ethoxytoluenesulphamide,OEt*CsH,Me*S02NH2 [4 : 1 : 21, melts at 143-144", and not at 136",as described by Heffter.It is at presentassumed by all writers that the normal reaction of the diazo-com-pounds when boiled with alcohol is that which results in the displace-ment of the diazo-group by hydrogen ; it is, however, certain that thereaction frequently takes place i n such a way as to form phenetoils:thus the sulphate or nitrate of diazobenzene yields benzene inextremely small quantity, but pheneto'il in very considsrable quantity,and it appears probable that the normal reaction is the one that givesthe phenetoll.The action in the above case is therefore represented not by theequation generally given, but byThis action has not been satisfactorily explained.A list of 15 similar cases is cited in illlistration.C6H3Me<!g:> + EtOH = OEt.C6H3Me*X03H + Nz.H. BORCtANlC CHEMISTRY.137Diazo- and Diazoamido-compounds. By 0. WAL LACH (Annulen,235, 233-255) .-Some of the diazo-compounds of the monaceticderivatives of the diamines (Abstr., 1883, 584) are quite stable in thedry state, and their hydrobromides can be obtained in a pure stateowing to their relatively slight solubility in water and alcohol.Aceticanhydride decomposes the dry diazo-compounds, yielding the aceticderivative of a phenol, thus acetoparatoluidine orthodiazobromideyields diacetamidocresol, OAc*C6H3Me*NHAc. The diazo-com-pounds unite w i t h nitro-ethane to form the mixed azo-compoundsdiscovered by V. Meyer (this Journal, 1875, 1202, and 1876, ii, 93),and they also combine with secondary amines, forming diazoamido-compounds. The latter substances are decomposed by boiling withstrong hydrochloric, hydrobromic, and hydriodic acids according to theequation RN : N*NR" + 2HCI = RC1 + Nz + KHR",HCl. Phenolsare the chief products of the action of dilute sulphuric acid ou themixed diazoamido-compounds.Benzene diaxopiperidide, C5NHlo*Nz*Ph, first described by Baeyerand Jaeger (this Journal, 1876, i, 273), can be readily prepared bypouring a dilute ice-cold solution of diazobenzene chloride (from100 parts of aniline) into a dilute cold aqueous solution of piperidine,100 pwts by weight mixed with 60 of potassium hydroxide.Everyprecaution must be taken to prevent the temperature of the mixturerising above 0". It is decomposed bywarm hydrochloric, hydrobromic, and hydriodic acids, yielding chloro-,bromo-, or iodo-benzene respectively, and piperidine.Toluene paradiazopiperidide, C6H4Me*Nz*C,NH,,,, crydallises incolonrless prisms. It is soluble in alcohol, light petroleum, and ether,and melts at 41". It unites with 2 mols. HC1 to form an unstablecchnpound.Toluene orthodiuzopiperidide and orthonitrotoluene para-diazoFiperidide are oily liquids. Puraiiitrotoluene orthodiazopiperididemelts at 50-51", and is decomposed by hydrobromic acid, yieldingbromonitrotoluene, C6H3MeRr*N0, [ 1 : 2 : 41. Nitrobenzene rrtetadiaxo-piperidide and benzene diazoconine and toluene paradiazoconine are oilyliquids.By the action of sodium nitrite on a soliition of acetotoluylenedi-amine in hydrobromic acid, the diazobromide,The piperidide melts a t 43".NHAc*C6H,Me*NzBr [Me : N,Br : NHAc = 1 : 2 : 41is obtained as ft yellow precipitate. In the dry state, this diazobromideis remarkably stable. It acts on an alcoholic solation of nitroethaneand sodium ethoxide, yielding a red precipitate of acetoparatoluidineorthodinzonitroethane,NHAc*CsH,Me*Xa*CHMe*NOz [Me : NzCzHaNOz : NHAc = 1 : 2 : 41.The precipitate dissolves in alkalis, and is reprecipitated by acids.It is deposited from an ethereal alcoholic solution in red needlesmelting a t 143".Acetoparntolu,idine orthodiazodiethylamide, NHAc.C6H3Me*N,*NEtZ,is deposited in colourless prisms when acetoparatoluidine orthodiazo-bromide is added to a cold solution of diethylamine. It meltsat 108"138 ABS'l'RACTS OF CHEMICAL PAPERS.Acetoparatoluidine orthodi(izo~iperidide melts at 154", and dissolvesin alcohol and in ether. When hydrogen chloride is passed intothe alcoholic solution, the diazochloride, NHAc*CsH,Me*N2C1, is pre-cipitated in a state of purity.In a dry state, the diazochloride is stable.It explodes when heated, and is decomposed by boiling with water orweak alcohol, yielding acetamidocresol.The diazopiperidide is de-composed by warm hydrochloric or hydrobromic acid, yielding ortho-chloro- or orthobromo-acetoparatoluidine and monochloro- or mono-bromotoluidine. w. c. w.Hydrazines. By E. FISCRER (Annalen, 236,198-199).--PhenyZ-hydrazine distils without decomposition under 35 mm. pressure. Itboils at 241-242" under a pressure of 750 mm. (column of mercurysurrounded by vapour). At 22*7" the sp. gr. of the base is 1*097",compared with water at 4".In the preparation of methylphenylhgdmzine, the author finds thatthe reduction of the nitrosamine (Abstr., 1878, 312) may be carriedout in aqueous instead of in alcoholic solution.The base boils a t 131"under 35 mm. pressure, and a t 227" under 745 mm. W. C. W.Phenylhydrazine- compounds. By C. B ij LOW (Annul en, 23 6,194-197) .-Malic, tart ark, and muck acids unite with phenylhydr-azine at 130", forming diphenylhydrazides. The malic compound,OHC2H,(CO*N2H2Ph)2, melts a t 218", the tartaric compound,C2H2(OH)2( CO*N2H2Ph)2, melts a t 226", and the mncic compoundat 238-240'. Pkenylucetic phenylhydrazide, CH2Ph*CO*N2H2Ph,melts at 168-169", and dissolves freely in alcohol and acetic acid.Ethyl oealate pheny1hydi.azide crystellises in plates and melts a t 119".Benzil phenylhydrazine, COPh*CPh :N,HPh, is formed by warmingequal molecular weights of benzil and phenylhydrazine. I t melts a t158-129". w. c. w.Dicyanphenylhydrazine-compounds. By J.A. BLADIN (Bw.,19, 2598-2604). - The anhydro - compound, NPh<N=CMe C(CN) : N>'. I previoiisly obtained by the action of acetic anhydride on dicyanphenyl-hydraziue (Abstr., 1885, 979) can be prepared by adding the calcu-lated quantity of pyruvic acid to an alcoholic solution of the cyano-compound and warming gently. The author regards this compoundas a derivative of the hypothetical triazole, NH<C= : N> ; i t willtherefore be pheny lmet hy 1 cyantriaxol e.The salts of the corresponding pheizylmethy ltriazolecarboxy lie acid,C2N,MePh.COOH, are described. The copper salt with 1& mols. H20,is obtained in the form of microscopic needles; the siZver salt withIf mols. H20 does not crystallise well ; and the lead salt with 2& mols.H20 forms small, white needles ; all these salts are sparingly soluble,whilst those of barium and the alkalis are easily soluble in water.Theethyl salt, C2N,MePh.COOEt, is a thick, bright-yellow oil, insoluble inwater, but readily soluble in alcohol, ether and benzene. With hydro-N'CORGANIC: CHEMISTRY. 139cLloric acid, a hydrochZoride, C2N7MePh*COOH,HC1, is obtained insmall, colourless tables, which are decomposed by water. The ttmide,which can be obtained by the action of hydrogen peroxide on dicyan-phenylhydrazine, crystallises in small, colonrless prisms, soluble inwater and alcohol, less soiuble in ether, and melting a t 170". Theanxidoxime is sparingly soluble in water, but more so in alcohol, andcrystallises in colonrless leaflets melting at 208-210".Acids andalkalis, with the exception of ammonia, dissolve it, whilst with aceticanhydride a compound crystallising in needles and melting a t 148" isobtained.PhenylmethyltriazoZe, C2N3HMePh, obtained by heating the acid a t180", is an oil which does not solidify at -15". It forms a platino-chloride, (C,N,HMePh),,H,PtCl, + H20, which crystallises from alcoholin lemon-yellow tables melting a t 122-124"; it is decomposed by water.To the compound CN,Ph.CN obtained by the action of nitrousacid on dicyanphenylhydr~zine (Abstr., 1886, l46), the author givesthe name phersylcya~tetraxolp, regarding it as a derivative of theCH-NH hypothetical tetrazole, NqNrN>. - w. P. w.Phenazine-derivatives.By A. BERNTHSENaTld H. SCHWEITZER (Ber.,19, 2604-2607).-011 diazotising Witt's toluylene-red, Cl5HlbN,HC1(Trans., 1879, 356), a compound, dimethami~omethylppher~axine,NMe2*CsH,( I \C6H,Me, is obtained, which forms beautiful dark-redneedles or flat prisms having a greenish lustre. It dissolves indilute acids with A TTiolet, and in concentrated sulphnric acid with areddish-brown coloration. Alcohol dissolves it to a red, and etherto a yellowish-red solution exhibiting golden-yellow fluorescence. Itshows considerable analogy to eurhodine, and, like that base, sublimeswithout decomposition.When, instead of nitrosodimethylaniline, 1 : 4 phenylenediamineacts on metatoluylenediamine in the presence of oxidising agents, 8" simple " toluylene-blue, and subsequently a " simple " toluylene-red are produced.On diazotising, the latter yields methylphen-azine; this class of dyes must therefore be regarded as derivedfrom phenazine. The formation of toluylene-blue is representedby the equation NMe2*C6H4*NH2 + NH2*C6H3Me*NH2 - 4H =.N-.N'N'Ntoluylene - red, NMe2*C H ' I \C6H2Me*NH2. The constitutional3\N/formula of the leuco-toluylene-red, NH<-c6H3(NMe)->NH, shows Rremarkable similarity to that of leucomethylene-blue.C6HZMe( NH2)W. P. W.Constitution of the Safranines. By A. BERNTHSEN (Ber., 19,2690-2693 ; comp. preceding Abstract).-The fact that an indamin140 ABSTRACTS OF CHEMICIAL PAPERS.is formed as an intermediate product in the preparation of pheno-safranines makes it probable that the phenyl-group in the latter iscombined with the same nitrogen-atom which connects the two otherbenzene nuclei.The constitution of leucophenosafranine (formed byoxidising equal mols. of paradiamidodiphenylamine and aniline)would thus be N P h < ~ ~ ~ $ ~ ~ ] > N H . This reaction, and the form-ation of safranines by the oxidation of a paradiamine (1 mol.) with amonamine (2 mols.), explains why the para-position to the amido-nitrogen cannot be taken up, and shows that 2 atoms of nitrogen arepresent in safranine as amido-groups.The following constitutional formula are suggested for pheno-safranine hydrochloride :-The first formula is in accordance with the analogy of the dye withthe thionine-group, and the fact that rosaniline yields a triazo-derira-tive, although its salts contain one imido- and two amido-groups.On the other hand, the presence of two intact amido-groups in thesafranine dye, and the fact that toluylene-red can also be diazotised,are in favour of the second formula (comp.also Abstr., 1885, 10%).N. H. M.Metanitromethylsalicylaldehyde and its Derivatives. By A.SCHNELL (Chew,. &ntr., 1886, 469--470).-A11 attempts to prepare a,hydroxymethoxybenzaldehyde by the amidation and diazotation ofthe above compound (first prepared by Voswinckel, Abstr., 1882,189) were unsuccessful. An amide was formed, but was so unstablethat it could not be isolated.When metanitromethylsalicylaldehyde is heated with sodium acetateand acetic anhydride, nzetanitro-orthomethox ycinnnamic acid,N0,*C6HJ(OMe)*CH:CH*COOH [CH : OMe : NO, = 1 : 2 : 51,is formed.It melts at 238", and when reduced with ammoniaandferrous sulphate yields metamido-orthomethozycirtlzanaic acid, whichforms yellow needles melting a t 189". Sodium nitrite and concen-trated hydrochloric acid convert this acid into orthometlzoxycinnamicacid diazochloride, C6H4( OMe) ( C3H302)*N : NC1, which is very unstable.The corresponding nitrate is much more stable ; it explodes at 151-152". When either of these salts is heated with water, nzetah?ydrory-orthornefl~ox~~cin~amic acid is formed, and yields yellow crystals meltingat 179-180'. When this acid is fused with potash, it is almostcompletely decomposed ; when methylated, it yields met12 yZ wetortho-dimethoxycinnamate (diwefhylgentisate), a thick, red-brown oil, whichyields the acid on saponification. The acid melts at 143": Tiemannand Muller (Abstr., 1882, 53) give the melting point as 76".ThiORGANIC CHEMISTRY. 141acid when oxidised with alkaline permanganate yields dimethyl-gentisaldehyde.These results prove the nitro-group to be present in the meta-position. L. T. T.New Chlorine-derivatives of Acetophenone. By H. GAUTIE R(Compt. rend,, 103, 812-8 14). - Trichloracetophenone, COPh*CClp-60 grams of trichloracetic chloride is mixed with 100 grams ofbenzene, heated to the boiling point of the latter, and aluminiumchloride added in emall quantities. After treatment with water, thedried product is fractionated under reduced pressure, and the portionboiling a t 135-155" under a pressure of 25 mm.is re-fractionated.About 20 to 25 grams of trichloracetophenone is thus obtained as acolourless liquid with a pungent odour and extremely burning taste.It remains liquid at, -21", and boils without decomposition at 145"under a pressure of 25 mm., and with slight decomposition a t 249'under atmospheric pressure; sp. gr. at 16" = 1.427. It is veryslowly oxidised by alkaline potassium permanganate, yieldingbenzoic acid ; when subjected to prolonged boiling with water, orwhen treated with very dilute alcoholic potash, the product is like-wise benzoic acid.Dichlorcrcetophercone, COPh*CHC12, is obtained in the same mannerfrom 50 grams of dichloracetic chloride and 100 grams of benzene;the yield being about 20 grams.It is a colourless liquid, with anodour and taste resembling those of the tri-derivative. It boilsunchanged a t 143" under a pressure of 25 mm., and with slightdecomposition at 247-248' under atmospheric pressure ; sp. gr. a t1.5" = 1.338. It is as difficult to oxidise as the tri-derivative, and isnot sensibly affected by boiling water. When subjected to prolongedtreatment with an alcoholic solution of po tassium acetate, the wholeof the chlorine is removed with formation of potassium chloride anda product which has not yet been examined.These derivatives afford further illustration of the stability ofchlorine in combination with the carbongl-group. It is attacked withdifficulty by reagents which readily remove the chlorine from theside-chains of benzene hydrocarbons, whilst energetic reagents act onthe ketonic group, and give rise to simpler substitution derivatives ofbenzene.C. H. B.Action of Sulphuric Acid on Aromatic Ketones, By K.KREKELER (Ber., 19,2623-2628 ; comp. Abstr., 1886, 538) .-Benzyl-?neb72 yZketoneszclpho?iic acid, SO3€€.C6H4*CH2*COMe, is prepared byheating benzyl methyl ketone with sulphuric acid on a water-bath.Acefophenonesulphonic acid, S03H*CsH4*COMe, is obtained by graduallyadding pyrosulphuric acid (4 grams) to acetophenone (1 gram)kept well cooled ; the intensely red liquid is then heated for halfa n hour on a water-bath. The lead salt dissolves very readily inwater. The sulphonic acid reacts with phenylhydrazine, and yieldsthe cornpouiid K H P h : CMe*C6H4*S03H(N,HPh) ; this crystallises inlustrous plates, readily soluble in alcohol.Isobzctyrothienonesul~honic acid, CHMez*CO*C4SH,.SO3H, is obtainedVOL.LII. 142 ABSTRACTS OF CHEMICAL PAPERS.by acting on the thisnone with pyrosulphuric acid in the cold. Thelead and barium salts are very readily soluble in watw, and canbe crystallised from dilute alcohol. The phenyZh;lldraxine-derivaSive,NzHPh : CPr@*C4SHz*S0,H-(N,HPh), crystallises in lustrous plates,readily soluble in alcohol, very sparingly in cold water.N. H. M.Plochl's Phenylglycidic Acid. By E. ERLENMEYER, Jun. (Bw.,19, 2576--2577).-The phenylglycidic acid prepared by Plijchl'smethod (Abstr., 1884, 604) yields well characterised hydroxylamine-and phenylhydrazine-deri vatives, and also gives the Laubenheimer-Victor Meyer thiophen reaction.From these facts, the author drawssuggested by the conclusion that the formulaPlochl cannot be sustained, and advances the view that the compound w. P. w.By A. LIPP(Ber., 19, 2643-2650) .--Paranitro~hen,yloxynci.ylic acid, first ob-tained by Erlenmeyer, is readily prepared by heating paranitrophenyl-a-chlorolactiu acid with alkalis ; it crystallises in glistening leaflets,which melt at 186-188" with complete decomposition ; when heatedwith sulphuric acid it yielda paranitrophenyIglyceric acid, whichcrystallises from water in small interlaced leaflets, melting at 167-168". In order to determine whether the constitution of this acid isCHPhGH-COOH\O/is probably phenylpyruvic acid.Para- and Ortho-nitrophenyloxyacrylic Acid.N02*CsH4* C H *C H*CO OH , or of a p-hydroxy-acid, its'O/that of a glycide,reaction with hydrochloric acid was studied ; nitrophenyl-P-chloro-lactic acid was formed, thus confirming the former view.This/3-lactic acid resembles the corresponding a-acid in appearance andbehaviour towards solvents ; it forms small, glistening crystals whichmelt a t 167-168'. When boiled with water, it is completely decom-posed into hydrochloric acid, carbonic anhydride, and a red resin ; itsbarium salt when heated yields paranitropbenethylaldehyde and car-bonic anhydride. Since the paranitrophenyl-a- and -P-chlorolacticacids yield the same nitrophenylacrylic acid, which in ita turn isreconverted into the p-lactic acid, the constitution of the oxyacrylicacid is analogous to that of glycidic acid, according to the formulawritten above.The orthonitrophenylacrylic acid, obtained by Baeyer, behaves likethe above in combining directly with hydrochloric and hydrobromicacids ; its constitution therefore is analogous.By R.STEPHAN (Chew. Centr., 1886, 470-471).-Tiemann, Friedlander, and Priest (Abstr., 1882, 50 and 56) haveshown that the cyanhydrins of aromatic aldehydes form an easysource for the preparation of substituted amido-acids. The authorfinds that the same holds good in the case of aldehydes of the fattyseries.Acetaldehyde cyanhydrin, when heated on the water-bath withaniline, yields a-unilidopropionitrile, NHPh*CHMe*CN, melting a t 92".V.H. V.Amido-acidsORGANIC CHEMISTRY. 143The hydrochloride forms crystals melting at 8 6 O , and giving up hydro-gen chloride very easily. The nitrile dissolves in boiling water withpartial decomposition into its components. Neither hydrochloricacid nor potash causes hydrolysis, but when heated with thesereagents the nitrile undergoes decomposition. When the nitrile isdowly added to concentrated sulphuric acid, ~-annilidop~opionaml:de isformed ; this melts at 140-141", and is decomposed when heated withstrong potash. Wit-h hydrochloric acid, it yields a-anilidopropionicacid, which melts at 163" and sublimes unchanged.Ortho- and para-toluidine form compounds similar to the above.a-Paratoluidopropionitrile melts at 82' ; the amide,CTH,*NH-C HMe-C 0 NH2,melts at 145", and is more unstaoble than the anilido-amide ; the freeacid forms colourless, hygroscopic scales melting at 152".a- Orthotoluidopropioi2.itrile melts at 72-73', the antide at 125", andthe acid at 116" when separated from alcoholic, but at 123" fromaqueous solutions.The hg drochlorides of these nit riles yield unstable, crystallineplatinochlorides.Bromine forms tribromo- subs ti tut ion products. a- Tribrom ad1 ido-propionitrile, C,H,Br,-NH*CHMeGN, forms yellow needles melting a tISO" ; a-orthotoluidodibromopropionitrile melts at 105", and a-para-toluidodibromopropionitrile at 11 7".L. T. T.Derivatives of Methyl Carbanilate. By W. HENTSCHEL (J. p r .Ghem.[2] , 34, 423427).-1n a former communication (Abstr.,1885, 792), the author has described the formation of methyl amido-sulphobenzoate from methyl carbanilate by the action of sulphuricacid. When the substance is decomposed with excess of bromine-water, and the solution allowed to remain for some days, a substanceof the formula C,H,O2NBr2 separates, which crystallises in needles,and melts at 96 5".This substance, in which two atoms of bromine have taken theplace of the sulphonic group, when warmed with sulphuric acid yieldsdibromsniline sulphate, which on decomposition with sodiumhydroxide gives ordinary dibromaniline (1 : 2 : 4).When treated with nitric acid of sp. gr. 1.45, the brominatedsubstance gives a nitro-compound, crystallising in silky needles,melting at 152O, and having the constitutionOMe~CO*NH*C6H2Br2*NO2 [NH : Br, : NO2 = 1 : 2 : 4 : 61.When heated with aqueous ammonia in a sealed tube, the nitro-compound yields dibromonitraniline (m.p. 127-5").The acid liquid containing methyl amidosulphobenzoate yields anitrocarbanilide when treabed with strong nitric acid. This formscolourless plates or prisms, melts at 189", and when heated withstrong hydrochloric acid in sealed tubes, yields a dinitraniline whichagrees in all respects with uusyinmetrical metadinitraniline.G. H. M144 ABSTRACTS OF CHEMICAL PAPERS.Ethyl Phthalylacetoacetate. By C. B~~LOW (Awualerc, 236, 184-194).-Ethyl phthalylacetoacetate, prepared by the method de-scribed by Fischer and Koch (Abstr., 1883, SOS), is decomposedby the action of sulphuric acid at 65" for half an hour, yieldingalcohol and acetic and phthalylacetic acids.It is also decomposedby prolonged boiling witb water o r with alkalis, but with a coldalcoholic solution of potassium hydroxide it yields a deliquescentcrystalline compound, C11H12K20s + C2H60, which is very solublein water. At the ordinary temperature, ammonia converts ethylphthalylacetoacetate into phthalyldiamide, but at a temperature of100" phthalimide is formed.Et h y 1 pheny 1 hy drazinep ht ha1 y laceton cetate, Cz,H,,N,04, forms thickplates, soluble in alcohol, in stroiig acetic and sulphuric acids, andin alkalis. It melts at 236-238", and on reduction with zinc-dust and acetic acid yields the ethylic salt of benzylacetoacetic-orthocarboxylic acid.This compound melts at 92", and dissolvesfreely in hot water, alcohol, ether, chloroform, and acetic acid.It is decomposed by boiling with baryta-water, yieldingb e m y Zacetoneort hocarbox y lic acid, C OOH*C6'E14*C H2*CH2*COMe. Thisacid dissolves freely in the usual solvents, and melts at 114'. Thephenylh ydraxine compound of eth y 1 benzy lacetoaceticorthocarboxylate,COOH*C6H4*CH,*CH(C00Et)~c~~e : NzHPh, forms pale - yellow,needle-shaped crystals. It melts with decomposition at 235", anddissolves freely in alcohol, ether, chloroform and carbon bisulphide.At the ordinary temperature, and more rapidly at loo", the com-pound splits UP into alcohol, water, and a new substance, C18H16N2O3,which melts at 228-229".w. c. w.Benzoic Sulphinide. By I. REMSEN and A. G. PALMEB (Amer.Chem. J., 8, 223--227).-Benzoic sulpliinide may be sublimed; it isdecomposed by simple evaporation with strong hydrochloric acidor by boiling with strong baryta-water, yielding orthosulphobenzoicacid. The following salts are described :-C7H,S03XK + HzO, verysoluble cryst,als ; C7H4S03NAg, sparingly soluble in boiling water, andseparating in long needles ; (C,H4S03N),Ba + l+HzO, easily solublein water and difficult to crjstallise; the methyl salt has also beenprepared, but not completely examined. H. B.Parethoxybenzoic Sulphinide. By I. REMSEN and A. G.PALMER (Amer. Chew. J., 8,227-229).--Etboxytoluenesulphonamide(this vol., p. 136) was oxidised in warm dilute aqueous solution withpotassium permanganate ; from the filtered and concentrated solution,hydrochloric acid precipitated parethoxybenzoic sulphinide,Eto*c6Ha<~~>NH.The substance forms needle-shaped crystals, melting at 257-258" ;it has not a sweet taste.The potassium and silver ealts,C,H,S04NK and C9H8S04NAg, are described. H. BORGANIC CHEMISTRY. 11-3Parabromobenzoic Sulphinide. By I. REMSEN and W. S.BATLEY (Amer. Chern. J., 8, 229-235) .-Parabromotoluenesulphon-amide (Hubner and Post, this Journal, 1874, 57) was oxidised withpotassium permanganate in considerable excess, when besides thesulphinide, there is also formed a considerable quantity of para-bromosulphobenzoic acid ; this substance is not formed if potash isalso added during the oxidation.Parabromobenzoic sulphinide issparingly soluble in cold water, volatilises at about 200°, melts at217", and is characterised by an extremely sweet taste, followed byan after-taste of extreme bitterness. The following salts are de-scribed :-(C7H303SNBr),Ba + 7+Hz0 ; (C7H303SNBr)2Ca + 7iH20 ;C7H,0,SNBrAg + 2+H20. When treated witlh phosphorus penta-chloride, and then with alcohol, the ethyl salt, C7H303SNBrEt, isobtained as a substance which after recrystallisation f rom hot alcoholmelts at 199-199.5". Attempts to prepare the ethyl salt from thesilver salt and ethyl iodide were unsuccessful, a mixture of at leasttwo substances being obtained.Benzoyltoluenesulphonamide and some of its Derivatives.By I. REMSEN and C.S. PALMER (Amer. Chern. J., 8, 235-243).-Somewhat similar t o the sulphiuides is the class of substances repre-sented by benzoylbeozenesulphonnmide, Ph*C@*NH-SQ,*Ph, andbenzoyltoluenesulphonamide, Ph*CO-NH*S02*CsH,Me, obtained by theaction of benzoic chloride on the corresponding amides. But theconstitution of these substances has not been definitely proved,and Wolkow has shown that benzamide when treated withbenzenesulphochloride yields not benzoylbenzenesulphonamide, buttoluenesulplionic acid and phenyl cyanide, and it is, therefore,possible that the above two substances are represented, not byR*S02*NH*COR, but by R-SO2*N : C(0H)R. On the first of thesesuppositions, two ethyl salts should be obtained, one, R*SO,*N Et*COR,from the silver or lead, salts and ethyl iodide, and the other,R*SO,*N : CR*OEt, by acting on the sulphonamide with phosphoruspentachloride and alcohol ; on the second supposition, only one ethylBalt can be prepared by either method, namely, R*S02*N CR*OEt.It has already been shown, and is confirmed by the authors, thatethereal salts of benzoyltoluene-sulphonamide cannot be obtained by theaction of phosphorus pentachloride and alcohol.Neither can they beobtained by the action of ethyl iodide on the lead or silver salts ofthe sulphonamide ; similar n gative results have been recorded by otherwriters.But although the ethereal salts of the sulphonamides cannot beobtained from the sulpbonamides, they may nevertheless be preparedindirectly. Benzoylnzethyltolue.nesuZ~honamide, C7H50*NMe*C7137S(32,crystallises with difficulty; i t melts at 58", and is prepared by theaction of benzoic chloride on methylparatolzceneszrIrphonamic~e,NHMe*S0,*C7H7. On adding water to its alcoholic solution, thelatter crystallises in plates melting at 75", is very stable, and isobtained by treating paratol uenesnlphochlorid e with methy lamine.BenzoylethyZtolzLenesulphonamide was prepared, but not analysed ;it is obtained from benzoic chloride and ethy7,parutoluenesulphonamide,H.B146 ABSTRACTS OF CHEMICAL PAPERS.NHEt.SO2*C,H7, melting at 58", and prepsred like the above methyl-compound.Benzoylphenyltolzcenssulphonamide crystallises readily from alcohol ;the crystals melt at 149" ; when boiled with alcoholic potash, it yieldsbenzoic acid and toluene-sulphanilide.It is prepared from phenyl-paratol.uenes.ulphonamic~e, NHPh*S02*C7H7, melting at 103", andalready prepared by Miiller.Separation of the Two Isomeric ToluidinesulphonicAcids. By E. A. SCHNEIDER (Amer. Chem. J., 8, 274).-The potassiumand sodium salts of paratoluidinemetasulphonic acid are very solublein water, but insoluble in cold aqueous potash, whilst the potassiumand sodium salts of paratoluidineorthosulphonic acid are veryeasily soluble in the same liquid at ordinary temperature.Action of Concentrated Sulphuric Acid on Hydraxine-toluenesulphonic Acids. By E. A. SCHNEIDER (Amer. Chem. J., 8,271-273).-1t was hoped that condensation might be effectedbetween the hydrazine- and sulphonic-groups.Parahydrazinetoluene-orthosulphonic acid apparently underwent no change. Parahydrazine-toluenemetasulphonic acid react's violently with sulphuric acid at 80" ;the product poured into water gives a bright red precipitate, notfurther examined, and the filtrate, with excess of soda, gives a yellowprecipitate which resembles in all its properties the basic substanceobtained by Gallinek and Richter (Abstr., 1886, 236) by heatingparatolylhydrazine with snlphuric acid, and is probably identicalwith it. H. B.H. B.H. B.Oxidation by Means of Potassium Permanganate. By I.REMSEN and W. H. ENERSON (Awer. (>hem. J., 8, 262--268).-1thas been stated " that acid oxidising agents tend to transform para-groups (hydrocarbon-chains) and leave ortho-groups unchanged, andthat alkaline oxidising agents tend to transform ortho-groaps andleave para-groups unchanged," and R.Meyer and Baur (Abstr., 1881,46) have adduced in favour of this the case of cymenesulphonic acid[Me : S03H : P r = 1 : 2 : 41, which with permanganate yields hydr-oxypropylsulphobenzoic acid [COOH : S03H : C3H70 = 1 : 2 : 41, butwith nitric acid yields sulphoparatoluic acid [CH, : S0,H: COOH= 1 : 2 : 41. On the other hand, Jacobsen has shown that metaxylene-sulphonamide [SO,H : Me : Me = 1 : 2 : 41 yields the same product ofoxidation [ SO,H : Me : COOH = 1 : 2 : 41 with either chromic acid orpotassium permanganate.Jacobsen's work is fully confirmed, and i t is also shown thatparaxylenesulphonic acid and paraxylenesulphonamide yield the sameoxidation products with permanganate, namely, sulphoterephthalicacid and a sulpho- or sulphamido-paratoluic acid.By fusing thelast-named compounds with potash, they are both converted into oneand the same hydroxytoluic acid, a-orthohomometahydroxybenzoicacid [Me : OH : COOH = 1 : 2 : 41, and hence the methyl-group firstoxidised is not that which is in the ortho-position relatively to thes u 1 phonic groupORGANIC CHE3lISTKT. 147The work of Meyer and Baur was then repeated and fully con-firmed, and finally the behaviour of cymene itself with alkalinepermanganate was examined. It was found that the products of theoxidation were almost equal quantities of terephthalic acid and ofhydroxypropylbenzoic acid, COOHgC6H~*C3H70, which was recognizedby converting it into propenylbenzoic acid and isopropenyl benzoicacid.Cymene treated with chromic acid yields as the first producttoluic acid, and hence the C~USB of the different behaviour of cymene-sulphonic acid towards alkaline permangarlate solution, and towardsacid oxidising agents (nitric acid) is not to be soughb for in the influenceof the sulphonic group on the hydrocarbon side-chains @eyer), but inthe difference between the side-chains themselves, the isopropyl-group yielding most easily to acid oxidising agents, the methyl-groupyielding most easily to alkaline oxidising agents. (Compare Abstr.,1886, 541.) H. B.Action of Bromine and Water on a-Metaisocymenesul-phonic Acid : Constitution of a- and p-Metaisoeymenesul-phonic Acids.By W. KELBE and N. v. CZARNOMSKI (Annalen, 235,272-299).-1n addition to the results which have previously ap-peared in this Journal (Abstr., 188%, 619 ; 188%, 1355 ; and 1886, 355),the authors describe the following compounds :-Lead p- bromotnetisocyme.nesulphonate, P b ( CIOH,2BrS03)2 + H,O,crystallises in ueedles, and is soluble in alcohol and in hot water.The barium salt forms colourless plates ; the copper salt glisteninggreen plates containing 4 mols. H20; and the potassium salt,C,,H,,Br*S(n3K + H20, silky needles. The sulphonamide,CloHrzBr*S02*NH2,melts a t 162" and dissolves in strong alcohol, from which solvent it isdeposited in transparent needles.After dryingover sulphuric acid, it melts a t 126".Its salts are much moresoluble than those of the /3-acid. The barium and copper saltscrystallise with 7 mols. H20. The potassium salt crystallises inneedles containing 1 mol. H20. It dissolves readily in water oralcohol. The sodium salt contains 2 mols. H20. The sulphonamideforms long, wliite, needle-shaped crystals. It melts at 170.5", and dis-bolves in hot water and alcohol.Pure a-bromisocymenc, CIOH13Br, boils a t 225' instead of 235"as previously stated (Abstr., 1882, 618).Dibromocyrnene is prepared by the action of bromine on an aqueoussolution of a-bromocymenesulphonic acid. It is an oily liquid boilinga t 272-273". Pare broniocymene is obtained as a strongly refractiveliquid when potassium p-bromometaisocymenesulphonate is decom-posed by superheated steam.I t boils a t 224", one degree lower thanthe a-compound, and is slowly oxidised by nitric acid, yielding bromo-nletatoluic acid (m. p. 152"), C6H3~eBr*COOH [1 : 4 : 3-j:Geizeral Conclusions.-when metaisocymene dissolves 1n sulphuricacid, the SOaH group displaces the H atoms at 4 or 6. Brominecc-Bronzisocynzei2.esulpponnic acid is very hygroscopic148 ABSTRACTS OF CHEMICAL PAPERS.displaces the H atom at 4 in a-cymenesulphonic acid, and at 6 in the/%-acid.When bromocymenes are dissolved in sulphuric acid, the sulphonicgroup takes the position 4 in the a-compound, and 6 in the p-corn-pound. The constitution of these compounds is shown in thefollowing table t-a. 8.Bromotoluic acids, Me : COOH : Br ....Bromocymene, Me : Pr : Br ............Cgmenesulphonic acid, Me : Pr : S0,H .Bromocymenesulphonic acid,Me:Pr:SOaH: Br..................Dibromocymene, Me : Pr : Br : Br ......Bromoisophthalic acid, COOH: COOH: BrSynthesis of Indole-derivatives. By E. FISCHER (Annulen,236, 116--126).-Many of the results contained in this paper havealready been published (Abstr., 1884, 52, 1180 ; and 1886,835).--Thefsxalodour of indole is most marked in skatole, and in the mono- anddi-methyl compounds with the exception of ihose substances in whichthe methyl-group is united to the N-atom. The odour and volatilityof the compounds is destroyed by the introduction of the phenyl-group. All indole-derivatives form crystalline picrates, and all theindoles with the exception of the carboxylic acids are reduced by zincand hydrochloric acid to hydro-bases.The pine-wood reaction is notexhibited by the carboxylic acids, nor by those derivatives in whichboth the 2' and 3's hydrogen-atoms are replaced by methyl, ethyl, &c.Nitrous acid converts indole and 1' methylindole into nitroso-compounds. It forms complicated products with 2' methyl or phenylindole, and converts 3' or 2', 3' substituted indoles into nitrosamines.1 : 3 : 6 1 : 3 : 41 : 3 : 6 1 : 3 : 41 : 3 : 6 1 : 3 : 41 : 3 : 4 : 6 1 : 3 : 6 : 41 : 3 : 6 1 : 3 : 4 w. c. w.1 : 3 : 4 : 6The following is a list of indoles derived from the hydrazines.Melting Boilingpoint. point.1'. ......... liquid 240"Monomethyl 2'. ......... 60" 2 723'.. ........95 265-26c(2' : 3' ...... 106 2851 ' : 2 ' ...... 56 ??13 : 1' 9, ?(1 :1' 9 , ?{Dimethyl.. 4 1 : 3' ...... liquid ...... ......* Note.-In the notation of the indole series, 1,2, 3, 4 refer to the positions in thebenzene-ring, and l', 2', 3' to the corresponding positions in the basic ring con-taining the nitrogen, where N = l', as shown in the annexed symbol :-1'1 N4 3' -EDITOBSORGANIC CHEMIST RT. 149Melting Boilingpoint. point.Trimethyl., 1' : 2' 3' .... liquid ? picrate melts at 150".Ethyl ..... l'.. ........ 9 ,2' : 3 ' . ..... ,, 291-293" ...... Methyl ethyl { : 1t9 ,Monophenyl { g:Diphenyl. .. 2' : 3 ' . ..... 123Benzyl .... l ' . . ........ 44.5"Naphthindole 2'. ......... liquid 222" under 18 mm. pressure.Methyl naphthindole, 2' .. 2 ,' ' ......... 18%"w. c. w.Indoles from Phenylhydrazine. By E. FISCHER (Annulen, 236:126--151).-Most of the compounds mentioned in this paper hamalready been described by the author (Abstr., 1886, 805). 2', 3' Di-methylindole, CeNH5Me2, prepared from the phenylhydrazine com-pound of methyl ethyl ketone, melts at 106" and boils at 285". Thenitrosamine, C8NH4Dlle2*N0 [NO = 1'3, melts at 61-62", and decom-poses at a higher temperature. 2' 3' kfelhylethylindole, C8NH5MeEt,prepared frpn the phenylhydrazine of methyl prop91 ketone, is an oilyliquid boiling at 291-293". The picrate crjstallises in dark redneedles. Phenylhydrazillelaevulinic acid,PhNzH : CMe*CH2*CH2*COOH,melts at 108", and at a higher teniperature splits up into water andthe anyhdride, C11H,,N20.This substance crystallises in colourlessplates. It melts at 106-107O and boils between 340" and 350" withpartial decomposition. Ethyl phenylhydrazinelmdinate melts a t110". Methylindoleacetic acid, prepared from this ethyl salt, meltsbetween 195" and 200", and splits up into carbonic anhydride andIndoles from Methylphenylhydrazine. By J. DEGEN ( A n n u l e n ,236, 151-164) .-The preparation of l', 2' dimethylindole,l', 2' methylphenylindole, and l', 2', 3' dimethylindolecarboxylicacid from the compounds of methylphenylhydrazine with acetone,acetophenone, and ethyl acetoace tate, respectively, has already beendescribed (Abst- ., 1886, 805). Dimethylindolecarboxylic acid crys-tslllises in six-sided plates.It melts at 185" with partial decompositioninto carbonic anhydride and l', 2' dimethylindole. l', 2', 3' DI-methylindoleacetic acid (Zoc. cit.) melts at 188" and decomposes a t200", yielding l', 2', 3' trimethylindole, an oily liquid which boilsabout 280° without decomposition. The picrate melts at 150".Trimethylindole is obtained i n a less pure state by the action of zincchloride on the compound of methy lphenylhydrazine with methylethyl ketone. l', 3' Dimethylindole is obtained in an impure state byacting on propylidenemethylphenylhydrazine with zinc chloride.2', 3' dimethylindole. w. c. w.w. c. w.Indoles from Metahydrazinebenzoic Acid. By A. RODER(Annalen, 236, 164-173). - Metahydraziiiebenzoic acid is con150 ABSTRACTS OF CHEMICAL PAPERS.vqniently prepared by adding the theoretical quantity of sodiumnitrite to 100 grams of metamidobenzoic acid suspended in a mixtureof 400 grams of water and 190 grams of strong hydrochloric acid.The liqiiid is poured into an ice-cold solution of sodium sulphite(4 mols.Na2S03 to 1 mol. amido-acid). As soon as the mixture turnsyellow, strong hydrochloric acid is added to precipitate the hydro-chloride of metahydrazinebenzoic acid. The free acid is obtained byadding sodium acetate to a solution of the hydrochloride. The acetonecompound is formed when acetone and sodium acetate or potassiumhydroxide are added to a solution of the hydrochloride. This sub-stance forms colourless needles melting a t 150". It is freely solublein alcohol and acetic acid, and is easily decomposed by warm mineralacids into acetone and hydrazinebenzoic acid.The ethylic saltCIOH11N2C)2Et, melts R t 90-91" and dissolves freely in alcohol, etherand acetic acid. Hydrazinebenxopjruvic acid, CloHloN204 + H20,melts a t 306-208" with decomposition, and is freely soluble in am-monia and fixed alkalis. The barium and sodium salts are crystalline.The ethyl salt, C,oH8N,04Et,, melts a t 101-102". It dissolves freelyin alcohol, ether, and in warm benzene. By the action of zinc chlorideon this componnd, the ethyl salt of indoledicarboxylic acid is formed,together with indole and a small quantity of another substance.Monethy 1 indoledicarboxylate crystallises in needles and melts a t 250"with decomposition.The free acidmelts a t 250" with decomposition, It dissolves freely in hot alcoholand in acetic acid. It has the constitution [(COOH), = 4 : 2' or 3 : 2'3.Hydrazinebenzoic acid unites with benzaldehyde, forming benxylideii e-hydrazinebetuoic acid. This acid cry stallises in plates, melts a t170-172", and is freely soluble in alcohol and acetic acid. Phenyl-glucosaxonecarboxylic acid melts at 206-208" with decomposition.Metahydrazinebenzoic acid unites with phenyl isothiocyanate, formingdiphenylthiosemicarbaxidecarboxylic acid, Cl4Hl,N30,. This substancecrystallises in colourless needles and melts at 204-205" with decom-It is freely soluble in alcohol.position. w. c. w.Aluminium Chloride Reaction. By R. ANSCH~~TZ (Annalen,235, 150-229 aud 299-341).The experimental results of theauthor's research on the aluminium chloride reactions have alreadybeen published (Abstr., 1883, 807, 809, 1132 ; 1884, 326, 753, 754,1034 ; 1885, 269, 768, 769). The following conclusions me deducedfrom these results.Dibenzyl and unsymmetrical dipheiiylethane (obtained by thoaction of aluminium chloride and benzene on the isomeric dibrom-ethylenes) correspond with the dibromethylenes in constitution.The synthesis of anthracene from a1 uminium chloride, benzene, andacetylene tetrabromide, indicates that the mesocarbon-atoms in anthra-cene are probably linked together. The formation of dimethyl-anthracene from toluene, acetylene tetrabromide, and aluminiumchloride, shows that the methyl-groups in dimethylanthracene, meltingat 225", are divided between the two benzene nuclei.Aluminiumchloride not only removes but also transfers the side-chains of methylORGANIC CHEMISTRY. 151and ethyl-benzenes from one molecule to another. Only the symme-trical tetraphenylethane is known.In many aluminium chloride reactions, theoretical yields areobtained when carbon bisulphide is used as a diluent.Symmetrical mesodimethylanthracene hydride is formed, togetherwith ethylbenzene and unsymmetrical diphenylethane, by the actionof benzene and aluminium chloride on ethylidene bromide or chloride,or on vinyl bromide. Ethyltoluene, unsymmetrical ditolylethane, andtetramethylanthracene hydride are formed by the action of aluminiumchloride on ethylidene chloride and toluene.A new dimethyl-anthracene is formed by heating the tetramethylanthracene hydridewith zinc-dust. w. c. w.By E.LIPPMANN (Monatsh. Chem., 7, 521-528) .-Benzoic peroxide canreact as a dehydrogenising agent, removing two hydrogen-atoms fromtwo molecules of an aromatic hydrocarbon. Thus from toluene ahydrocarbon, ClaHl,, is formed ; the hydrocarbon boils a t 258-262", isstrongly refractive, and of aromatic odour, sp. gr. 1.0032; it isisomeric with stilbene and diphenylethylene, and as, on oxidation,it yields benzoic acid only, its constitution is probably expressed by theDehydrogenation by Means of Benzoic Peroxide.,-. -7formula <z:> CH2, that of a benzylidenetolylene.6 4Similarly from xylene, a bydrocarbon, Cl6HI6, is obtained as arefractive liquid, boiling at 260-270", sp.gr. 998 ; as being isomericwith ditolylethylene and dimethjlstillene, it is named dixylylene.Formation of Substituted Stilbenes. By K. ELBS (J. pr. Chem.[2], 34, 340--342).-0n endeavouring to extend Strakosch's methodof synthesis of stilbene-derivatives by the action of potash on benzyl-derivatives, the reaction wit.h orthonitrobeiizyl chloride was successful,but in the case of parabromo benzyl bromide the corresponding alcoholwas obtained together with ethyl parabromobenzoate ; the lattersubstance, the derivation of which in the above reaction is notsatisfactorily explained, is a colourless viscid liquid, boiling at 236"under a pressure of 713 mm., of odour resembling pears, soluble in mostmenstrua with the exception of water, saponified only with difficulty.Substituted Stilbenes.By K. ELBS and F. BAUER (J. p r . Chem.[2], 34, 343--347).-Paradinitrostilbene is not altered by potassiumpermanganate ; on oxidation with chromic acid i n acetic acid solution,it is readily converted into paranitrobenzoic acid. With bromine, itforms paradinitrosLiZbene bromide, NOa.CGHb*CHRr*CHBr*CGH4.N02,a white, crystalline powder melting above 300", but dedomposing evenat 110" with evolution of hydrobromic acid and the formation of para-dinitrotolane ; it is sparingly soluble in most menstrua. When anacetic acid solution of paradinitrostilbene bromide is boiled withpotassium acetate, ethyl paradinitrohydrobeneoin acetate,is formed ; this crystallises in small, yellow crystals, melting at 340",moderately soluble in alcohol, ether, and acetic acid.V.H. V.V. H. V.NOz*O6Hk*CH (OAc)*CH ( OAC) *C6H4*NO2152 ABSTRACTS OF CHEMICAL PAPERS.Paradinitrotolane, NO-,*C6H4*C i C*C6H4*NO2, obtained as dewribedabove, and best purified by sublimation, crystallifies in needles meltingat 288" ; it usually separates from solvents in the amorphous form.V. H. V.Euxanthone-group. By C. GRAFBE and A. FEER (Ber., 19,2607-2614).-Spiegler (Abstr., 1854, 1182) ascribed to benzo-phenone oxide the constitution < g:z:E<>, as it reacts neither withhydroxylamine nor with phenylhydrazine. The authors suggest forthis compound the constitution CsB4-G-L6H4 ; this would accountfor the negative result with hydroxylamine, as well as for the fact thati t yields dihydroxybenzophenone when fused with potash (Richter,Abstr., 1884,324).Orthodihydroxybenzophenone (Richter, loc.cit.) boils at 330-334"with partial decomposition into water and benzophenone oxide. Thepotassium salt has the formula CO(C,H,*OK),. The phen ylhydrnaineand hydron: ylainine-cowpounds melt at 152" and 99" respectively. Themethyl salt was found to melt at 104" (not 98") ; it undergoes nochange when heated with alcoholic potash at 150" ; the hydroxylamine-deyivative melts at 188". The ethyl salt crystallises from alcohol incolourless needles me1 ting at 109" ; the pheir ylhydraaine-cmpoundmelts at 114". Whenparacresol salicylate is subjected to the same treatment as the phenjlsalt in the preparation of benzophenone oxide (Siefert, Abstr., 1885,0 0A/\-The acetyl-derivative melts at 96" (not 83").loss), the compound C6H,<-O->C6H3Me CO is formed; this is veryreadily soluble in hot alcohol and melts at 106".&-Naphtholsalicylate yielded a-naphthopheitorte oxide, C1,H1002 ; i t melts at 155",and dissolves very readily in hot toluene. The picrate is yellowish-red.t3-Xaphthophenone o&de crystallises in needles melting at 140".When euxanthonic acid is fused with potash, it is converted intoquinol ; it has therefore the constitutionCsH,(OH)2*CO*C6H,(OH), [CO : OH : OH = 6 : 1 : 41.An ethyl salt was obtained which reacts with hydroxylamine.N. H. M.Preparation of Dinitronaphthylamine : Metanitrophenyl-azodirnethylamidobenxene. By R.MELDOLA (Ber., 19, 2683-2684) .--a-Naphthylamine is boiled for several hours with acetic acid ;the theoretical amount of nitric acid (sp. gr. 1.5) diluted with glacialacetic acid is then gradually added to the warm solution of the aceto-naphthalide and the whole warmed until the reaction is finished.The product is then poared into cold water, filtered, and washed wellwith cold water. The precipitate whilst still moist, is mixed in smallquantities with strong sulphuric acid and warmed ; it is then pouredintq cold water, and the orange-red precipitate washed with water ; itmay be purified by recrystallisation from alcohol. The yield of crudesubstance is almost theoreticalOROANIC CHEMISTRY.153Metanitrophenylazodimethylamidobenzene (Staedel and Bauer,Abstr., 1886, 944) has already been fully described by the author(Trans., 1884,120). N. H. M.Eurhodines and Laurent's Naphthase. By 0. N. WITT (Ber.,19,2791-2796).-The eurhodo2, C14H8 <i>CloH5*OH, is obtained byNfusing sodium diphenylenenap h thaquinoxalinesulphonate (Abstr.,1886, 889) with potash until the yellow colour suddenly changesto a pure cinnabar-red. When the product is diluted withwater andtreated with hidrochloric acid in excess, the hydrochloride separatesas a cinnabar-red, insoluble powder. If acetic acid is used in the placeof hydrochloric acid, the free eurhodol separates in orange-yellowcrystalline flakes. It is insoluble in all solvents and can only bepurified by recrystallising the hydrochloride from boiling phenol.When heated, it sublimes with partial decomposition.Sulphuric aciddissolves it with a pure deep blue colour whicL changes immediatelyon addition of very little water to a splendid carmine-red ; when theblue solution is heated to a certain point i t becomes successively violet,red, and yellow.Na-/3-NaphthapzcinoxaZine, CloH6/ I \CIOH6, is prepared by the actionof P-naphthaquinone on orthonaphthylenediamine in acetic acidsolution ; it is purified by crystallisation from naphthalene. It formsyellow needles melting sharply at 275". It dissolves in sulphuricacid, yielding a pure violet solution which becomes orange-yellowwhen diluted ; when further diluted, the free base is precipitated.I tsublimes readily in long, yellow needles, and when quickly heateddistils as a yellow oil which soon solidifies. It is identical withLaurent's naphthase (Annalm, 9, 384 ; compare also Nietzki andGoll, Abstr., 1885, 545).By A. SCHLIEPER (Anna-Zen, 236, 17P-l84).-The P-naphthylhydrazine described by E.Fischer (Abstr., 1886, 555) unites with acetone, forming the com-pound CloH,*NzH : CILIe,. This substance crystallises in prisms of apale-yellow colour. It melts at 65.5", and is freely soluble in alcohol,ether, benzene, acetone, and in (hot) light petroleum. E'thylidenep-naphthy lhydrazine, CloH7*N,H : CHMe, forms three-cornered plates,soluble in hot alcohol, benzene, and chloroform. It melts at 228-129'.~-NaphthyIhydrazinepyrz~vic acid, C,,H7-N2H CMe-COOH, forms yel-low needles.This acid melts at lW", and decomposes with evolutionof carbonic anhydride. It dissolves in hot alcohol and acetic acid.The ethyl salt melts at 131", and is freely soluble in alcohol, ether,benzene, and acetic acid. On fusion with zinc chloride, /3-naphthindoleis prodnced ; ,8-naphthindolecarbox~lic acid is formed as an inter-mediate product. After purification by conversion into the picrate,,kI-naphthindole, CIoH6< CH>CH, boils at 222" under 18 mm. pres-The dry eurhodol is electric.'N'N. H. M.Indoles from p-Naphthylhydrszine.N154 ABSTRACTS OF CHEMICAL PAPERS.sure, and above 360" under the ordinary atmospheric pressure. Itdissolves in alcohol, ether, benzene, and acetic acid with fluorescence.Strong hydrochloric acid forms a crystalline compound with it.P-Naphthindolecarboxylic acid, c~o~6<,,>c*coo~, crystallises incolourless plates, soluble in alcohol and acetic acid.It melts at 226"with evolution of carbonic anhydride. The sodium and barium saltsare sparingly soluble in cold water. The ammonium and potassiumsalts are much more soluble.NHNH Methylnaphthindole, c,OH6< CH>CMe, f porn acetone-p-naphthyl-hydrazine, boils between 37 4' and 320" under a pressure of 223 mm. Itis freely soluble in alcohol, ether, and benzene. The picrate melts at1 76". On reduction with nascent hydrogen, hydrornethyZ-P-na~hth-i d o l e is obtained as an oily liquid, boiling between 190 and 200" under20 mm. pressure.It is a strong base, and with mineral acids, formssalts which are very soluble in water. w. c. w.Action of Monamines on Citric Acid. By H. HECHT (Bw., 19,2614--:!618).-0CitrotrinzethyZamide, C6H,0,(NHMe)3, is prepared byadding a strong solution of methylamine to a concentrated solution ofinethyl citrate in absolute alcohol, and keeping the product oversulpburic acid for some time. It separates in prisms melting a t 124' ;i t is very readily soluble in cold water, and is not acted on by alkalior hydrochloric acid.Citrodinaphtlzy lamine, CloH,*N : C6H504*NH*C,oH,, is formed when amixture of citric acid (1 mol.) and P-naphthylamine (3 mols.) isheated at 140-150" for several hours. It crystallises in six-sidedplatew melting at 233". It is insoluble in water or hydrochloric acid,sparingly soluble i n alcohol.The trinaphthylamide, C6H,04(NH*C,oH,),, is obtained by heatingthe dinaphthylamide with naphthylamine (eq.mols.) a t 150-160" ; itforms microscopic, prismatic crystals readily soluble i n alcohol, in-soluble in water ; it melts a t 215", and is very stable.Citrodinctphth ylamic acid, OH*C6H504(NH*C,oH,),, is prepared byheating the djnaphthylamide with an excess of concentrated ammoniafor six hours a t 170". It crystallises from alcohol in slender, microscopicneedles melting a t 172" ; i t is readily soluble in alkali, insoluble inwater.Monobasic ncrphth yzamine cif rate, C6H5O8,NCloH,, separates as a rose-coloured Pubstance when a hot, concentrated alcoholic, solution of citricacid (1 rriol.) is mixed with p-naphthylamine (1 mol.) and cooled.Itmelts at 89", dissolves readily i n alcohol, ether, nitrobenzene, andwater.Compounds isomeric with the above were prepared from a-naphthyl-amine in a similar manner. Citrodiiiaphth~lamide is purified by precipi-tating the solution in glacial acetic acid with water; it crystallisesfrom benzene in six-sided plates melting at 194"; i t is insoluble inhydrochloric acid. 3, crystal-lises in microscopic, rhombic prisms vhich melt at 129". Boilingalkali solution and acids do not act on it. CitrodinaplLt7~yZarninio acidThe silver salt was prepared.Citrotrin aph t hy lomide, C6H504( NHORGANIC CHEMlSTRY. 155cryshllises in small groups of needles melting a t 149" ; the alcoholicsolution reacts slightly acid.The silver salt is sparingly soluble inwater. N. H. M.Action of Ammonia on Ethyl Acetonedicarboxylate : Syn-thesis of Pyridine-derivatives. By H. N. STOKES and H. v. PECH-MANN (Bey., 19,2694-27 1'7) .--Ethyl p-hydroxamidoglutamate (Abstr.,1885, 1202) is readily soluble in hot water and in alcohol ; the aqueoussolution decomposes gradually,. giving off ammonia. It gives a deepred coloration with ferric chloride.The compound obtained by the action of alkalis on ethyl P-hydrox-nmidoglutamate and described as glutazine (loc. cit.), is shown to be a,pyridine-derivative, probably having the constitutionIt melts at ahout 300" with evolution of ammonia, is moderatelysoluble in hot water, almost insoluble in hot alcohol, and insoluble inother solvents.The neutral solution acquires a deep-red colour onaddition of ferric chloride ; on warming, the solution turns dark-green without becoming turbid. The liydrochloride (with 1 mol. H,O)q s t a l l i s e s in prisms readily soluble in alcohol ; water decomposes it.The sulphate was prepared. The sodium, amm,oniutn, and barium saltsare very soluble.Pentabromacetylacet,amide (Zoc. cit.) melts at 148" ; a t a highertemperature, it gives off bromine and hydrogen bromide. It is in-soluble in water, readily soluble i n alcohol, ether and glacial aceticacid, moderately in chloroform. When heated with water, it is con-verted into dibromacetsmide, bromoform, and carbonic anhydride.Eoiling alcoholic ammonia converts it into dibrornomalonamide (melt-ing a t 200*5°) arid bromoform.AcetyZgZutazine, NH<Co.CH,>C CO*CH, : NAc, is obtained by heatingglutazine with acetic chloride at 100-120".It crjstallises from waterin small lustrous plates, which darken at 230" and melt a t 285-290'.When warmed with ferric chloride. i t acquires a brilliant violet colour.The arnnwizium (with 1 mol. H20), silver, and barium salts were pre-pared.2, 4, 6 Trihydroxypyridine itl prepared by boiling glutazine for3 4 minutes with an excess of strong hydrochloric acid and thenevaporating the solution in clock glasses as quickly as possible on awater-bath. The dry residue is extracted with cold alcohol and thesolution quickly evaporated ; the thick syrup so formed is mixed with alittle water and a solution of caustic soda (0.3 gram to 1 gram glutazine)in twice its weight of water added, the whole being kept cool.Thecrystalline product is washed with a little water and dried. It formsyellow, microscopic needles which swell up when heated at 220-230"and give off water. It dissolves readily in hot water, but is insolublei n other solvents. When treated with ferric chloride, i t gives a deep-red coloration. Bromine-water converts it into pentabromacetylacet-amidc. It reacts strongly acid and decomposes carbonates. The salt156 ABSTHAUTS OF CHEMICAL PAPERY.of the alkalis and alkaline earths are very readily soluble in water.When distilled with zinc-dust, it yields a small quantity of pyridine.Hydroxylamine h yd rochl oride reacts with trih y dox ypyridine, yieldinga monoxime, C,NH,O, N*OH + H20.The latter is a heavy, sandypowder consistiiig of hexagonal plates ; it melts a t 196196O withevolution of gas. It is rather soluble in hot water, less so in alcohol.When treated with strong soda solution, it becomes blue; withammonia, it gives a yellowish-red colour which chanqes t o intensepurple when warmed. It is alsoformed by acting on glutazine with hvdroxylamine. The phenylhydr-mine-compound (obtained from both trihydroxypyridine and glutazine)forms plates readily soluble in hotl alcohol ; it melts a t 230".When trihydroxypyridine is heated with ammonium acetate at120-140", it is converted quaiititntivelv into glutazine,Trihydrozypyridin e anhiidride, C10H805N2, is formed as the chiefproduct in the decomposition of glutazine by boiling dilute sulphuricacid.It crystallises in flesh-colonred, microscopic prisms ; it is verystable, and melts only at a high temperature. It is insoluble in allneutral solvents except water, which dissolves i t slowly. It dissolvesreadily in an excess of alkali.The oxime forms salts with acids.The hydrogen barium salt,( CloH705N2)zBa + 4H20,forms yellow prisms insoluble in water and alcohol. The normalalkali and alkaline earth salts are readily soluble in water ; they arenot decomposed by carbonic anhydride. .The hydrochloride crystal-lises in needles readily soluble in alcohol ; it is decomposed by water.The sulphate crystallises from water in prisms.The anhydride canbe converted into trihydroxypyridine by evaporating its aqueoussolution.The way in which glutazine is formed shows that the nitrogenof the pyridine-ring has the para-position to the side-chain con-taining nitrogen, and the ortho-position to both the oxygen-atoms.Hence the three oxygen-atoms in trihydroxypyridine must be sym-metrical to one another and to the nitrogen, and trihydroxypyridine istherefore analogous to phloroglucinol. The analogy of the two com-pounds is seen in their yielding anhydrides and in their behaviourtowards ammonia and hydroxylamine (compare Baeyer, Abstr., 1886,350). It is probable that the yyridine-derivative exists in two forms,a,~ shown in the following formulee:-3, 5 Dichloro-2, 6-dihydroxy-4-amidopyridine (Zoc.cit.) forms shortflat needles melting a t 241.5" ; it dissolves sparingly in hot water andalcohol, readily in alkali and dilute hydrochloric acid.2, 4, 6 Trichloro-4-~midopyridine forms long colourless needlesmelting a t 157.5"; it is very readily soluble in alcohol, readily indilute hydrochloric acid, and insoluble in alkali; it sublimes un-changed.2, 3, 5 Trichloro-6-hydroxy-4-amidopyrid ine, melting at 282", is vei-yreadily soluble in hot weter, moderately in hot alcohol, sparingly iORGANIC CIHEIIISTRY. 157ether and benzene. It is a monobasic acid, and decomposes carbo-nates. The sodium saZt is rather soluble in water, sparingly inalc7hol.2, 3, -5, 6 Tetrachloro-4-amidopyridine melts a t 212O, and sublimesunchanged. It is insoluble in water, soluble in alcohol and benzene.It can be boiled with strong sulphuric acid without decomposition.When heated with fuming hydriodic acid a t 200°, black crystals of aniodiize-dprivative melting below 80" are formed.This, by solution indilute sulphuric acid and precipitation with alkali, is converted intowhat is probably dichloramidop~rii7ilte; it melts at 158". When thet etrachloro-compound is boiled wihh sodium ethoxide and alcohol,2, 3, 5 f~ichloro-6-ethoxy-4-amido~yridine is formed ; this crystallisesin needles which melt a t 83". It distils wilh steam, is insoluble inwater, alkali, and dilute acids, very readily soluble in alcohol, ether,henzene, &c. Dilute hydrochloric acid converts it (at rather above100") into trichlorhydroxynmidopyridine (m.p.282O) and ethyl chloride.Dick loro-d ipth oxy- 3-arnidopyridine, C,N,H,Cl, (OE t ) 2, and dichloro- 2-~~ydroxyetho~y-4-amidopyridine, C,?5i2H,Cl,(OH)*OEt, are formed byheating tetrachloramidopyridine with excess of sodium ethoxide andalcohol a t 190". The former crystallises in long needles melting a t98" ; it is very readily soluble in alcohol and ether, insoluble in water,alkalis, and dilute acids, and distils with steam. The latter crjg-tallises from very dilute alcohol in flat needles which melt a t 161.5'.It dissolves readily in alcohol, ether and alkalis, and is insoluble indilute acids. The two compounds are also formed from trichlor-hydroxy*imidopyridine and from the diethoxy-compound b y the actionof sodium ethoxide and alcohol a t 190".N. H. 31.Correction. By A. LADENBURG and C. F. ROTH (Ber., 19, 2586 ;compare Abstr., 1885, 994).-The authors state that in the mixtureof bases of high boiling point from animal oil examined by them,aniline was present and accumulated in the fraction 174-176', fromwhich they separated the supposed new lutidine. A repetition of theexperiments has not yet been possible owing to a difficulty in obtain-ing the material. w. P. w.Derivatives of Picolinic and Nicotinic Acids. By E. SEYF-FERTH ( J . p ~ . Chem. [2], 34, 241--263).-At the outset, unsuccessfulexperiments are described, made with a view of obtaining hexahydm-picolinic acid from the acid itself by the action of various hyclro-genising agents.But in each case either the acid was not acted on orwas decomposed with formation of picoline and its hydro-derivatives.Chlomyicolinic acid, C,NH&l*COOH, is obtained by boiling chloro-picoline trichloride, C,NH,Cl*CCI, (from picolinic acid and phos-phoric chloride), with 80 per cent. sulphuric acid, and pouring theproduct into water. It cr.ystallises in needles and prisms, oftenshowing twinning. It melts a t 180", is sparingly soluble in cold water,readily soluble in hot water, alcohol and chloroform. It has stronglyacid properties and does not form salts with dilute mineral acids.I t s culcium salt crystallises with 1H,O in transparent prisms, andits harz'um salt in nodular aggregates. Both salts are sparinglyVOL. L11. 158 ABSTRACTS OF CHEMTCAL PAPERS.soluble in cold, but readily in hot water ; its silver salt is a voluniinous,flocculent precipitate.With reducing agents, it yields picoline andpicolinic acid.ChZorohydroxypico7inic acid, OH*C5NH&1*COOH, formed simul-taneously with the above, crptallises in clusters of needles, meltsabove 315", is sparingly soluble in cold, readily in hot water, alcohol,and ether. Like the above acid, it does not combine with mineral acids.These acids are not identical with those obtained by Ost (Abstr.,1883, 794). With phosphoric chloride, nicotinic acid yields an oilcontaining chlorine, and this, when boiled with sulphuric acid, isconverted into chlorhydroxy- and dichloro-nicotinic acids, togetherwith trichloropyridine.The first of these acids crystallises in mono-clinic prisms and needles, melting at 302", sparingly soluble in cold,readily in hot water and alcohol. The aqueous solution gives withsilver nitrate a white, flocculent precipitate, soluble in ammonia, andwith ferric chloride a dirt.y red precipitate. Its barium salt crys-tallises in transparent rhomhic prisms.Tricklorop y ridine, C5NH zC13, crystallises in colourl ess needles, me1 tinga t 64", insoluble in water, soluble in alcohol, ether and benzene.Dirhloronicotinic acid crystallises in small, white, grouped needles,m2lting a t 138"; its e t h y l salt forms colourless needles, melting a t50", sparingly soluble in water, but soluble in alcohol, ether, andchloroform. V. H. V.Bromoquinoline.By A. CLAUS and F. COLLISCHONN (Ber., 19,2763-2769).-It was previously mentioned (this vol., p. 60) thatwhen quinolinepropiobromide dibromide is heated, the hydrobromideof a new monobroruoquinoline is formed. The bromo-compound isheated a t 170" for some time, and then at 190" ; a crystalline residueis thus obtained without carbonisation. The bromoquinoline is sepa-rated from the quinoline that may be present by distilling with steam :the hydrobromide of the bromo-compound is decomposed, the free basegoing over with the steam, whilst the quinoline salt remains bebind. Itis a slightly yellow oil, having an odour resembling that of quinoline ;it boils a t 273-274" (uncorr.). The hjjdrobronde forms characteristicenvelope-shaped crystals, which dissolve sparingly in cold water withpartial decomposition, more readily in alcohol, and is almost insnlublein chloroform.When carefully heated a t about, 190", it sublimeswithout having melted. The hydrochloride sublimes readily withoutme1 ting. The PZatinochZoride, (C9NH6Br)2,H2PtC16, crystallises fromdilute hydrochloric acid in slender, orange-coloured needles. Thenitrate and su7phate melt respectively atp 180" and 182-183" (uncorr.).The dichroinate crptallises in flat, short prisms, which melt a t 144-145" with decomposition. The compound ( C9NHBr)2,AgN03 meltsat 172-173", and detonates at a high temperature with evolution ofred vapour. The same brornoquinoline is obtained when an etlheredsolution of bromine is added to a solution of quinoline in ordinaryether (containing alcohol) ; a yellow precipitate is formed.The lattercrystallises from chloroform in lustrous, garnet-coloured crystals, melt-ing a t 88" (uncorr.). Analysis points to the formula C,NH,,HBr,Br,.When exposed to air it gives off bromine. The hydrochlorideORGANIC CHEMISTRY. 159C,H,,HCl,Br,, forms small, orange-coloured crystals melting a t 100-105". When the hydrobromide of the quinoline dibromide is heatedat NO", it is converted with evolution of hydrobromic acid intobromoquinoline hydrobromide.When bromoquinoline is oxidised with potassium permanganate,Friedlander and 0 s termayer's oxalylanthranilic acid (Abstr., 1882,732), melting a t 210" (not 200°), and bromopyridinedicarboxylic acid,C5NH2Br(COOH)2, are obtained.The latter forms yellowish crystals,readily soluble in water, alcohol, ether, &c. ; it melts a t 165" withevolution of carbonic anhydride and formation of bronzonicotinic acid,melting at 183" (uncorr.).The bromoauinoline described above is identical with that obtainedby La Coste'(Abstr., 1881, 741) by brorninating yuinoline hydro-chloride. N. H. M.Synthetical Experiments with Ethyl Acetoacetate. ByL. KNORR (Annalen, 236, 69-1 151.-The action of ethyl ncetoacetateon aniline a t different temperatures has already been investigatedby the author (Abstr., 1884, 334). The anilide of acetoacetic acid,previously described as /3-phenylamido-a-crotonic acid, melts a t &5Oand decomposes on distillation, yjelding symmetrical diphenylcarh-amide.On the addition of bromine to a solution of the anilide inchloroform, an unstable additive product is formed, which c?ecom-poses when the mixture is warmed, yielding the a d i d e of mouo-bromacetoacetic acid, COMe*CHBr*CO*NHPh. This substance crys-tallises in plates, and melts at 138" with decomposition. Isonitruso-acetoucetic anilide, COMe-C(NOH)*CO*NHPh, crystallises in prisniq,and is freely soluble in alcohol, ether, acettic acid, arid light petroleum.It melts at 99-100". On reduction with zinc and acetic acid, a crys-talline compound, melting between 212" and 215", is obtained.The formation of hydroxylepidine (0,-m eth y karbostyril),C,NH,Me*OH [Me : OH = 4' : 2'1,by the action of dehydrating agents on acetoacetic anhydride, has beenalready described (Abstr., 1884, 334 and 1198), and this substancehas been described under the names of hydroxymethylquinoline andhydroxyquinaldine. On distillation with zinc-dust, it, is convertedinto y-Zepidine, and it yields chlorolepidine when treated with phos-phoric chloride (Abstr., 1885, 274).Chlorolepidiqe, C,NH,MeCl[Me : C1 = 2' : 4'1, melts a t 59" and boils a t 296" (cow.) ; i t yieldsy-methylquinoline when reduced with hydriodic acid, and also whendecomposed by water a t 200".Methozylepidine, C9NH5Me*OMe, formed by the action of potawiummethoxide on chlorolepidine, is an oily liquid boiling a t 275-276'.It forms a crystalline platinochloride. Ethoxylrpidine melts a t 51"and boils at 250" under 342 mm pressure.Chlorolepidine reacts withaniline, forming pken yllqidinaniine, a crystalline compound meltingat 129-130". The platinochloride melts at 235".Methyllepidone or dimethylpseudocarbost?/ril, C6H4<NMe'. CMe ' CH co > , hasalready been described by the author M dimethylpseudoquinoxylm 160 ABSTRACTS OF CEEhilCAL PAPERS.270"liquidvolatilestupetyinganhydrous, spar-ingly soluble(Abstr., 1885, 274). It can be prepared by the action of methyliodide on hydroxylepidine, by the condensation of methylaniline andethyl acetoacetate, and also by heating methoxylepidine a t 280".Methyllepidoiie melts a t 130- 132", and sublimes without decomposi-tion. It is a strong base,forming salts which are not decomposed by water. The platino-chloride, (C,,HllNO),,H2PtCl~ + 3H20, decomposes a t 214-21 5".Nascent hydrogen converts methyllepidone into a sparingly solublecrystalline compound, which melts a t 258".With bromine-water,methyllepidone forms bronaometh yllepidine, CIIH,,NOBr. This com-pound crjstallises in needles and melts at 172". It is insoluble inwater and alkalis, but dissolves i n dilute acids and forms a cmptallineplatinochloride. On the addition of bromine to a solution o€ methyl-lepidone in chloroform, a dibromo-additive product appears to beformed. It is decomposed by warm water, forming rnonobromo-met hyllepidone.The properties of methyllepidone, methoxy lepidine, and lepidineare seen in the following table :-It boils a t 290" under 250 mm. pressure.25 3-25 5"liquidvolatilepenetrating,anhydrous, spar-ingly solubleMethyllepidone.I----Boiling point ........Melting point.......I n steam.. ..........Odour ..............Ylatinochloride ......Bromine-water ......290" under 250 mm.non-volatilevery faintcontains 3H20, ' soluble in hot Hc1monobromide130-132"Methoxylepidine. 1 Lepidine.I--- -----w. c. w.Metaquinolinecarboxylic Acid. By Z. H. SKRAUP and P. BRUNNER(Montrtsh. Ckem., 7, 519--520).-1t is here shown that the seventhquinolinecarboxylic or the met aquinoliuebenzocarboxylic acid, re-cently obtained by Tortelli from a-amidophthalic acid by means ofthe glycerol reaction, is also formed in small quantities, fogefherwith its isomeride, from meta-amidobenzoic acid, by means of thesame reaction.In previous experiments, its formation was overlooked(Abstr., 1882, 71).-2583) .-Further experiments on a larger scale, and with purematerials, have confirmed the author's previous results (Abstr., 1886,478). a-AZZyZpyridine boils a t 187*5-192*5", and is a stronglyrefracting liquid of sp. gr. 0.9595 a t 0", sparingly soluble iu water,and having a distinct conyrine-like odour. The platinochloride,(C3H,*C,H,N)2, H2PtC16, melts at 185-186", and crystallises in needlessparingly soluble in water. The auroohloride melts at 135-136" ;the mercuriocbloride and cadmio-iodide are also described. By theaction of sodium on an alcoholic solution at the boiling point, a-allyl-V. H. V.Synthesis of Active Conine. By A. LADENBURG (Em., 19, 257ORGANIC CHEMISTRY.161pyridine is reduced almost quantitatively to a-propylpiperidine. Thisbase has a sp. gr. 0.8626 a t (I", and boils at 166-167" ; its hydro-chloride crystallises in white, silky needles, melting a t 203-205". Iusmell, solubility, Rpecific gravity, and physiological action, a-pro-pylpiperidine resembles conine, and not only are the platinochlorides,aurochlorides, and cadmio-iodides similar, but when a-propylpiperidineis converted into conyrine by Hofmann's method, a blue fluoresceiiceis obtained just as with conine. This fluorescence is due to a naccompanying product, for if the fluorescent base after separation fromunaltered conine be converted into the plntinochloride, the conyrineregenerated from it is no longer fluorescent.Conyrine pbtino-chloride from conine crystallises in monoclinic forms : a : b : c =1.0614 : 1 : 1-5374; g = 87" 8'; and thecrystals from the syntheticalbase give practically the same values on measurement.z-Propylpiperidine, however, in addition to the lower melting pointof its hydrochloride, is optically inactive, and must be regarded as aphysical isomeride of conine. To effect a separation into twooptically active bases, a sterilised nutritive solution containing 0.5 percent. of the tartrate was seeded with Penicillium glaucum, but with-oyt result. The active base, however, was obtained by introducinga crystal of the salt into a very concentrated solution of a-propyl-piperidine hydrogen tartrate; a slow separation of crystals took place,which yielded a dextrorotatory base, wbose specific rotation wm[a]D = 13" 87', compared with [a]D = 13" 79' for conine.The hydro-chloride of the synthetical active base melts a t 217.5", that of coninea t 217-5-218*5".From the mother-liquor, a lmvorotatory base was obtained, butit contained a large proportion of the dextrorotatory modification,which could not be further separated by the crystallisation method.However, on converting this lsvorotatory mixture into the cadmio-iodide, i t was found that after crystallisation, the crystallised salt?yielded a base which was less laevorotatory than before, whilst framthe mother-liquor a base was obtained, which in a 50 per cent. alcoholicsolution gave a rotation of -3" 30' in a decimetre tube, comparedwith 3" 10' for conine under the same conditions.w. P. w.Reduction of Nicotine. By A. LIEBRECHT (Ber., 19,2587-2598).-The author gives reasons for regarding nicotine as a pp.hexn-hydrodipyridyl, in which one of the pyridine nuclei has taken up two,and the other four atoms of hydrogen. The author not havingsucceeded in obtaining dipyridyl by the oxidation of nicotine, hasexamined the complete reduction prodiict obtained from its solutionin absolute alcohol by the action of sodium (comp. Abstr., 1886, 161).Dip@eridyZ, CloHmN2, is a colourless, oily liquid, solidifying a t a lowtemperature, and having an odour like that of piperidine. It hasa sp. gr. = 0.9561 at do, is laevorotatory, boils at 230-252" withoutdecomposition, and is volatile to some extent with steam.I n water,alcohol, and ether, it is readily solnble, and on exposure to light orthe air it turns slowly yellow. Contrary to expectation, dipiperidylacts only as a feehle poison. Dipiperidyl is a bi-acid base : its simplesalts art: very soluble and do not readily crystallise, although som162 ABSTRACTS OF CHEMICAL PAPERS.of the double salts crystallise well. The hydrochloride is verydeliquescent ; the periodide, CloH20N2,2HI,21z, crystallises in brownneedles, which lose iodine on drying in the air. The platinochloride,C,&,oN2,HzPtC16, forms small, red prisms, which on rapid crystalha-tion, separate either singly or in staurolite-like groups : it melts at202-203". The aurochloride, C18H20N2,2HA~C14, crystallises inyellow laminae, melting at 131-132", and is sparingly soluble inwater.A mercuriochloride, CloHmNz,2HC1,5HgCl,, crystallises insmall sparingly soluble tables. Carbon bisulphide combines withdipiperidyl, forming a, yellow salt, easily soluble in water and alcohol,less soluble in benzene and insoluble in ether. It readily becomesresinified, and when its alcoholic solution is boiled with mercuricchloride, the odour of allylthiocarbimide is evolved.Diacetodipiperidyl, CloN2H~&2, is prepared by heating the base withacetic anhydride a t 170" for six hours. It is a yellow, oily liquid,boiling a t 400-410° with slight decomposition, and does not solidifyin a freeeing mixture.The action of methyl iodide results in the formation of thehydriodides of two bases, dimethyl- and trimethyl-dipiperidyl, ofwhich the former is readily soluble, whilst the latter is insolublein water.Bimetli yldipiperidy2, C10N2H18Me2, is an oil boiling at 230-332",soluble in water in all proportions, and slightly volatile with steam.Its salts, with the exception of the merczcriochloride,CloH18~le2N2,2HC1,2Hg;CI,,&re readily soluble, and can scarcely be crystallised ; theplatinichZoride,Cl,H,,Me2N2,H2PtC16, forms small dark red ciystals.l'rimeth?lldipi~erid~E, C10H1,Me3N2, is obtained as a yellow oil ofrepulsive odour resembling that of methylamine, boiling a t 205-212"; i t is insoluble in water, and is not volatile with steam, Thesalts are very easily soluble and seem to be uucrystallisable, theplatinochloride, C,oH,,Me3N,,H,PtC16, is insoluble in alcohol and etber.'l'be action of methyl iodide does not appear to yield a higher methyl-Sparteine. By E.BAMBERGER (Annalen, 235, 368-376).-Sparteine was discovered by Stenhouse (this Joui-nal, 1851, 223), andits compounds were afterwards investigated by Mills (this Journal,1862, 1). The author has re-examined these bodies, and his resultsin many oases differ from the observations of Mills. Sparteineboils a t 311--311*5', under a pressure of 723 mm. The sulphate,C15H29N2,H2S0~, forms large, transparent prisms, which are verysoluble in water. The hydriodide, C,,H,,N,,HI, forms glistening, four-sided plates, which probably belong to the rhombic system. It i Rfreely soluble in alcohol and in hot water.When aqueous hydriodicacid acts on sparteine, a resinous mass is formed, from which thedihydriodide can be obtained in silky needles, by boiling the alcoholicsolution with animal charcoal.The compound C,,H,,N,Et12, which Mills obtained by the action ofethyl iodide and alcohol on sparteine at loo', is decomposed byated base than trimethyldipiperidyl. w. P. wORQANlC CHEMISTRY. 163sodium hydroxide solution, forming an oily liquid, which can beseparated into sparteine and sparteine ethiodide, by means of ether.Spurtsine ethiodide, CI,H,,N,,EtI, is formed by the action of ethyliodide on sparteine. It crystallises in thick prisms, and dissolvesfreely in water and alcohol. Sparteine methiodide crystallises inrhonibic plates; a : b : c = 0.8989 : 1 : 1.6009.Themethylhydroxideis a deliquescent substance, with a strongly alkaline reaction. Thecarbonate cryetallises in needles. When sparteine is oxidised withpotassium permanganate, the chief product is oxalic acid ; acetamideis also formed, together with a small quantity of a pyridine-derivative. w. c. w.Pseudomorphine. By 0. HESSE (Annulen, 235, 229-232).-When potassium hydroxide (2 mols.) and potassium ferricyanide(1 mol.) are added to a solution of pure morphine hydrochloridedissolved in 40 parts of water, pseudomorphine is deposited ; 100 partsby weight of morphine yield 88.4 parts of pseudomorphine. Thisresult shows that the reaction takes place according to the equation9Cl7H,,NO3 + 2KOH + 2K,FeCy6 = 2CI7H,*NO3 + 2H20 +2K,FeCyG(the yield is theoretically 99.6 per cent.); not according to thefollowing reaction : 2C17H19N03 + ZKOH + 'LK,FeCy, = C17H17N0 3 +CI7Hl9NO3 + 2H20 + 2K,FeCg6 (the yield is only 49.65 per cent.ofthe morphine employed). This shows that the formula for pseudc-morphine is C17H,8N03*C17H18N03, as proposed by Polstorff (Abstr.,18g9, 405), instead of C17H17N03, as formerly proposed by the author(Abstr., 1884, 616). w. c. w.Papaverine. By G. GOLDSCHMIEUT (Monnatsh. Chern., 7, 485405).-In this paper derivatives of papaveraldine, and the most con-venient method for its preparation, are described.The nitrate, Cz0H ,,N05,HN03, crystallises in citron-yellow needles ;the picrate, in needles grouped together in voluminous aggregates ; theozime, C20HSON206, in flat, white needles melting a t 245" ; the methiodide,in golden prisms melting a t 135" with decomposition ; and the etho-bromide, in large prisms melting a t 270".Papareraldine, if heated only for a short time with potash, yieldsreratric acid together with small quantities of a dimethoxyquinoline,the constitution of which is at present uncertain.With tin and dilute hydrochloric acid, papaverine yields a tetra-hydro-derivative, C,,H,,NO,, which crystallises in small, white prismsmelting a t 200", soluble in benzene and acetone, sparingly soluble inether and' petroleum.Its hydrochloride crystallises in transparentprisms of the monoclinic system, melting with violent decompositiona t 290" ; when injected internally, it causes albuminuria with inflamma-tion of the kidneys.The m i d sulyhate forms acicular, and the acidoxalate prismatic crystals ; the dichromafe, glistening prisms ; and thepic?-ate, lemon-yellow needles. The platznochloride crystallises inminute yellow needles, and the stannochloride in concentrically groupedneedles.I n an additional note, the author defends the formula C,H',,NO, forpapaverine, as against C21H21NO4, that proposed by Hesse, Beckett164 ABSTRACTS OF CHEMICAL PAPERS.and Wright, and others; exception is also taken to a statement ofHesse relative to the existence of an alkaloid, pseudopapaverine.V. H. TT.Papaverine Salts. By R. JAHODA (Mortutsh. Chem., 7, 506-516).-As a further proof of the formula C20H21N04, proposed for papa-verine, a number of its salts have been prepared and analysed; theresults attained afford a strong confirmation of the above view.The neutral succinate forms large tabular crystals melting at 171",soluble in hot water; the bettzoute, triclinic crystals ( a : b : c =0.459: 1 : 0.680; 9 = 95.27"), melting at 145", soluble in alcohol, insolublein water; the salicylate, monoclinic crystals ( u : b : c = 1.161 : 1 : 1.685;T,I = 102.39), melting at 130" ; the diodide of the hydroiodide,C2oH21NO,,HI,I2,purple crystals of the monoclinic system.The hydrochloride gives with halogen salts of the metals doublecrystalline salts, of which the following are described :-The cadtriio-chloride, ( C20H21N0,,H Cl),CdCI,, small crystals, of the tetragonalsystem ; a : a : c = 1 : 1 : 0.646, melting at 176" ; the cad,mio-brQmideand -iodide, white precipitates, melting at 150" and 180' respectively ;and the zincoiodide, crystallising in small leaflets. V. H. V.Constitution of Cinchonine. By Z. B. SKRAUP (MonatsF,. Chem.,7, 517-518).-The author criticises the view of Bisohoff and Rachthat cinchonic acid is ~-~-dicarboxyl-6-valerolactone (Abstr., 1886,1012) ; R study of the syrupy oxidation product of cinchonine andquinine has indicated the presence of an amorphous acid, C,HI3NOa, abase of the formula CgHI,N02, difficult to obtain in the free state,although its salts form well-developed crystals, as also of a base of theformula C9H7N0, probably identical with kynurine, and an amor-phous substance of the supposed composition C13H'13N02, and ofdoubtful origin. V. H. V.Specific Rotatory Power of Piperidine Bases. By A. LADEN-BURG (Ber., 19, 2584).--Ti'he results obtained in a previous paper(this vol., p. 160) are in accordance with Le Bel-Van't Hoffs hypo-thesis, since a-propylpiperidine contains an asymmetric carbon-atomiu its constitutional formula. As this is true of all a-alkyl-derivativesof piperidine, the author has examined a-pipecoline and a-ethyl-piperidine, and by converting them into their dextrotartrates hasmcceeded in obtaining optically active modifications of each. Uextro-rotatory a-pipecoline has a specific rotatory power of 21" 8'. w. P. w.Action of Bromine on Dimethylpiperidine ; New Synthesisof Piperidine-derivatives. By G. MERLLNG (Rer., 19, 2628-2632).-The author previously obtained (Abstr., 1884, 1385) by the actionof bromine on dimethylpiperidine, two compounds-bromodimethyl-piperidineammonium bromide and a hydrobromide. The latter isnow shown to be dibromodimethylpiperidine hydrobromide. Whenthe free base is warmed with alcohol, the alkaline solution becomesneutral, and characteristic crystals of monobromodimethylpiperidineORGANIC CHEMISTRY. 165ammonium bromide separate. These reactions can be explained bythe consti tutiond formula 5tss:gned by Ladenburg to dimethylpiperi-dine : CH,: CH*CH2*CH,*CH:,*NMe2. The constitution of di bromodi-methylpiperidine and the ammonium bromide would then beCH2Br*CHBr*CH2*CH2*CH2-NMe2 and C H 2 < ~ ~ B r ~ ~ ~ > N M e 2 B r . 2-The formation of the hydrobromide of dibromodimethylpiperidine isprobably due to 2 mols. of the free base reacting with one another ; thisview was strengthened by the discovery of a base free from bromine inthe 1:ist mother-liquor from dibromodimethylpiperidine hydrobromide.Haemin Crystals. By K. BIEFALVI ( O h m . Centr., 1886, 499)-Blood free from chlorine yields no hsmin (chlorohsmatin) crystalswhen heated with glacial acetic acid. The author finds, however, thatif NrtC1, NaBr, KBr, NH4Br, NaI, or K I be first added to the blood,crystals resembling chlorohsmat,in are formed.N. H. M.L. T. T.Diastase, By C. J. LINTNER (J. pr. Chem. [2], 34, 378-394). -The author has examined the different metbods proposed for the pre-paration of pure diastase, and determined the diastatic activity of thesubstances obtained, He adopts Kjeldahl's law of proportionality(Abstr., 1880, 562), and uses the modification of Kjeldahl's methodfor determining diastatic activity, described in a former paper (Abstr.,1886, 386). In place of his former metlhod for preparing solublestarch, he now recommends the following :-A quantity of pure potato-starch is mixed with a sufficient quantity of 7.5 per cent. hydrochloricacid to cover i t ; it is then allowed to remain for seven days a t theordinary temperature or for three days a t 40", when the starch liaslost the power of gelatinising. The structure of' t,he starch, however,remains unaltered. It is t'hen well washed with cold water until everytrace of acid is removed, and dried in the air. So obtained it issoluble in hot water to a bright and limpid solution. A 2 per cent.solution will remain clear for some days, but 10 per cent. solutions setto a jelly-like mass on cooling. The acid used must riot exceed'7.5 per cent. as 10 per cent. acid causes the gelatinisation of the starch ;with sulphuric acid, however, i t requires at least 15 per cent, aciddigested a t 40" to eft'ect the conversion into soluble starch. Lintneruses a 2 per cent. solution of this soluble starch instead of that pre-pared by the method previously given.The dinstatic activity of the precipitated diastases is expressed as100, when 3 C.C. of a solution of 0.1 gram diastase in 250 C.C. wateradded to 10 C.C. of a 2 per cent. starch solution produces in one hour, a tthe ordinary temperature, sufficient sugar to reduce 5 c.c, of Fehling'ssolution. Diastase is best prepared from green nialt or from air-driedmalt. Lintner examined the preparation obtained from these maltsby extraction with water and glycerol and subsequent precipitationwith alcohol, both before and after heating a t 70",and obtained, in allcases, a substance with a comparatively slight diastatic activity. Asthe result of his experiments, he recommends the following method ofpreparation :-1 part of green malt or sifted air-dried malt is extractedwith 2 to 4 parts of 20 per cent. alcohol for 24 hours. The filtere166 ABSTRACTS OF CHEMICAL PAPERS.extract is mixed with 2+ volumes absolute alcohol ; the precipitatequickly settles, and is washed on a filter with absolute alcohol ; it isthen transferred to a mortar, well mixed with absolute alcohol, thrownon a filter, and thoroughly washed with absolute alcohol and ether.Finally, it is dried i n a vacuum over sulphuric acid. So obtained it isa light, yellowish-white powder with great diastatic activity. It ispurified by repeated solution in water and precipitatiorl with alcohol,and finally by dialysis. Loea's method of purification by means ofprecipitation with lead acetate is not to be recommended, since diastaseloses three-fourths of its activity in the process. By purification, boththe percentage of nitrogen and the diastat,ic activity are increased,whilst the amount of ash, which consists entirely of normal calciumphosphate, is. diminished. A preparation obtained from green maltcontained 8.3 per cent. nitrogen and diastatic activity = 96. Aftertwo precipitations the nitrogen = 9.06 per cent., and the activity= 100. This submitted to dialysis had the percentage of nitrogenraised to 9.9, and the percentage of ash diminished from 10.6 to 4-79.These and other analyses show that the diastatic activity increaseswith the amount of nitrogen. A purified diastase gave the followingnumbers on analysis, calculated on the ash-free substance. For thepurpose of comparison the analyses of other soluble ferments aregiven :-C. H. N. 8.Diastase. . . . . . . . . . 46.66 7.35 10.42 1.12 (Lintiier).Pancreatic ferment 46.57 7.17 14.95 0.95 (Hufner).Invertase . . . . . . . . 43.9 8.4 9.5 0.6 (Barth, Donatlh).Emulsin .. . . . . . . 43.5 7.0 11.6 1.3 (Bull).Diastase gives all the reactions for the albuminoyds, but not thecharacteristic biuret reaction for peptones ; it gives, however, a,characteristic blue coloration with tinctme of guaiacum and hydrogenperoxide, which is soluble in ether, benzene, chloroform, and carbonbisnlphide, but not in alcohol. This reaction is given by no othersoluble ferment or protein substance.Note.-Lintner appears to have overlooked the fact that O'Sullivan(this Journal, Trans., 1884, 2) described an almost identical method ofpreparing pure diastase.Action of Diastase and Invertin. By H. MULLER (Ann.Agronom., 12,481-482).-The autlior has studied the action of theseferments under conditions such as prevail in the plant-cell, with a viewt o elucidate their physiological importance. Both ferments are activeat O", but the activity increases until the neighbourhood of 50" isreached : the temperatures being 0", lo", 'LO", 30", 40" ; the energy ofdiastase is expressed by the numbers 7, 20, 38, 60, 98, and that ofinvertin by the numbers 9, 19, 36, 63, 93.Under ordinary conditions, cell-say contains much carbonic anhydride,and is exposed to a pressure of several atmospheres. Both of thesecircumstances accelerate the activity of the ferments. Even at theordinary pressure, saturation of the liquid with carbonic anhydridemay have the effect of tripling the energy of diastase, and in presenceG. H. Ill.G. H. MPHTSIOLOGICAL CHEMISTRY. 167of carbonic anhydride diastase has the power of acting on starch.which has not been boiled to a paste. Between the limits of 2 and20 per cent., concentration of a sugar solution has little effect on theaction of invertin, which is a little more feeble in strong solutionsthan in weak ones, but the accumulation of invert sugar is stronglyopposed to the continuance of the reaction. J. M. H. M

ISSN:0368-1769    

DOI:10.1039/CA8875200122

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

PHTSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a l C h e m i s t r y . 167 Natural and Artificial Digestion. By T. PFEIFFER (Zeit. physioE. Chern., 11, 1--24).-The author has previously criticised the work of Stutzer on this subject (see Abstr., 1886, 1053). Additional experi- ments on pigs are now brought forward, and from them the following results are drawn:- 1. A comparison of the method of natural digestion of the nitro- genous constituents of the food combined with the investigation of the products of metabolism, with the method of artificial digestion of the food-stuff by pepsin and trypsin as devised by Stutzer, shows that there is an almost absolute agreement between the tw.0. 2. By the help of Stutzer’s method, the digestibility of the nitro- genous constituents of the food can be estimated with sufficient accuracy.This always gives results which agree more closely than those obtained with the method hitherto used, in which the products of nitrogenous metabolism in the faces are not investigated. W. D. H. Glycogen in the Liver of New-born Dogs. By B. DEMANT (Beit. physiol. Ohem., 11, 142-144) .-In the intra-uterine condition, the liver is stated to be very poor in glycogen. Hoppe-Seyler states the opposite to be the case. The present research investigates the matter in the case of the dog ; the glycogen was estimated by Brucke’d method, and the result found wa8 that in the days following birth glycogen was present in exceedingly large quantities ; this is illus- trated by the following table :- Percentage quantity of glycogen in the liver.Age of animal. 1 hour ................. 11.389 34 hours ................ 9.527 3 hours ................ 5.443 4 days .................. 2.697 11 ,, .................. 2 792 12 ,, .................. 3.664 Fully grown .............. 1.661 W. D. H. Lactic Acid in Animals. By A. HIRSCHLER (Zeit. physiol. Chem., 11, 41--42).-Lactic acid has been described as occurring in the grey matter of the brain, and in the parenchymatous juices of the spleen, thymus, lymphatic glands, 85c. Which variety of lactic acid this is,168 ABSTRACTS OF CHEMICAL PAPERS. has not yet been investigated. The present research is concerned with this question in relation to the spleen and lymphatic glands of the ox. Lactate of zinc was obtained by Hoppe-Seyler’s method, with the modification that the finely chopped organ was extracted by 0.5 per cent.sulphuric acid instead of by cold water ; in this way, more lactic acid is obtained. By estimation of the water of crystallisation of the zinc salt, and of the hydroqen and carbon, the conclusion is drawn that both in the spleen and lymphatic glands it is sarcolactic acid which is present. Pigments of Melanotic Sarcomats. By K. A. H. M~RNER ( Z e d . physioZ. Chem., If, 66-140) .-The name maEanin has been hitherto used for the pigments occurring in the eye, hair, and skin, in patho- logical new growths, and also for the decomposition products of chromogens in urine. The black pigmerit of tohe retina has been investigated by Berzelius, who found it contained a small quantity of iron, by Scherer who found no iron, and also by Rosow and Sieber.The percentage composition obtained by the various observers shows great discrepancies, and this, with their methods of preparing the pigment, renders it probable that they were not dealing with a pure substance. Concerning the black pigmeut of the skin of negroes and of the hair, still less is known, and although some few percentage estinintions hare been made by Sieber, the result cannot be described as a convincing one. The pigment of melanotic tumours was first investigated by Heintz, who found that it was soluble in alkalis with dificulty, and that it contained no iron. An elementary analysis gave the following figures : C = 53.40, H = 4.02, and N = 7.10 per cent. Dressler made a similar investigntion, and found in the pigment a small quantity of iron.Berdez and Nencki named the pigment Phywmtorusiit; they found it to be insoluble in water, alcohol, and ether, easily soluble in solutions of fixed alkalis or their carbonates, and in ammonia ; from such solu- tions it was precipitable by acids, but waH somewhat soluble in excess. The preparation cont,ained carbon, hydrogen, oxygen, and nitrogen, sulphur in large amount (10 67 per cent.), but no iron, phosphorus, or chlorine. In horses, they found in melanotic tumours a pigment with somewhat different properties, which they called hippntslunin. In the urine of some of these patients, a pigment has been found which according to some is an excess of the ordinary urine pigments, and according to others is the same pigment that occurs in the tumour.It is turned a dark-brown colour by the action of nitric acid ; and in some cases a similar change occurs after mere exposure. The uncertain and contradictory statements of previous observers cannot but render uncertain which of the above statements is correct. Again, in other cases of these tumours, particles of a brown pigment are found in the blood, the corpuscles having the normal shape and colour ; similar granules have been occasionally described in the urine and urinary passages. The present research was undertaken with the material supplied by a patient, the full particulars of whose case are given. During life, the urine showed the peculiar coloration above-mentioned ; after W. D. H.PIIY EIOLOGICAL CHEMISTRT.169 A. Pigment insoluble i n acetic acid- 1. From the tumour.. .. . . .. . . 2. From the baryta precipitate. 3. From the lead precipitate . . B. Pigment soluble in acetic actd- 3. From the tumour.. . . .. .. . . 4. From the tarvta precipitate. 5. From the lead precipitate . . death, the tumour itself was investigated. I t s situation was the shoulder; secondary growths were present in the liver, but none in the kidney substance. The blood, except for a low percentage of hemoglobin, was normal. The colouring matter did not give any absorption-bands, but produced a general dimming of the spectrum, especially towards the violet end. The methcds by which the pigment was investigated were : first, by the spectrophotometer to determine the extinction coefficients in different parts of the spectrum; and, secondly, by elementary analysis.Although the quantity of material a t hand was small, and therefore some results are incomplete, and others put forward with reserve, yet certain definite conclusions were arrived at. The pigment was found to contain iron, which also was estimated spectrophotometrically, as well as by the usual methods ; the spectro- photometric method consisted in converting the iron of the ash into ferric thiocyanate, and comparing its extinction coefficients with those obtained from a solution of ferric chloride of known strength similarly treated, Iron was present in small quantities; the failure o f some previoufi observers to obtain the proof of its presence is acccunted for by their having used hydrochloric acid in the preparation of the pigment.It is found that this acid dissolves out nine-tenths of the iron from the pigment. Baryta-water causes a precipitate in the urine, arid this carries down n ith it a good deal of the pigment ; this is filtered off. In the filtrate, the remaining portions of the pigment are carried down with the precipitate caused by lead acetate. For the method adopted for separating the pigment from the tissues of the tumour, the original paper must be consulted. The pigment obtained from these three sources is a brownish, amorphous powder when dry. It is partly soluhle in acetic acid, and partly insoluble. The following table represents the percentage composition, and the relative absorption for the region wave-length = 562, for these different preparations :- 553'2 6-00 55-76 5.95 - - - - - - 58 *07 8 *03 I C.1 H. I N. 1 5. I Be. Percentages. 1-1- ----- 12.30 12 -27 - - - 11 '08 - 7.97 9 *01 8 -30 5 -90 4 -75 - 0 '072 0.20 0 *23 0.21 0 -19 0 -20 Abso~p- tion. 0 '00038 0 '00039 0 '00029 0 '00094 0 '00114 0 '00056 There are thus two pigments, although perhaps it may be that tile170 ABSTRACTS OF CHEMICAL PAPERS. two are produced from a mother-substance by the action of the acid. They differ from one another in percentage composition, and in absorptive power. They resemble one another in solubilities, except with regard to acetic acid, and in colour to the naked eye. The high percentage of sulphur in the pigment insoluble in acetic acid agrees with the similar condition in phymatorusin. An important point brought out is the identity of the tumour pigment with that in the urine; it is probably brought to the urine by the blood, in which feebly alkaline liquid it is slightly soluble.It is not the same pigment as occurs in normal urine; that gives quite a different spectrophotometric chart. W. D. H. Cobra Poison. By C. J. H. WARDEN (Chem. News, 54,197-199 ; 209-217 ).-Two samples of air-dried snake-venom contained respec- tively 16.26 and 15.43 per cent. of water. Fresh venom yields 25-50 per cent. of solid residue. For the author’s experiments, the solution of the dried venom in distilled water was injected under the skin of the back of white or piebald China mice. A dose of 0.012 gram of anhydrous venom was fatal in four minutes, and the rapidity of action decreases as the quantity of poison administered is diminished; with 0.000016 gram, the animal may live three hours, whilst 0.000008 gram is not fatal.Very large and very small doses cause convulsions, inter- mediate doses do not. In the case of white mice, the fatal ratio of poison to body weight appears to be about 1 : 10,000,000. Heating the solution of the venom soon produces marked coagulation, but it j s only after heating for some time that the toxic activity is reduced, hence prolonged heating at a moderate temperature is more effective for such a purpose than short periods at higher temperatures. Similay remarks apply to the action of picric acid, which causes an abundant precipitate in solutions of the poison, and in some experiments a marked reduction in the toxic action when the filtered solution was employed.D. A. L. Urine of the Tortoise. By T. W. MILLS (J. PhysioE., 7, 453- 457).-The urine of the tortoise is liquid, ranging in colour from colourless to light amber, and is of an acid reaction. I n some cases, it is green from admixture with bile in the cloaca. Albumin is invariably present ; although probably this is derived from the intes- tine, vici the cloaca. On allowing the urine to stand, the albumin having been removed, a deposit of uric acid crystals, of an orange colour occurs. On many occasions uric acid crystals were found in the urine without any treatment; these were always colourless. By Heintz’s hydrochloric acid method, the amount of uric acid in the urine was estimated, and found to be several times greater than in human urine.Urea is altogether absent. The inorganic constituents do not differ in kind from those found in the urine of m m . W. D. H.PHTSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a l C h e m i s t r y .167Natural and Artificial Digestion. By T. PFEIFFER (Zeit. physioE.Chern., 11, 1--24).-The author has previously criticised the work ofStutzer on this subject (see Abstr., 1886, 1053). Additional experi-ments on pigs are now brought forward, and from them the followingresults are drawn:-1. A comparison of the method of natural digestion of the nitro-genous constituents of the food combined with the investigationof the products of metabolism, with the method of artificial digestionof the food-stuff by pepsin and trypsin as devised by Stutzer, showsthat there is an almost absolute agreement between the tw.0.2.By the help of Stutzer’s method, the digestibility of the nitro-genous constituents of the food can be estimated with sufficientaccuracy. This always gives results which agree more closely thanthose obtained with the method hitherto used, in which the productsof nitrogenous metabolism in the faces are not investigated.W. D. H.Glycogen in the Liver of New-born Dogs. By B. DEMANT(Beit. physiol. Ohem., 11, 142-144) .-In the intra-uterine condition,the liver is stated to be very poor in glycogen. Hoppe-Seyler statesthe opposite to be the case. The present research investigates thematter in the case of the dog ; the glycogen was estimated by Brucke’dmethod, and the result found wa8 that in the days following birthglycogen was present in exceedingly large quantities ; this is illus-trated by the following table :-Percentage quantity ofglycogen in the liver.Age of animal.1 hour ................. 11.38934 hours ................ 9.5273 hours ................ 5.4434 days .................. 2.69711 ,, .................. 2 79212 ,, .................. 3.664Fully grown .............. 1.661W. D. H.Lactic Acid in Animals. By A. HIRSCHLER (Zeit. physiol. Chem.,11, 41--42).-Lactic acid has been described as occurring in the greymatter of the brain, and in the parenchymatous juices of the spleen,thymus, lymphatic glands, 85c. Which variety of lactic acid this is168 ABSTRACTS OF CHEMICAL PAPERS.has not yet been investigated.The present research is concernedwith this question in relation to the spleen and lymphatic glands ofthe ox. Lactate of zinc was obtained by Hoppe-Seyler’s method, withthe modification that the finely chopped organ was extracted by 0.5per cent. sulphuric acid instead of by cold water ; in this way, morelactic acid is obtained. By estimation of the water of crystallisationof the zinc salt, and of the hydroqen and carbon, the conclusion isdrawn that both in the spleen and lymphatic glands it is sarcolacticacid which is present.Pigments of Melanotic Sarcomats. By K. A. H. M~RNER ( Z e d .physioZ. Chem., If, 66-140) .-The name maEanin has been hithertoused for the pigments occurring in the eye, hair, and skin, in patho-logical new growths, and also for the decomposition products ofchromogens in urine.The black pigmerit of tohe retina has beeninvestigated by Berzelius, who found it contained a small quantity ofiron, by Scherer who found no iron, and also by Rosow and Sieber.The percentage composition obtained by the various observers showsgreat discrepancies, and this, with their methods of preparing thepigment, renders it probable that they were not dealing with apure substance. Concerning the black pigmeut of the skin of negroesand of the hair, still less is known, and although some few percentageestinintions hare been made by Sieber, the result cannot be describedas a convincing one.The pigment of melanotic tumours was first investigated by Heintz,who found that it was soluble in alkalis with dificulty, and that itcontained no iron. An elementary analysis gave the following figures :C = 53.40, H = 4.02, and N = 7.10 per cent.Dressler made a similarinvestigntion, and found in the pigment a small quantity of iron.Berdez and Nencki named the pigment Phywmtorusiit; they found itto be insoluble in water, alcohol, and ether, easily soluble in solutionsof fixed alkalis or their carbonates, and in ammonia ; from such solu-tions it was precipitable by acids, but waH somewhat soluble in excess.The preparation cont,ained carbon, hydrogen, oxygen, and nitrogen,sulphur in large amount (10 67 per cent.), but no iron, phosphorus,or chlorine. In horses, they found in melanotic tumours a pigmentwith somewhat different properties, which they called hippntslunin.In the urine of some of these patients, a pigment has been foundwhich according to some is an excess of the ordinary urine pigments,and according to others is the same pigment that occurs in thetumour.It is turned a dark-brown colour by the action of nitricacid ; and in some cases a similar change occurs after mere exposure.The uncertain and contradictory statements of previous observerscannot but render uncertain which of the above statements is correct.Again, in other cases of these tumours, particles of a brown pigmentare found in the blood, the corpuscles having the normal shape andcolour ; similar granules have been occasionally described in the urineand urinary passages.The present research was undertaken with the material supplied bya patient, the full particulars of whose case are given.During life,the urine showed the peculiar coloration above-mentioned ; afterW. D. HPIIY EIOLOGICAL CHEMISTRT. 169A. Pigment insoluble i n aceticacid-1. From the tumour.. .. . . .. . .2. From the baryta precipitate.3. From the lead precipitate . .B. Pigment soluble in aceticactd-3. From the tumour.. . . .. .. . .4. From the tarvta precipitate.5. From the lead precipitate . .death, the tumour itself was investigated. I t s situation was theshoulder; secondary growths were present in the liver, but none inthe kidney substance. The blood, except for a low percentage ofhemoglobin, was normal.The colouring matter did not give anyabsorption-bands, but produced a general dimming of the spectrum,especially towards the violet end. The methcds by which the pigmentwas investigated were : first, by the spectrophotometer to determinethe extinction coefficients in different parts of the spectrum; and,secondly, by elementary analysis. Although the quantity of material a thand was small, and therefore some results are incomplete, and othersput forward with reserve, yet certain definite conclusions were arrivedat. The pigment was found to contain iron, which also was estimatedspectrophotometrically, as well as by the usual methods ; the spectro-photometric method consisted in converting the iron of the ash intoferric thiocyanate, and comparing its extinction coefficients with thoseobtained from a solution of ferric chloride of known strength similarlytreated, Iron was present in small quantities; the failure o f someprevioufi observers to obtain the proof of its presence is acccuntedfor by their having used hydrochloric acid in the preparation of thepigment.It is found that this acid dissolves out nine-tenths of theiron from the pigment.Baryta-water causes a precipitate in the urine, arid this carriesdown n ith it a good deal of the pigment ; this is filtered off. In thefiltrate, the remaining portions of the pigment are carried down withthe precipitate caused by lead acetate. For the method adopted forseparating the pigment from the tissues of the tumour, the originalpaper must be consulted.The pigment obtained from these threesources is a brownish, amorphous powder when dry. It is partlysoluhle in acetic acid, and partly insoluble.The following table represents the percentage composition, and therelative absorption for the region wave-length = 562, for thesedifferent preparations :-553'2 6-0055-76 5.95- -- -- -58 *07 8 *03I C. 1 H. I N. 1 5. I Be.Percentages.1-1- -----12.3012 -27 -- -11 '08 -7.979 *018 -305 -904 -75-0 '0720.200 *230.210 -190 -20Abso~p-tion.0 '000380 '000390 '000290 '000940 '001140 '00056There are thus two pigments, although perhaps it may be that til170 ABSTRACTS OF CHEMICAL PAPERS.two are produced from a mother-substance by the action of the acid.They differ from one another in percentage composition, and inabsorptive power.They resemble one another in solubilities, exceptwith regard to acetic acid, and in colour to the naked eye. The highpercentage of sulphur in the pigment insoluble in acetic acid agreeswith the similar condition in phymatorusin. An important pointbrought out is the identity of the tumour pigment with that in theurine; it is probably brought to the urine by the blood, in whichfeebly alkaline liquid it is slightly soluble. It is not the samepigment as occurs in normal urine; that gives quite a differentspectrophotometric chart. W. D. H.Cobra Poison. By C. J. H. WARDEN (Chem. News, 54,197-199 ;209-217 ).-Two samples of air-dried snake-venom contained respec-tively 16.26 and 15.43 per cent.of water. Fresh venom yields 25-50per cent. of solid residue. For the author’s experiments, the solutionof the dried venom in distilled water was injected under the skin ofthe back of white or piebald China mice. A dose of 0.012 gram ofanhydrous venom was fatal in four minutes, and the rapidity of actiondecreases as the quantity of poison administered is diminished; with0.000016 gram, the animal may live three hours, whilst 0.000008 gramis not fatal. Very large and very small doses cause convulsions, inter-mediate doses do not. In the case of white mice, the fatal ratio ofpoison to body weight appears to be about 1 : 10,000,000. Heatingthe solution of the venom soon produces marked coagulation, but itj s only after heating for some time that the toxic activity is reduced,hence prolonged heating at a moderate temperature is more effectivefor such a purpose than short periods at higher temperatures. Similayremarks apply to the action of picric acid, which causes an abundantprecipitate in solutions of the poison, and in some experiments amarked reduction in the toxic action when the filtered solution wasemployed. D. A. L.Urine of the Tortoise. By T. W. MILLS (J. PhysioE., 7, 453-457).-The urine of the tortoise is liquid, ranging in colour fromcolourless to light amber, and is of an acid reaction. I n some cases,it is green from admixture with bile in the cloaca. Albumin isinvariably present ; although probably this is derived from the intes-tine, vici the cloaca. On allowing the urine to stand, the albuminhaving been removed, a deposit of uric acid crystals, of an orangecolour occurs. On many occasions uric acid crystals were found inthe urine without any treatment; these were always colourless. ByHeintz’s hydrochloric acid method, the amount of uric acid in theurine was estimated, and found to be several times greater than inhuman urine. Urea is altogether absent. The inorganic constituentsdo not differ in kind from those found in the urine of m m .W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8875200167

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 171 Chemistry of Vegetable Physiology and Agriculture. Reduction of Copper Sulphate during By H. QUANTIN (Compt. rend., 103, tion. Alcoholic Fermenta- 888-883) .-In exmri- ments on-a small scale, it is found that copper existing in the for’m of copper sulphate to the extent of 0.05 gram per litre, is completely precipitated in the form of copper sulphide during alcoholic fermenta- tion. On a large scale, doubtless a still larger quantity would be removed, but the quantity given is greater than would ever be intro- duced into the wort as a result of the use of copper sulphate as a remedy for mildew. Since moist copper sulphide is readily oxidised, it is important to avoid any akation of the lees containing it. The Rulphide is the only salt of copper which is insoluble in the must of grapes.C. H. R. Alcoholic Fermentation of Dextrin and Starch. By U. GAYON and E. DUBOURG (Compt. rend., 103, 885--887).--The authors have met with a species of Mucor which has the power of converting dextrin and starch into sugar, and then fermenting the sugar but, like Mzccor circin,elloides, it has not the power of inverting cane-sugar, and transforming it into alcohol. Other non-inversive ferments. on the other hand, have not the power of fermenting dextrin and starch. In beer wort or solutions of glucose, this mucor develops rapidly in large, spherical, ferment cellulen. Jn dextrin or starch, i t a t first forms mgcelial tubes, which soon swell up, divide, and form themselves into globular masses. In yeast-water containing sugar, the mucor forms only A bulky, unicellular mycelium.The fermentation of dextrin takes place somewhat slowly, and that of starch requires still longer. The dextrin existing in beer is readily saccharified by this mucor and converted into alcohol, if the alcohol already in the beer is expelled before adding the ferment. Eurotium oryze, used in the manufacture of “koji,” secretes a diastase which converts rice into a true malt, and this d a n t also inverts cane-sugar, but it camnot carry fermentation any fu&her. C. H. B. Method of Preventing Secondary Fermentations. By .U. GAYON and G . DuPEwr (Compt. rend., 103, 883-885).-The addition of tannin in quantities of 0.5-1 *O gram per litre gives good results, but does not prevent the development of Mjycoderma aceti.Salts of bismuth, even in small quantities, completely prevent secondary fermentations. The addition of 0.1 gram of ba,sic bismuth nitrate per litre almost entirely prevents any increase in the acidity of the wort, and by keeping the yeast pure produces a distinct increase in the proportion of alcohol. The character of the results is seen from the following table. The first column in each set of expe- riments shows the behaviour of the wort containing the bismuth salt, and the second column shows the behaviour of the ordinary wort :-172 ABSTRACTS OF UHEMIOAL PAPERS. ~- 200 c ~ n 0 1060 0.25 1029 32' 6.7 4.94 I A* 200 cane 1060 0-25 1030 33' 26.5 4-71 Capacity of vat in hectolitres . . . . Source of mdasses.. . . . . . . . . . . . .Density of molasses wort,. . . . . , . Proportion of maize wort.. . . .. . Density of maize wort , . .. , , .. ,. Maximum temperature. . , . , . . . . . Increase of widity.. . . . . . . , , . . . . Percentage of alcohol in product . Difference in amount of alcohol . . 200 cane 1060 0'25 1035 33' 4.5 4.96 1075 0 . 1 1031 35' 2 -5 5 -87 -0 200 cane 1060 0.25 1034 32 5 36.0 4.37 600 beetroot 1075 0 . 1 1031 35O 13 -0 5-74 -13 C. H. B. Is Free Nitrogen formed during Putrefaction? By A. EHRENBERG ( Z e d . physiol. Chem., 11, 145-179) .-Considering the important part that nitrogen plays in the organisms of plants and animals, many researches have been undertaken to determine, first, whether the atmospheric nitrogen takes any part in the nutrition of organisms, especially low organisms like bacteria, or whether as a result of decomposition, nitrogen in the free state is formed; the conclusions drawn by various workers are most contradictory.The preseiit research is devoted only to the investigation of the question 8s to whether nitrogen is formed in putrefactive processes. The author intends to pursue the subject further in relation to nitrifica- tion. By means of an apparatus, which is described and figured, the use of caoutchouc stoppers is dispensed with, as diffusion takes place through these ; wherever a stopcock is necessary, it is immersed in a trough of mercury. The gases formed by various putrefying mix- tures were analysed. The method of gas analysis is preferable to that of nitrogen estimations, since certain nitrogenous compounds, formed by putrefaction (e.g., of the quinoline and pyridine groups), undergo dissociation at a high temperature.The substances investi- gated were dried blood moistened with cow's urine, cow's urine alone or mixed with calcium carbonate, and the dung of horses and COWS. These substances were mixed with some liquid in which putre- faction was taking place, and the investigation carried out in the presence of pure oxygen, so that only the agrobic organisms could a c t ; carbonic anhydride was formed, but no nitrogen. I n other experiments carried out in the absence of oxygen on a mixture of broth, sugar, peptone, sodium phosphate, sodium chloride, and sodium nitrate, it was also found that no nitrogen was formed. These experiments were carried out in an atmosphere of carbonic anhydride, in which only the anaikobic bacteria would be able to act.It was also found that during the slow combustion of organic materials no nitrogen was formed. W. D. H. Absorption of Carbonic Anhydride by Leaves. By P. P. DEHERA~X and MAQUENNE (Ann. Agronom., 12, 526-534).--The authors cite determinations which confirm the conclusions already arrived at by them, namely, that the absorption of carbonic anhydrideVEGETABLE PHY SIOLOOY AND AGRICULTURE, 173 by vegetable tissues ie a true phenomenon of solution, varying with the temperature, as in all cases of absorption of gas by an inert solvent, and which, consequently, when the leaf respires in an atmosphere kept at constant pressure, gives rise to a supersaturation comparable with that of a mass of water into which calcium carbonate and hydrochloric acid have been introduced simultaneously.This absorption of carbonic anhydride by leaves is extremely rapid, at any rate when the leaves are in a vacuum, in consequence of the large surface exposed. By A. MUNTZ (Am. Agro?iom., 12,399-400). -Unripe rye grain contains a notable proportion of svnanthrose, a sugar analogous to cane-sugar, and only found up to the present in the roots or tubercles of certain Synantheracese. The synanthrose in the dry grain was on May 25th 45 per cent. t o 21.55 per cent. starch, and on July 12th 6.83 per cent. to 68.78 per cent. starch. There is atill some synanthrose in the ripe grain after being kept for months. The uniipe grain of wheat also contains synanthrose, which, however, does not persist, but is gradually replaced by cane-sugar ; wheat also contains an inverting ferment capable of transforming synanthrose into reducing sugars.200 grains of wheat weighed after desiccation at 9 A.M. 10.042 grams ; after exposure to the sun for 12 hours they weighed 8.648 grams, the loss being due to slow combustion. The young colza seed contains cane-sugar and a reducing sugar having the rotatory power of invert, sugar; at maturity, cane-sugar alone remains. By determining from time to time the sugar, starch, fat, and nitrogenous matter in a constant number of colea seeds during an increase in weight from 121 mgrms. to 498 mgrms., the author finds that the glucose diminishes gradually and disappears, the cane- sugar increases, the starch, always present in small quantity, gradually diminishes, the nitrogenous and fatty matters constantly increase.It, therefore, appears that the seed itself does not contain the carbo- hydrates which undergo transformation into oil ; but analyses of the pod or siliqna at various dates show that sugar and starch con- stantly flow there, and disappear after a short sojourn, thus probably furnishing the material out of which the oil of the seed is elaborated. So-called Soluble Starch. By J. KRAUS (Ann. Agronom., 12, %40-541).-Janis and Schenk have found in the epidermis of Omitho- yaksrn and of Gageu a substance dissolved in the cell sap which strikes k blue colour with iodine. Nageli has shown that it is not sfarch, and believes it to be an albuminoid.The author, having met, with this same substance in the epidermis of some Arums, has come t o the conclusion that it is allied t o the tannim. Chloriodide of zinc colours it rose, ferric chloride and ferrous sulphate strike a brownish-green ; on the other hand, potassium dichromate and Gardiner's reagent give no reactions, The substance behaves like a tannin in being developed under the influence of light, and in persisting without alteration in dead or dying leaves. That iodine should strike a blue colour with a tannin is not surprising, since Giessinayer has shown that a solution of tannin gives with a weak solution of iodine, in feebly J. 116. H. M. Ripening of Seeds. J. M. H. M. VOL. LIT, n174 ABSTRACTS OF CHEMICAL PAPERS. alkaline water, a bright red colour, and Nasser has recognised that tannic and gallic acids and pyrogallol, in the presence of neutral salts or acids, are coloured red-purple by iodine. Substances contained in the Roots of Hydrastis Canadensis.By M. FREUND and W. WILL (Ber., 19, 2797-2803).-Perrins (Pharm. J . Trans. 121, 3, 546) obtained from the root of Hydrasfis, berberine and another alkalo'id to which he ascribed the name hydras. tine. The authors found that the latter is best obtained by extracting the finely powdered roots with ether. It melts at 132" and crystallises in the rhombic system; a : b : c = 0.8461 : 1 : 0-3761. The solution in chloroform (1.2759 gram to 50 c.c.) has a rotatory power [a]= = -67.8" ; in aqueous hydrochloric acid, [a]= = + 12i.3". Analyses of the compound confirm the formula CzzHz3NOs, ascribed to it by Mahla (Amer.J. Sci. [el, 36,57). It reacts with methyl iodide, yielding the compound CZzHzqNO6,MeI. This crystallises from alcohol or water in needles melting at 208". When hydrastine is dissolved in hydro- chloric acid and treated with potassium permanganate, it is converted into opianic: acid. Nitric acid acts on hydrastine, yielding a base melting at 115", very readily soluble in chloroform, alcohol, and ether. Hydrastine is not changed when fused with potash. These experi- ments show that great analogy exists between hydrastine and narcotine. Another compound was isolated from the roots of the Hydrastis; it crystalliscs well and melts at 100". It does not contain nitrogen. It dissolves unchanged in hot strong hydrochloric acid and in warm aqueous potash, and appears therefore to be a lactone.J. M. H. M. N. H. M. Valuation of Manures. By P. P. DEHBRAIN (Ann. A ~ T o ~ I o ~ . , 12, 436-444).-The author expresses the value of a manure or manurial constituent for a particular soil or crop in the following manner. If R is the yield per hectare on the manured plot, and R' that on the unmanured plot, V the price of the produce, and P the weight of manure used, then the value of the unit of weight of the manure for that soil and crop is (R-R')V . In the case of nitrogenous manures, if N, the weight of nitrogen in the manure, be substituted for P in the above expression we get as quotient the value of the unit of nitrogen in that particular form and case. Applying this method to the results of field experiments at Grignon, the author shows the different values that the unit of nitrogen may have in different forms and under different circumstances. Thus with green maize in 18i9- fr.c. 6 60 The kilo. of nitrogen in farmyard manure was worth. . . . 9, ,, nitrate of soda ,, .... 2 34 >, ,, flesh manure (large dressing) . . 0 88 99 >, 9 , ,, (small ,, ) . . 1 43 The experiments with oats from 1875-1879 yield the following values :-VEGETABLE PHYSIOLOGY AND AGRICULTURE. 175 fr. c . Nitrogen in farmyard manure. ...... 3 26 per kilo. ,, nitrate of soda.. ........ 3 68 ,, ,, mixture of the two.. .... 4 17 Production of Farmyard Manure. By A. MUNTZ and C. GIRARD (Ann. Agronom., 12, 429-436) .-By exact experiments, the authors have sought to establish the proportions of the total manurial elements in the food consumed which become stored up in the increase of live-weight, recovered in the manure, and lost.The food given was weighed and analysed, the increase of live-weight or the quantity of milk yielded during the duration of the experiments noted, and the manure carefully collected and analysed. The following results were obtained : 32 sheep kept in a fold with asphalt floor so as to prevent loss of manure, gave the following results :- J. M. H, M. Nitrogen consumed. ......... 21.817 kilos. ,, convertedinto flesh.. 4.300 ,, = 21.7 per cent. ,, recovered in manure. 5-588 ,, = 19.72 ,, ,, lost. .............. 12.129 9, = 55.58 ,, Some of this great loss of nitrogen ie due to escape into the air of ammonium carbonate; the air of the fold was found to contain about 0.008 gram ammonia per cubic metre, or 400 times as much as normal air.Two Normandy cows were each fed daily with 53+ kilos. of lucerne and 49 kilos. of water, and each furnished 33 kilos. of solid excreta and 18 kilos. of urine. The weight of the animals increased by 15 kilos. during the experiment, and they furnished 361 litres of milk. kilos. 0'544 3.104 = 21.95 per cent. Nitrogen consumed. ......... 14.146 ,, assimilated as flesh.. Y , ,, in milk.. 2 5 6 0 } ,, in manure.. ........ 7.461 =52.75 ,, ,, l o s t . .............. 3,581 =2530 ,, The loss is much less than in the case of the sheep, probably because the fermentation being less active, less ammonium carbonate is formed. Quantity of Fertilising Matter supplied to the Soil by Crazing Sheep.-With a ration of green lucerne and straw litter, 2.230 kilos. of manure were produced for 4.085 kilos. of lucerne consumed and 0.9 kilo. of water drunk. The phosphoric acid in the forage was 2.952 kilos., and in the manure 2.955 kilos. ; the potash in the forage 13.002 kilos., and in the manure 15.280 kilos., there was therefore no loss of these fertifising constituents ; the distribution of the nitrogen was as under :- The sheep increased in weight 30 kilos. kilos. Nitrogen consumed. ........... 14 548 ,, assimilated as flesh.. .. 1.089 = 7.50 per cent. ,, in manure. .......... 6.349 = 43-64 ,, ,, lost ................ 7.110 = 48.87 ,, ln2176 ABSTRACTS OF CHEMICAL PAPERS. With an earth litter the loss of nitrogen was much less, as the following figures show :- kilos.Nitrogen consumed. ........... 13.707 ,, fixed by animal ...... 1.379 = 10.06 per cent. ,, in manure .......... 9.042 = 65-96 ,, ,, lost ................ 2.376 = 23.98 ,, Phosphoric acid in fodder ...... 2 820 9, ,, manure.. .... 3260 Potash in fodder .............. 13.235 ,, manure.. ............ 12.017 The advantage of earth litter over straw litter, and of the custom of folding on the soil instead of stabling, is demonstrated by these experiments. With lucerne hay and straw litter, the following results were obtained. kilos. Nitrogen consumed. ........... 23.011 ,, fixed by animal ...... 1.670 = 7.25 per cent. ,, in manure.. ......... 8.899 = 38.67 ,, ,, lost ................ 12.442 = 51.08 J.M.’H. M. Manurial Value of Basic Steel Slag. By J. WRIGHTSON and J. M. H. MUNRO (An%. Agronom., 12, 488-495).*-The basic steel cinder or Thomas slag eiiiployed in these experiments had the following composition :-CaO, 41-54 ; MgO, 6.13 ; A1203, 2.60 ; FeO, 14.66 ; F203, 8.64; MnO, 3 81 ; Vz03. 0.29 ; SiOl, 7.40; Pz05, 14.32 ; SO3, 0.31 ; S, 0.23 ; total 99.93. Side by side with this were tried ground Cambridge coprolites containing 25.1 per cent. P2O5 ; mineral super- phosphate of ordinary quality containing 12.0 per cent. soluble P205 ; rich (Curagoa) superphosphate containing 20.1 per cent. soluble P205 ; and also precipitated pho5phate of lime prepared from basic cinder by Scheibler’s process. This precipitated phosphate contained 30.89 per cent. P205, with CaO, 29.91 ; FezO,, 3.62 ; SiO,! 7.53; water, 18-72; the P,05 in this product is practically all soluble in ammonium citrate.The experiments were made in duplicate on a thin, light, chalky soil at Downton (Wilts), and on a stiff clay nearly destitute of lime at Ferryhill (Durham), with plots & acre i n area. Duplicate plots of each dressing were employed at both stations ; there were 35 plots in each series, and they were so arranged as to permit a comparison of every manured plot with one or more udjrtced unmanured plots ; the special comparisons between the different manures were also obtained from adjacent plots. Swedes were grown at Downton, and yellow Aberdeen turnips at Ferryhill; the mean yield of the six unmunured Downton plots was 2360 roots, weighing6 cwts.0 qr. 14 lbs., and that of the six uiznianured Ferryhill plots was 362 roots, weighing 2 cwts. 2 qrs. 7 lbs. On the unmariured plots at Ferryhill, most of the young * ‘‘ Report of Experiments made to ascertain the manurial value of Basic Cinder produced at the works of the North Eastern Steel Co., Limited,” Middlesborough, 1886.VEGETBBLE PBY SIOLOGY ASD AGRICULTURE. 177 plants were unable to withstand the attack of the fly, on the manured plots, failure from this cause did not take place. The following table shows the mean increases over the unmanured plots obtained both at Downton and Ferryhill with the different manures :- --- 2 cwts. basic cinder.. ......... 54 lbs. superphosphate.. ...... 35 lbs. Precipitated phosphate.. 45 lbs. superphosphate........ 45 lbs. basic cinder .......... 28 lbs. rich superphosphate.. .. 17 lbs. precipitated phosphate.. 78i lbs. basic cinder.. ........ 45 lbs. ground coprolites ...... lbs. P20,. -- 32 -0 6 -5 10 -9 5.4 6.5 5 - 6 5 *3 11 *2 11 -2 Increase per plot & acre. Downton, cwts, qrs. lbs. 9 2 2 0 8 3 15 7 0 20 5 3 25 5 0 3 4 2 15 3 3 13 2 3 5 0 1 2 Ferryhill. owts. qrs. lbs. 12 1 14 14 0 21 10 3 7 9 1 7 11 0 21 10 1 7 9 0. 21 10 1 15 & . 2 0 At Downton, on a thin, chalky soil, it will be seen that 4 cwts. per acre of basic cinder was a little inferior to an equal weight of super- phosphate, but vastly superior to the same quantity of ground coprolites. If dressings of these manures containing equal weights of phosphoric acid are compared, it is found that the unit of B205 in basic cinder is a little inferior in efficiency to that in superphosphate, inferior also to that in precipitated phosphate, but decidedly superior to the unit of phosphoric acid in ground coprolites.Making the same comparisons at Ferryhill on this clay soil, deficient in lime, it is found that soluble phosphoric acid loses a great deal of its superiority over the insoluble forms. 4 cwts. per acre of basic cinder is actually a better manure than an equal weight of superphosphate, and but very little inferior to a dressing of superphosphate containing an equal weight of phosphoric acid; in fact, on this soil, soluble phosphate, cinder phosphate, and precipitated phospbate are very near each other in efficiency, with coprolite phosphate a little way behind.At Downton, a heavy dressing of basic cinder gave the best result, at Ferryhill, a dressing of 4 cwts. per acre was almost as efficacious as one of 20 cwts. per acre. The general conclusion deducible from these experiments is that phosphoric acid exists in basic cinder in a condition to be easily assimilated by plants, and that in this respect it resembles soluble phosphoric acid and precipitated phosphoric acid much more than the insoluble phosphoric acid of ground mineral phosphates, hence Thomas- slag is likely to occupy an important position as a phosphatic manure. In the two years 1884 and 1885 there were no signs of injury to the crop even from the heaviest drsssingsof basic cinder, namely, 1 and 2 tons per acre. Besides the precipitated phosphate prepared from basic cinder, two other patented preparations were included in the series of experiments, but in view of the very striking results obtained with178 ABSTRACTS OF CHEMICAL PAPERS.the raw ground cinder, these proposals lose much of their interest. According to one of these patents (Munro and Wrightson, No. 250, A.D. IS%), ground basic cinder is used as a precipitating agent for the soluble phosphoric acid of rich superphosphate, and by mixing the two substances in suitable proportions, a manure of moderate richness is obtained, free from any excessive proportion of oxides of iron, and containing phosphoric acid in three highly assimilable forms,-soluble, “ precipitated,” and cinder phosphoric acid. The plots on which thin manure was tried show that the efficacy of the soluble phosphoric acid was not weakened by partial precipitation, and that the cinder phosphoric acid in the compound manure exercised a manurial effect over and above that due to the phosphoric acid of the superphosphate. The manufacture of a superphosphate from basic cinder itself has also been tried and patented (‘Munro, No.7740, A.D. 1885). When treated with the proper quantity of sulphuric acid, basic cinder is converted into a light green, dry, friable, and very open substance containing a large proportion of calcium sulphate, soluble phosphate of lime, and about 12 per cent. of crystallised ferrous sulphate. (A p.ortion of the phosphoric acid exists as soluble ferrous phosphate.) In mew of the recent experiments of Griffiths, it was thought that the ferrous sulphate contained in this manure might exert a beneficial effect on vegetation, instead of being, according to the common belief, an absolute poison. The effect of ferrous sulphate on vegetation seems to depend on the dose, a small quantity being sometimes beneficial, and a large one invariably noxious. On the experimental pfots to which the “ dissolved cinder ” was applied, the effect of the ferrous sulphate appeared to be uniformly disadvantageous.The dissolved cinder in all cases had some manurial value, giving increases over the unmanured plots, but these increases were less than were obtained with the same quantity of cinder not dissolved by acid, so that the sulphate of iron appears to have neutralised a part of the benefit derived from the phosphoric acid.J. M. H. M. Influence of the Ferrous Oxide in Basic Cinder on the Growth of Plants. By J. M. H. MUNRO (Middlesborough, 1886).-This report contain8 experiments supplementary to those which formed the subject of the preceding Abstract. Seeds of various sorts-barley, white turnips, clover, white mustard, garden cress-were sown in mixtures of garden soil with basic cinder, in order t o ascertain whether the large proportion of ferrous oxide i u the basic cinder exercises any unfavourable influence on germination or growth. In order to put this question to the severest test, enormously exaggerated doses of basic cinder were employed, namely, 10 per cent. of the mixed soil, 25 per cent., 50 per cent., and pure basic cinder without any soil.Mcst of the seeds tried germinated even in the pure basic cinder, and some of the plants lived until starved for want of nitrogenous food. Ail the other mixtures produced plants which flowered and seeded in due course-the barley plants in the mixture of equal parts of basic cinder and garden soil were actually better than those grown in garden soil alone, and produced full ears of grain of unimpaired germinating power. Since basic cinder is an alkaline substance containing freeAEALYTICAL CHEMISTRY. 179 lime, it is only natural that in the three strongest mixtures fewer seeds germinated than in the three weaker mixtures or in garden soil alone. The conclusion arrived at is that the ferrous oxide contained in basic cinder is without injurious influence on germination or gro w t h.J. M. H. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 171Chemistry of Vegetable Physiology and Agriculture.Reduction of Copper Sulphate duringBy H. QUANTIN (Compt. rend., 103, tion.Alcoholic Fermenta-888-883) .-In exmri-ments on-a small scale, it is found that copper existing in the for’m ofcopper sulphate to the extent of 0.05 gram per litre, is completelyprecipitated in the form of copper sulphide during alcoholic fermenta-tion. On a large scale, doubtless a still larger quantity would beremoved, but the quantity given is greater than would ever be intro-duced into the wort as a result of the use of copper sulphate as aremedy for mildew. Since moist copper sulphide is readily oxidised,it is important to avoid any akation of the lees containing it.TheRulphide is the only salt of copper which is insoluble in the must ofgrapes. C. H. R.Alcoholic Fermentation of Dextrin and Starch. By U.GAYON and E. DUBOURG (Compt. rend., 103, 885--887).--The authorshave met with a species of Mucor which has the power of convertingdextrin and starch into sugar, and then fermenting the sugar but,like Mzccor circin,elloides, it has not the power of inverting cane-sugar,and transforming it into alcohol. Other non-inversive ferments. onthe other hand, have not the power of fermenting dextrin and starch.In beer wort or solutions of glucose, this mucor develops rapidly inlarge, spherical, ferment cellulen. Jn dextrin or starch, i t a t first formsmgcelial tubes, which soon swell up, divide, and form themselves intoglobular masses.In yeast-water containing sugar, the mucor formsonly A bulky, unicellular mycelium.The fermentation of dextrin takes place somewhat slowly, and thatof starch requires still longer. The dextrin existing in beer is readilysaccharified by this mucor and converted into alcohol, if the alcoholalready in the beer is expelled before adding the ferment.Eurotium oryze, used in the manufacture of “koji,” secretes adiastase which converts rice into a true malt, and this d a n t alsoinverts cane-sugar, but it camnot carry fermentation any fu&her.C. H. B.Method of Preventing Secondary Fermentations. By .U. GAYON and G . DuPEwr (Compt. rend., 103, 883-885).-The additionof tannin in quantities of 0.5-1 *O gram per litre gives good results,but does not prevent the development of Mjycoderma aceti.Salts of bismuth, even in small quantities, completely preventsecondary fermentations.The addition of 0.1 gram of ba,sic bismuthnitrate per litre almost entirely prevents any increase in the acidityof the wort, and by keeping the yeast pure produces a distinctincrease in the proportion of alcohol. The character of the results isseen from the following table. The first column in each set of expe-riments shows the behaviour of the wort containing the bismuth salt,and the second column shows the behaviour of the ordinary wort :172 ABSTRACTS OF UHEMIOAL PAPERS.~-200c ~ n 010600.25102932'6.74.94I A*200cane10600-25103033'26.54-71Capacity of vat in hectolitres .. . .Source of mdasses.. . . . . . . . . . . . .Density of molasses wort,. . . . . , .Proportion of maize wort.. . . .. .Density of maize wort , . .. , , .. ,.Maximum temperature. . , . , . . . . .Increase of widity.. . . . . . . , , . . . .Percentage of alcohol in product .Difference in amount of alcohol . .200cane10600'25103533'4.54.9610750 . 1103135'2 -55 -87-0200cane10600.25103432 536.04.37600beetroot10750 . 1103135O13 -05-74-13C. H. B.Is Free Nitrogen formed during Putrefaction? By A.EHRENBERG ( Z e d . physiol. Chem., 11, 145-179) .-Considering theimportant part that nitrogen plays in the organisms of plants andanimals, many researches have been undertaken to determine, first,whether the atmospheric nitrogen takes any part in the nutritionof organisms, especially low organisms like bacteria, or whether as aresult of decomposition, nitrogen in the free state is formed; theconclusions drawn by various workers are most contradictory.Thepreseiit research is devoted only to the investigation of the question8s to whether nitrogen is formed in putrefactive processes. Theauthor intends to pursue the subject further in relation to nitrifica-tion. By means of an apparatus, which is described and figured, theuse of caoutchouc stoppers is dispensed with, as diffusion takes placethrough these ; wherever a stopcock is necessary, it is immersed in atrough of mercury. The gases formed by various putrefying mix-tures were analysed.The method of gas analysis is preferable tothat of nitrogen estimations, since certain nitrogenous compounds,formed by putrefaction (e.g., of the quinoline and pyridine groups),undergo dissociation at a high temperature. The substances investi-gated were dried blood moistened with cow's urine, cow's urinealone or mixed with calcium carbonate, and the dung of horses andCOWS. These substances were mixed with some liquid in which putre-faction was taking place, and the investigation carried out in thepresence of pure oxygen, so that only the agrobic organisms coulda c t ; carbonic anhydride was formed, but no nitrogen. I n otherexperiments carried out in the absence of oxygen on a mixture ofbroth, sugar, peptone, sodium phosphate, sodium chloride, andsodium nitrate, it was also found that no nitrogen was formed.These experiments were carried out in an atmosphere of carbonicanhydride, in which only the anaikobic bacteria would be able toact.It was also found that during the slow combustion of organicmaterials no nitrogen was formed. W. D. H.Absorption of Carbonic Anhydride by Leaves. By P. P.DEHERA~X and MAQUENNE (Ann. Agronom., 12, 526-534).--Theauthors cite determinations which confirm the conclusions alreadyarrived at by them, namely, that the absorption of carbonic anhydridVEGETABLE PHY SIOLOOY AND AGRICULTURE, 173by vegetable tissues ie a true phenomenon of solution, varying withthe temperature, as in all cases of absorption of gas by an inertsolvent, and which, consequently, when the leaf respires in anatmosphere kept at constant pressure, gives rise to a supersaturationcomparable with that of a mass of water into which calcium carbonateand hydrochloric acid have been introduced simultaneously.This absorption of carbonic anhydride by leaves is extremely rapid,at any rate when the leaves are in a vacuum, in consequence of thelarge surface exposed.By A.MUNTZ (Am. Agro?iom., 12,399-400).-Unripe rye grain contains a notable proportion of svnanthrose, asugar analogous to cane-sugar, and only found up to the present inthe roots or tubercles of certain Synantheracese. The synanthrose inthe dry grain was on May 25th 45 per cent. t o 21.55 per cent.starch,and on July 12th 6.83 per cent. to 68.78 per cent. starch. There isatill some synanthrose in the ripe grain after being kept for months.The uniipe grain of wheat also contains synanthrose, which, however,does not persist, but is gradually replaced by cane-sugar ; wheat alsocontains an inverting ferment capable of transforming synanthroseinto reducing sugars. 200 grains of wheat weighed after desiccationat 9 A.M. 10.042 grams ; after exposure to the sun for 12 hours theyweighed 8.648 grams, the loss being due to slow combustion. Theyoung colza seed contains cane-sugar and a reducing sugar havingthe rotatory power of invert, sugar; at maturity, cane-sugar aloneremains. By determining from time to time the sugar, starch, fat,and nitrogenous matter in a constant number of colea seeds duringan increase in weight from 121 mgrms.to 498 mgrms., the authorfinds that the glucose diminishes gradually and disappears, the cane-sugar increases, the starch, always present in small quantity, graduallydiminishes, the nitrogenous and fatty matters constantly increase. It,therefore, appears that the seed itself does not contain the carbo-hydrates which undergo transformation into oil ; but analyses ofthe pod or siliqna at various dates show that sugar and starch con-stantly flow there, and disappear after a short sojourn, thus probablyfurnishing the material out of which the oil of the seed is elaborated.So-called Soluble Starch. By J. KRAUS (Ann. Agronom., 12,%40-541).-Janis and Schenk have found in the epidermis of Omitho-yaksrn and of Gageu a substance dissolved in the cell sap which strikesk blue colour with iodine.Nageli has shown that it is not sfarch, andbelieves it to be an albuminoid. The author, having met, with thissame substance in the epidermis of some Arums, has come t o theconclusion that it is allied t o the tannim. Chloriodide of zinc coloursit rose, ferric chloride and ferrous sulphate strike a brownish-green ;on the other hand, potassium dichromate and Gardiner's reagent giveno reactions, The substance behaves like a tannin in beingdeveloped under the influence of light, and in persisting withoutalteration in dead or dying leaves. That iodine should strike a bluecolour with a tannin is not surprising, since Giessinayer has shownthat a solution of tannin gives with a weak solution of iodine, in feeblyJ.116. H. M.Ripening of Seeds.J. M. H. M.VOL. LIT, 174 ABSTRACTS OF CHEMICAL PAPERS.alkaline water, a bright red colour, and Nasser has recognised thattannic and gallic acids and pyrogallol, in the presence of neutral saltsor acids, are coloured red-purple by iodine.Substances contained in the Roots of Hydrastis Canadensis.By M. FREUND and W. WILL (Ber., 19, 2797-2803).-Perrins(Pharm. J . Trans. 121, 3, 546) obtained from the root of Hydrasfis,berberine and another alkalo'id to which he ascribed the name hydras.tine. The authors found that the latter is best obtained by extractingthe finely powdered roots with ether. It melts at 132" and crystallisesin the rhombic system; a : b : c = 0.8461 : 1 : 0-3761.The solutionin chloroform (1.2759 gram to 50 c.c.) has a rotatory power [a]= =-67.8" ; in aqueous hydrochloric acid, [a]= = + 12i.3". Analyses ofthe compound confirm the formula CzzHz3NOs, ascribed to it by Mahla(Amer. J. Sci. [el, 36,57). It reacts with methyl iodide, yielding thecompound CZzHzqNO6,MeI. This crystallises from alcohol or water inneedles melting at 208". When hydrastine is dissolved in hydro-chloric acid and treated with potassium permanganate, it is convertedinto opianic: acid. Nitric acid acts on hydrastine, yielding a basemelting at 115", very readily soluble in chloroform, alcohol, and ether.Hydrastine is not changed when fused with potash.These experi-ments show that great analogy exists between hydrastine andnarcotine.Another compound was isolated from the roots of the Hydrastis;it crystalliscs well and melts at 100". It does not contain nitrogen.It dissolves unchanged in hot strong hydrochloric acid and in warmaqueous potash, and appears therefore to be a lactone.J. M. H. M.N. H. M.Valuation of Manures. By P. P. DEHBRAIN (Ann. A ~ T o ~ I o ~ . , 12,436-444).-The author expresses the value of a manure or manurialconstituent for a particular soil or crop in the following manner. IfR is the yield per hectare on the manured plot, and R' that onthe unmanured plot, V the price of the produce, and P theweight of manure used, then the value of the unit of weight ofthe manure for that soil and crop is (R-R')V .In the case ofnitrogenous manures, if N, the weight of nitrogen in the manure, besubstituted for P in the above expression we get as quotient the valueof the unit of nitrogen in that particular form and case. Applyingthis method to the results of field experiments at Grignon, the authorshows the different values that the unit of nitrogen may have indifferent forms and under different circumstances. Thus with greenmaize in 18i9-fr. c.6 60 The kilo. of nitrogen in farmyard manure was worth. . . .9, ,, nitrate of soda ,, .... 2 34>, ,, flesh manure (large dressing) . . 0 8899 >, 9 , ,, (small ,, ) . . 1 43The experiments with oats from 1875-1879 yield the followingvalues :VEGETABLE PHYSIOLOGY AND AGRICULTURE.175fr. c .Nitrogen in farmyard manure. ...... 3 26 per kilo.,, nitrate of soda.. ........ 3 68 ,,,, mixture of the two.. .... 4 17Production of Farmyard Manure. By A. MUNTZ and C.GIRARD (Ann. Agronom., 12, 429-436) .-By exact experiments, theauthors have sought to establish the proportions of the total manurialelements in the food consumed which become stored up in the increaseof live-weight, recovered in the manure, and lost. The food given wasweighed and analysed, the increase of live-weight or the quantity ofmilk yielded during the duration of the experiments noted, and themanure carefully collected and analysed. The following results wereobtained : 32 sheep kept in a fold with asphalt floor so as to preventloss of manure, gave the following results :-J.M. H, M.Nitrogen consumed. ......... 21.817 kilos.,, convertedinto flesh.. 4.300 ,, = 21.7 per cent.,, recovered in manure. 5-588 ,, = 19.72 ,,,, lost. .............. 12.129 9, = 55.58 ,,Some of this great loss of nitrogen ie due to escape into the air ofammonium carbonate; the air of the fold was found to contain about0.008 gram ammonia per cubic metre, or 400 times as much as normalair.Two Normandy cows were each fed daily with 53+ kilos. of lucerneand 49 kilos. of water, and each furnished 33 kilos. of solid excreta and18 kilos. of urine. The weight of the animals increased by 15 kilos.during the experiment, and they furnished 361 litres of milk.kilos.0'544 3.104 = 21.95 per cent.Nitrogen consumed.......... 14.146 ,, assimilated as flesh..Y , ,, in milk.. 2 5 6 0 } ,, in manure.. ........ 7.461 =52.75 ,,,, l o s t . .............. 3,581 =2530 ,,The loss is much less than in the case of the sheep, probablybecause the fermentation being less active, less ammonium carbonateis formed.Quantity of Fertilising Matter supplied to the Soil by Crazing Sheep.-With a ration of green lucerne and straw litter, 2.230 kilos. ofmanure were produced for 4.085 kilos. of lucerne consumed and0.9 kilo. of water drunk.The phosphoric acid in the forage was 2.952 kilos., and in themanure 2.955 kilos. ; the potash in the forage 13.002 kilos., and in themanure 15.280 kilos., there was therefore no loss of these fertifisingconstituents ; the distribution of the nitrogen was as under :-The sheep increased in weight 30 kilos.kilos.Nitrogen consumed............ 14 548,, assimilated as flesh.. .. 1.089 = 7.50 per cent. ,, in manure. .......... 6.349 = 43-64 ,,,, lost ................ 7.110 = 48.87 ,,ln176 ABSTRACTS OF CHEMICAL PAPERS.With an earth litter the loss of nitrogen was much less, as thefollowing figures show :-kilos.Nitrogen consumed. ........... 13.707,, fixed by animal ...... 1.379 = 10.06 per cent.,, in manure .......... 9.042 = 65-96 ,,,, lost ................ 2.376 = 23.98 ,,Phosphoric acid in fodder ...... 2 8209, ,, manure.. .... 3260Potash in fodder .............. 13.235 ,, manure.. ............ 12.017The advantage of earth litter over straw litter, and of the customof folding on the soil instead of stabling, is demonstrated by theseexperiments.With lucerne hay and straw litter, the following results wereobtained.kilos.Nitrogen consumed............ 23.011,, fixed by animal ...... 1.670 = 7.25 per cent. ,, in manure.. ......... 8.899 = 38.67 ,,,, lost ................ 12.442 = 51.08J. M.’H. M.Manurial Value of Basic Steel Slag. By J. WRIGHTSON and J.M. H. MUNRO (An%. Agronom., 12, 488-495).*-The basic steel cinderor Thomas slag eiiiployed in these experiments had the followingcomposition :-CaO, 41-54 ; MgO, 6.13 ; A1203, 2.60 ; FeO, 14.66 ;F203, 8.64; MnO, 3 81 ; Vz03. 0.29 ; SiOl, 7.40; Pz05, 14.32 ; SO3,0.31 ; S, 0.23 ; total 99.93. Side by side with this were tried groundCambridge coprolites containing 25.1 per cent.P2O5 ; mineral super-phosphate of ordinary quality containing 12.0 per cent. soluble P205 ;rich (Curagoa) superphosphate containing 20.1 per cent. soluble P205 ;and also precipitated pho5phate of lime prepared from basic cinder byScheibler’s process. This precipitated phosphate contained 30.89 percent. P205, with CaO, 29.91 ; FezO,, 3.62 ; SiO,! 7.53; water, 18-72;the P,05 in this product is practically all soluble in ammonium citrate.The experiments were made in duplicate on a thin, light, chalky soil atDownton (Wilts), and on a stiff clay nearly destitute of lime atFerryhill (Durham), with plots & acre i n area. Duplicate plots ofeach dressing were employed at both stations ; there were 35 plots ineach series, and they were so arranged as to permit a comparison ofevery manured plot with one or more udjrtced unmanured plots ; thespecial comparisons between the different manures were also obtainedfrom adjacent plots.Swedes were grown at Downton, and yellowAberdeen turnips at Ferryhill; the mean yield of the six unmunuredDownton plots was 2360 roots, weighing6 cwts. 0 qr. 14 lbs., and thatof the six uiznianured Ferryhill plots was 362 roots, weighing 2 cwts.2 qrs. 7 lbs. On the unmariured plots at Ferryhill, most of the young* ‘‘ Report of Experiments made to ascertain the manurial value of Basic Cinderproduced at the works of the North Eastern Steel Co., Limited,” Middlesborough,1886VEGETBBLE PBY SIOLOGY ASD AGRICULTURE. 177plants were unable to withstand the attack of the fly, on the manuredplots, failure from this cause did not take place.The following tableshows the mean increases over the unmanured plots obtained both atDownton and Ferryhill with the different manures :----2 cwts. basic cinder.. .........54 lbs. superphosphate.. ......35 lbs. Precipitated phosphate..45 lbs. superphosphate. .......45 lbs. basic cinder ..........28 lbs. rich superphosphate.. ..17 lbs. precipitated phosphate..78i lbs. basic cinder.. ........45 lbs. ground coprolites ......lbs. P20,.--32 -06 -510 -95.46.55 - 65 *311 *211 -2Increase per plot & acre.Downton,cwts, qrs. lbs.9 2 2 08 3 157 0 205 3 255 0 34 2 153 3 132 3 50 1 2Ferryhill.owts.qrs. lbs.12 1 1414 0 2110 3 79 1 711 0 2110 1 79 0. 2110 1 15& . 2 0At Downton, on a thin, chalky soil, it will be seen that 4 cwts. peracre of basic cinder was a little inferior to an equal weight of super-phosphate, but vastly superior to the same quantity of groundcoprolites. If dressings of these manures containing equal weights ofphosphoric acid are compared, it is found that the unit of B205 inbasic cinder is a little inferior in efficiency to that in superphosphate,inferior also to that in precipitated phosphate, but decidedly superior tothe unit of phosphoric acid in ground coprolites. Making the samecomparisons at Ferryhill on this clay soil, deficient in lime, it is foundthat soluble phosphoric acid loses a great deal of its superiority overthe insoluble forms. 4 cwts.per acre of basic cinder is actually a bettermanure than an equal weight of superphosphate, and but very littleinferior to a dressing of superphosphate containing an equal weight ofphosphoric acid; in fact, on this soil, soluble phosphate, cinderphosphate, and precipitated phospbate are very near each other inefficiency, with coprolite phosphate a little way behind. At Downton,a heavy dressing of basic cinder gave the best result, at Ferryhill, adressing of 4 cwts. per acre was almost as efficacious as one of 20 cwts.per acre. The general conclusion deducible from these experimentsis that phosphoric acid exists in basic cinder in a condition to be easilyassimilated by plants, and that in this respect it resembles solublephosphoric acid and precipitated phosphoric acid much more than theinsoluble phosphoric acid of ground mineral phosphates, hence Thomas-slag is likely to occupy an important position as a phosphatic manure.In the two years 1884 and 1885 there were no signs of injury to thecrop even from the heaviest drsssingsof basic cinder, namely, 1 and 2tons per acre.Besides the precipitated phosphate prepared from basiccinder, two other patented preparations were included in the series ofexperiments, but in view of the very striking results obtained wit178 ABSTRACTS OF CHEMICAL PAPERS.the raw ground cinder, these proposals lose much of their interest.According to one of these patents (Munro and Wrightson, No.250,A.D. IS%), ground basic cinder is used as a precipitating agent for thesoluble phosphoric acid of rich superphosphate, and by mixing the twosubstances in suitable proportions, a manure of moderate richness isobtained, free from any excessive proportion of oxides of iron, andcontaining phosphoric acid in three highly assimilable forms,-soluble,“ precipitated,” and cinder phosphoric acid. The plots on which thinmanure was tried show that the efficacy of the soluble phosphoricacid was not weakened by partial precipitation, and that the cinderphosphoric acid in the compound manure exercised a manurial effectover and above that due to the phosphoric acid of the superphosphate.The manufacture of a superphosphate from basic cinder itself has alsobeen tried and patented (‘Munro, No.7740, A.D. 1885). Whentreated with the proper quantity of sulphuric acid, basic cinder isconverted into a light green, dry, friable, and very open substancecontaining a large proportion of calcium sulphate, soluble phosphateof lime, and about 12 per cent. of crystallised ferrous sulphate.(A p.ortion of the phosphoric acid exists as soluble ferrous phosphate.)In mew of the recent experiments of Griffiths, it was thought that theferrous sulphate contained in this manure might exert a beneficialeffect on vegetation, instead of being, according to the common belief,an absolute poison. The effect of ferrous sulphate on vegetationseems to depend on the dose, a small quantity being sometimesbeneficial, and a large one invariably noxious. On the experimentalpfots to which the “ dissolved cinder ” was applied, the effect of theferrous sulphate appeared to be uniformly disadvantageous. Thedissolved cinder in all cases had some manurial value, giving increasesover the unmanured plots, but these increases were less than wereobtained with the same quantity of cinder not dissolved by acid, sothat the sulphate of iron appears to have neutralised a part of thebenefit derived from the phosphoric acid. J. M. H. M.Influence of the Ferrous Oxide in Basic Cinder on theGrowth of Plants. By J. M. H. MUNRO (Middlesborough, 1886).-Thisreport contain8 experiments supplementary to those which formed thesubject of the preceding Abstract. Seeds of various sorts-barley, whiteturnips, clover, white mustard, garden cress-were sown in mixturesof garden soil with basic cinder, in order t o ascertain whether thelarge proportion of ferrous oxide i u the basic cinder exercises anyunfavourable influence on germination or growth. In order to putthis question to the severest test, enormously exaggerated doses ofbasic cinder were employed, namely, 10 per cent. of the mixed soil, 25per cent., 50 per cent., and pure basic cinder without any soil. Mcstof the seeds tried germinated even in the pure basic cinder, and someof the plants lived until starved for want of nitrogenous food. Ailthe other mixtures produced plants which flowered and seeded in duecourse-the barley plants in the mixture of equal parts of basic cinderand garden soil were actually better than those grown in garden soilalone, and produced full ears of grain of unimpaired germinatingpower. Since basic cinder is an alkaline substance containing freAEALYTICAL CHEMISTRY. 179lime, it is only natural that in the three strongest mixtures fewerseeds germinated than in the three weaker mixtures or in garden soilalone. The conclusion arrived at is that the ferrous oxide containedin basic cinder is without injurious influence on germination orgro w t h. J. M. H. M

ISSN:0368-1769    

DOI:10.1039/CA8875200171

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

AEALYTICAL CHEMISTRY. 179 A n a1 y t i c a 1 C h e m i s t r y. Apparatus for Gas Analysis. By 0. PETTERSSON (Zeit. anal. C'hem., 25, 479-484) .-The principle on which the measurements are made is similar to that employed for air analysis (this vol., p. 180). The standard volume of air is, however, contained in ft special bulb con- nected with the eudiometer through the differential manometer. The gas is introduced by a side tube from a bell-glass inverted in a mercury trough. The absorptions take place in Orsat tubes connected with the eudiometer by stopcocks. There are also wires for explo- sions. M. J. S. Universal Spectroscope for Qualitative and Quantitative Chemical Analysis. By G. KRUSS (Bey., 19, Y739--2746).-A modified form of Bunsen and Kirchhoffs spectroscope is described with sketches.New Volumetric Method for Determining Fluorine. By F. OETTEL (Zeit. anal. Chem., 25, 5u5--511).--The fluorine is measured a s silicon fluoride in a special form of eudiometer. The decomposi- tion vessel is tt stoppered flask with the neck above the stopper enlarged into a cup for holding mercury. A tube branching from the neck is ground into the top of the eudiometer, the joint being also covered with mercury. The eudiometer is connected at its lower end with a mercury tube like that of the nitrometer. The graduation begins 10 C.C. below the t'op of the eudiometer, and 10 C.C. of sul- phuric acid are introduced above the mercury. To obtain sulphuric acid suitable for the decomposition, ordinary acid is heated with sublimed sulphur until it begins to fume, then poured off from the fused sulphur and evaporated to two-thirds of its volume.The fluoride (which if decomposable by cold acid may be enclosed in a tube sealed by n drop of fused acid potassium sulphate) is placed in the flask with ignited quartz-powder. AEter reading the mercury level and tempera- ture, 50 C.C. of acid is added and the stopper inserted. The acid is slowly heated to boiling, whilst the pressure is kept below that of the atmosphere, to prevent leakage. When decomposition is complete, the whole is allowed to cool and the volume of the gas read off. A correction of 1.4 C.C. is added for the solubility of silicon fluoride in sulphuric acid. The results are equal in accuracy to those obtained by Fresenius' method, and the whole determination requires only three hours, of which two are occupied by the cooling.M. J. S.180 ABSTRACTS OF CHEMICAL PAPERS. Air Analysis on a BTew Principle. By 0. PETTERSSON (Zeit. anal. C'hem., 25, 467-478).-11he principle of this method of deter- mining the moisture and carbonic anhydride in atmospheric air con- sists in performing all the operations in a closed system, in which the influence of barometric variations and changes of temperature is eliminated by adjusting the pressure of the gas undergoing measure- ment to equality with that of a constant quantity in one part of the apparatns. The apparatus consists of a pipette with its lower tube graduated, and connected with an adjustable mercury reservoir by a flexible tube. There is a stopcock at its upper end for the introduction of the air for analysis.Below this stopcock are branched in the upper tubes (furnished with Atopcocks) two rather larger pipettes filled respec- tively with phosphoric anhydride and strongly dried soda-lime. The lower tubes of these two pipettes are connected (by stopcock tubes) with the two ends of a sensitive differential manometer, which is a horizontal tube slightly curved and containing as index a drop of coloured sulphuric acid or high-boiling petroleum. The pipettes are all immersed in the same vessel of water. The whole apparatus having been filled with the air for analysis, the mercury having been adjusted to the zero of the graduated stem, and equality of pressure having been established by opening for a moment all the stopcocks, the measured volume of air is compressed into the phosphoric anhy- dride pipette by admitting mercury until it fills the measuring tube.In 30 minutes all the moisture will have been absorbed. The dried air is re-expanded into the measuring tube ; the stopcocks to the mano- meter are opened, and the level of the mercury is adjusted till the pressure is again equal in all the pipettes. Since the qumtity of gas in the soda-lime tube has remained unaltered it serve8 as a standard volume, although external pressure and temperature may have varied, and the reading of the mercury in the graduated tube at once gives the volume of the aqueous vapour absorbed. The same process is repeated with the soda-lime pipette, in which the carbonic anhydride is absorbed, and now the air in the phosphoric anhydride pipette is employed as the standard volume.M. J. S. Assay of Iron Pyrites for Sulphur Available for Sulphuric Acid Manufacture. By J. C. WELCH ( A d y s t , 11, 209--213).-1n one method, the pyrites is mixed with calcium h-jdroxide and heated in a tube in a current of oxygen; the cont'ents of the tube are dissolved in hydrochloric acid and boiling water, and precipitated with barium chloride ; the presence of lime and iron in solution is perhaps objec- tionable. The results are only approximate. In the second method, which answers very well indeed, the pyrites is heated in a current of oxygen, the issuing gases are passed through bromine dissolved in hydrochloric acid and water, and the liquid is then boiled and precipi- tated with barium chloride.The secoud method is better than the method depending on heating with fumiug nitric acid, even in the w e of lead sulphide. D. A. L.ANALTTlCAL CHEMISTRY. 181 Volumetric Determination of Sulphuric Acid. By H. WILSING (Beit. anal. Chcm., 25, 560-561).-A measured excess of barium chlorlde is added to the neutral solution, and the excess is then determined by titration with sodium carbonate, using phenol- phthalei’n as indicator. The liquid is to be boiled while titrating. Substances precipitable by soda must first be removed. Volumetric Determination of Sulphates. By H. QUANTIN (Chem. News, 54, 233--234).-The solution of the sulphate under examination is well mixed with a hydrochloric acid solution of barium chromate to precipitate the sulphuric acid ; itl is then neutralised with ammonia to remove the excess of barium chromate.The filtrate, containing chromate equivalent to the original sulphate, is acidifid with sulphuric acid and titrated with ferrous sulphate, using potas- sium ferricyanide as indicator. Various necessary precautions are noted. D. A. L. M. J. S. Determination of Nitric Acid by Absorption of Nitric Oxide in Standard Potassium Permanganate Solution. By H. N. MOKSE and A. F. LINN (Arner. Chem. J., 8, 27&280).--The nitric acid is reduced by fei-rous chloride and hydrochloric acid in a current of carbonic anhydride. As ordinary marble contains air that cannot be removed by boiling with water, the author uses a saturated solu- tioii of sodium hydrogen carbonate containing a quantity of the same salt in suspension.The nitric oxide and carbonic anhydride pass through an empty tube and a set of potash bulbs, the latter contain- ing a strong solution of potassium carbonate to arrest all acid vapours. The washed gases are absorbed in two, long, slanting tubes containing a measured quantity of potassium permanganate. When the absorption is complete, the tubes are emptied and the contents decolorised by dilute sulphuric acid and a measured quantity of oxalic acid, the excess being titrated back with standard permanganate solution ; the tubes are cleaned by rinsing with a portion of the sulphuric and oxalic acids. The method yields very accurate and concordant results, Lawrence Smith’s Plan for Estimating Alkalis in Silicates. By P.HOLLAND (Chenz. News, 54, 242-243).-The author’s results indicate, firstly, that when carefully performed as directed, practically all the alkali is extracted at one operation ; secondly, that the form of crucible recommended by Smith minimises the loss of salts by vola- tilisation. D A. L. H. B. Analysis of Silicates. By W. M. HUTCBINGS (Chem. Neu7s, 54, 173-1 74).-The following method is recommended for mineral deter- minations in silicates. Alkalis are determined by flame colorations, metallic oxides by blowpipe tests, alkaline earths, alumina, and their approximate quantitative relation to one another and to iron by the following method :-A small quantity of the finely-powdered mineral is gently fused with seven times its weight of ammonium fluoride, the fluorides obtained are mixed with sodium carbonate and med in small qnantiiies at a, time in a, platinum-wire loop before182 ABSTRACTS OF CHEMICAL PAPERS.very hot flame, the beads are powdered and treated with water, alumina passes into solution, whilst iron and the alkaline earths remain undissolved. A mixture of cuprous iodide and sulphur in con- nection with the aluminium plate forms a very delicate test for small quantities of bismuth and lead. Both this mixture and Turner's flux keep good for many years. Glycerol is of more general use for boric acid testing than Turner's flux ; in presence of copper for example. D. A. L. Separation of Zinc'from Iron, Cobalt, and Nickel. By P. v. BERG (Zeit. anal. C'hern., 25, 512-519) .-Hampe has published (Chem. Zeit., 9, 543) a process for precipitating zinc from a solution containing the above metals, by converting them into formates and treating with hydrogen sulphide. He, however, found a large quan- tity of free formic acid necessary to completely prevent the simul- taneous precipitation of the other metals.The author shows that by diluting the solution until it contains only about 0.1 per cent. of zinc oxide, a much smaller quantity of formic acid (1 per cent. of 1.2 sp. p.) ensnres a practically complete separation, except in the case of cobalt, which requires a double precipitation. Monochloracetic acid is still more efficient, a single precipitation being sufficient even with cobalt. To the dilute solution, heated to 50-60", as much ammonia is added as is equivalent to the zinc present, then a small excess (about 2.6 grams to 450 c.c.) of mono- chloracetic acid ; hydrogen sulphide is t'hen passed slowly through the liquid. In either case, filtration must be commenced immediately the hydrogen sulphide is i n excess, and the precipitate must not be allowed t o dry on the sides of the beaker.It is washed with water containing hydrogen sulphide and a little of the organic acid. The test analyses communicated are satisfactory, but the conditions were not varied. M. J. S. Aluminium Sulphate containing Aluminium Hydroxide and Free Sulphuric Acid. By H. HAGER (Arch. Pharna. [3], 24, 852). -If the neutral sulphate contains any hydroxide, the crystnllised salt gives a more or less turbid solution with 2 parts of distilled water. To detect free sulphuric acid, Jorissen's test is applied thus:-A couple of drops of gurjun balsam is warmed with 3 C.C.of acetic acid. About 0.23 gram of the powdered aluminium sulphate is added and warmed gently. I n the absence of free sulphuric acid, a whitish or yellowish mixture is formed; in the presence of free acid, a blue coloration appears within a few minutes. Determination of Aluminium in Presence of a Large Pro- portion of Iron. By R. T. THOMSON (Chem. News, 54, 252-253).- The methods depending on boiling with a caustic alkali and subsequent precipitlation, or on direct precipitnkion by sodium thiosulphate, were found tto be ineffectual, therefore the following methoda of treatment are recommended for getting rid of the great bulk of the iron ; the first works best except when much manganese is present, therefore under such circumstances the secoiid method should be used.1st method : J. I'.ANALYTICAL CHEMISTRY. 183 Reduce the iron to the ferrous state by means of a cnrrent of sul- phurous anhydride, and boil off the excess, when cool add phosphoric acid or ammonium or sodium phosphate, in excess of that required to precipitate all the alumina, then ammonia until a faint permanent cloudiness is formed, finally excess of ammonium acetate. Should the precipitate contain much iron (it always retains a little), it is washed, redissolved in hydrochloric acid, and again treated with sulphurous anhydride, &c. 2nd method: Add ammonia to the I-educed iron solution until a slight cloudiness forms, then excess of ammonium acetate, boil, and if the precipitate contains much iron repeat the reduction and precipitation. In either case, when a sakisfactory precipitate is obtained, it is dissolved in hydrochloric acid, boiled with a little nitric acid, nearly neutralised with caustic soda, then boiled with large excess of the last reagent.The alumina is then precipitated as phosphate, the precipitate being washed with a hot 1 per cent. solution of ammonium nitrate, containing about 0.1 gram per litre of ammonium dibydrogen phosphate, and is weighed as Al,P,O,. Test results are very satisfactory. The presence of titanium does not interfere with the process. Silica in the Estimation of Manganese in Pig-iron, and Estimation of Phosphorus in Pig-iron and Steel. By ,L.. M. DEANE (Chem.News, 54, 174-175). - When samples of pig-iron containing more than 2 per cent. of silicon are analysed by the ordinary method, an appreciable amount of silica escapes separation, and is finally precipitated with the manganese. The ignited oxide of manganese should therefore be treated with hydrochloric acid, and the silica mixed with it determined in the usual way. For the estimation of phosphorus, the substance is dissolved in nitric acid, evaporated to dryness, redissolved in hydrochloric acid, and again evaporated to dryness. The residue is dissolved in hydrochloric acid, the silica separated, the solution evaporated nearly to dryness, a few drops of nitric acid added, and the heating continued until all nitrous fumes have escaped. The cold solution is mixed with cold water, and the phosphoric acid precipitated and weighed as ammonium phos- phoniolybdate.D. A. L. By L. BLUM (Zeit. anaZ. Chem., 25, 519-520). - From a, solution containing nickel, cobalt, zinc, manganous and ferric chlorides, with tartaric acid and excess of ammonia, potassium ferrocyanide throws down all the metals except the iron. A clear filtrate can be obtained after boil- ing, but the precipitate cannot be washed. A solution containing 0.00004 gram of manganese and 0.01 gram of ferric chloride per C.C. gives a distinct precipitate. Detection of Stannic Sulphide in Presence of Antimonious Sulphide. By A. GRIFFITH (Analyst, 11, 166165).-When a solu- tion containing antimonious sulphide is shaken with ether, and allowed to remain at rest, the sulphide rises to the surfzice with the ether ; stannic sulphide does not behgve in this manner.Therefore, when a solution containing both these sulphides is shaken with ether in D. A. L. Direct Separation of Manganese from Iron. M. J. S.184 ABSTRACTS OF CHEMICAL PAPERS. sufficient quantity, the antimonious sulphide rises to the surface arid exposes the otherwise obscured stannic sulphide. The test does not work with stannous salts. D. A. L. Production and Measurement of Gold and other Minute Metallic Spheres to Determine their Weight. By G. A. Goz- DORF (Chenz. News, 54, 231-232) .--The minutle quantity of pure gold obtained in the assay of very poor ores, &c., is dried on the aluminium plate and taken up by a red-hot boric acid bead in a platinum-wire loop; when heated before the blowpipe the gold is obtained as an almost perfect sphere.The boric acid is dissolved off, and the minute sphere of gold measured under the microscope, A sphere 0.024 mm. diameter = 0*000002178 of a grain of gold has been examined. The modes of calculating are explained. Silver spheres may be obtained and measured in a similar manner; but for copper, lead, and other metals, the boric acid is replaced by sodium carbonate, a s the former would dissolve a perceptible amouut of these metals. D. A. L. Estimation of Carbon in the Organic Constituents of Water. By A. HERZFELD (Ber., 19, 2618--2621).-The method is a modifica- tion of that proposed by Degener. The substance is boiled with chromic acid in a flask provided with a reflux condenser, the upper end of which is connected with a chloride of calcium tube.In the middle of the calcium chloride is a layer of powdered antimony, which absorbs any chlorine evolved from the substance. The car- bonic anhydride is estimated in an improved form of Rose’s apparatus. Estimation of Nitrates in Water by Means of Aluminium. By S. HARVEY (Analyst, 11, 181--186).--The author bas adopted the following plan, after considerable experience with the method :- 70 C.C. of the water is mixed in a bottle with 30 C.C. of 10 per cent. aqueous soda, a strip of aluminium foil, about 0.75 gram, is put in, the bottle is closed with a stopper carrying an open tube filled with glass beads, and the whole placed under a bell-jar until the reaction (which is aided by warmth) is complete, The contents and wash- ings are made up to a definite volume, and, if possible, Nesslerised directly, otherwise they must be distilled, &c.In cases where free ammonia has to be expelled from the original water, the 70 C.C. is only made slightly alkalirie n t first, the 30 C.C. of soda being added subsequently. After keeping some time, a reduction in the quantity of ammonia is observed in waters which have not been previously boiled, this is presumedly due to a re-oxidation. Accurate results are obtained. Cane-sugar, or salts of iron, calcium, or magnesium, do not affect the result. N. H. M. Certain sources of error are indicated. D. A. L. Estimation of Glycerol in Wines. By M. BARTH (Chent. Centr., 1886, 504-S05>.-10U C.C. of wine is concentrated to about 10 c.c., 1 gram of powdered quartz and about 3-4 C.C.of 40 per cent. milk of lime added, and the whole evaporated to dryness. ‘the glycerol isANALYTICAL CHEMISTRY. 185 then extracted with alcobol and finally with ether, the alcohol and ether evaporated on the water-bath, and the glycerol weighed. Assay of Carbolic Soap. By A. H. ALLEN (Analyst., 11, 103- 106). -In the method recommended, the hydrocarbons are removed loy agitating the soap, dissolved in soda and water, with ether, and the fatty acids are precipitated by means of brine. An aliquot part of the resulting solution is acidified with sulphuric acid and titrated with bromine-water until the solution is permanently tinged of a faint yellow colour ; the bromine-water is standardised immediately before or after use by a solution of phenol or cresol.The remainder of the solution may be used for preparing a larger quantity of the bromine- derivative for qualitative purposes. Estimation of Invert Sugar. By A. HERZFELD (Chem. Centr., 1836, 603).-In the method described by the author (Chem. Centr., 85, 604), the time taken in the preliminary heating of the liquid influences the result obtained. The tables given were constructed from experiments wherein this preliminary heating occupied four minutes. The author recommends the following precautions :-An asbestos plate with a circular opening of 6.5 cm. diameter is placed on the wire gauze, and the flask placed on that, the Bnnsen burner being placed at such a height that the flame plays over the whole of the exposed part of the flask, and heats the liquid to boiling in from 34 to 44 minutes.With these precautions, the results are very con- stant. L. T. T. L. T. T. D. A. L. Titration with Fehling's Solution. By E. BECKMANN (Zed. anal. Chem., 25, 529-53O).-Mang persons find a difficulty in recog- nising the point at which the blue colour disappears. This seems to be due to an optical illusion which causes the colourless liquid to appear complementary in colour t o the yellowish-red cuprous oxide. It may to some extent be obviated by adding a drop of zinc chloride, which promotes the separation of the cuprous oxide, hut the safest way is to filter and test for copper, which is easily done by placing two thicknesses of filter-paper together, touching one side with the turbid fluid and testing the liquid which soaks through to the other.With diabetic urine, however, it is still necessary to rely on the dis- appearance of the blue colour. By C. 0. CURTMAN (J. Phnrm. [ 5 ] , 14, 523-524).-To 4 C.C. of liquid (wine, beer, &c.) is added 2 C.C. of methyl alcohol, or failing this, the same amount of ethyl alcohol, and then, with care, 2 C.C. of pure sulphuric acid. After mixing, the liquid is heated for about two minutes, allowed to cool for eight or ten minutes, then heated just to boiling, when, if salicylic acid is present, a distinct odour of oil of wintergreen is perceptible. If only traces of acid be present, i t may be necessary to allow the liquid to stand, and to heat a third time especially if methyl alcohol has been replaced by ethyl alcohol.Altbough other ethereal salts are M. J. S. Detection of Salicylic Acid.1-8 B ABSTRACTS OF CHEMICAL PAPERS. formed in contact with beer and wine, besides methyl salicylats, the odour of the latter is the most characteristic and the most easily perceived. I n examining condensed milk, fats, or other solids and semi-solids, the sample is digested i n dilute alcohol at 20-30" for some hours, with frequent agitation. After filtration and concentra- tion, methyl alcohol and sulphuric acid are added as before described ; 0.001 part of salicylic acid in a food, &c., can be thus detected. Specific Gravity and some other Characters of Waxes and Allied Substances. By A. H. ALLEN ( A d y s t , 11, 223-228).- Methods are described for obtaining fragments of wax, &c., free from air bubbles, for specific gravity determinations ; also a method of taking gravities of waxes, &c.(heated by a suitable arrangement to 98-99"), by means of a Westphal balance and glass-rod plummet. The obserred gravities indicate that waxes are denser than fats or glycerides in the solid state, but that the reverse is the case with the melted substances. Sperm and bottle-nose oil are shown to be different in composition from spermaceti. Evidence is adduced in support of the glyceride as opposed to the wax-like character of Japan wax (see also next Abstract). The relation of high gravity to high melting point i n paraffin is noted. J. T. D. A. L. Saponification of Fixed Oils. By A. H. ALLEN (Analyst, 11, 145--147).-The author has collected, grouped, and tabulated results obtained by various investigators in the examination of a large variety of fatty substances by Kcettstorfer's saponification method. Oils con- sisting of olein mixed with comparatively small quantities of stearin or palmitin, whether of animal or vegetable origin, neutralise about the same quantity of potash-from 18-93 to 19.66 per cent.Oils from cruciferous plants require 17.02 to 17.9 per cent. of potash to neu- tralise them. Vegetable dr.yine(. oils require 18.7 to 19.6 per cent. These numbers are not characteristic, but show that linoleic acid must have a higher atomic weight than is generally supposed. With marine animal oils, also, the numbers obtained are not Characteristic, varying from 18.51 in cod-liver oil to 21-88 in porpoise oil, which con- tains much valeric acid: marine waxes, however, require only from 12-30 to 14.74, much less than the marine oils.The butter class contains-butter-fat requiring 22.15 to 23-24. cocoa-nut oil 24.62 to 26.84, palm-nut oil 22.00 to 24.76 per cent. of potash. The various mixtures of palmitin, stearin, and olein require from 19 to 20 per cent. of potash for their neutralisation. Beeswax requires 9.2 to 9.7; Chinese wax 6.5 ; castor-oil 17.6 to 18.15 ; Japan wax 21.01 to 22.25. Adams' Method for Milk Analysis. By A. R. ALLEN and W. CHATTAWAY (Analyst, 11, 71-73) ; and W. THOMSON (ibid.,-73- 75 ; compare also A bstr., 1886, 583) .-Allen rolls up a piece of string with the paper to keep the folds of paper from touching one another ; hence ensuring exposure of a more extensive surface.He also ties a, cap of filter-paper over the bottom of the coil. With this modified cod, suspended by a loop in the string, 5 C.C. of milk may be r u n direct from a pipette on to the coil without fear of loss, and then the objec- D. A. L.ANALYTICAL CHEMXSTRY. 187 tionable two weighings may be dispensed with. Thomson recommends distributing the 5 C.C. of milk on an extended strip of filter-paper, drying quickly, coiling and then extracting the fat in usual manner. D. A. L. Separation of Morphine and Strychnine from Fatty Matters. By FOCKE (J. Pharwt. [ 5 ] , 13, 360--361).-According to the aiithor, the following method gives good results. Exhaust the suspected matter with hot alcohol charged with tartaric acid.Filter after cooling, and evaporate on the water-bath. Take up the residue with 10 times its weight of witer and add an excess of baryta-water. After some hours, add a slight excess of sulphuric acid, allow to remain for some time, filter and remove excess of acid by means of barium chloride. Filter and evaporate again so as to completely expel the hydrochloric acid of the barium salt. The residue is taken up with absolute alcohol, and the solution is evaporated to dryness on the water-bath. The new residue, which is slightly acid, is dissolved in water and extracted with etber, which removes the fatty matter taken up by the water. The aqueous solution, after being made alkaline, is again treated with ether, the ethereal solution evaporated, and the residue treated with water acidified with hydrochloric acid, which only dissolves the alkaloids.By SAYUELSON (Chem. Zeit., 10, 998).-When mixed with an aqueous solution of sodium nitrate, white wine remains clear, but the colour becomes darker. In genuine red wines, a precipitate forms and the supernatant liquid becomes yellow, sometimes only after some time ; this is not the case with artificially coloured wines. I n a mixture of red and white wines, the amount of precipitate formed is inversely proportional to the quantity of white wine present. White wines coloured red with bilberry, mallow, red poppy, or orseille colouring matter do not gix-e any precipitate. Red wines mixed with coloured white wines yield, in addition to the precipitate, the following reactions : with bilberry or mallow colours, a violet liquid ; with orseille, a cherry- red liquid ; with red poppy, a bright red liquid.The addition of cider to white wine can be detected by sodium nitrate, as cider is coloured dark-brown by this reagent and after some time gives a slight precipi- tate. D. A. L. J. T. Detection of Artificial Colouring in Red Wine (Claret). Estimation of Tannin. By H. DIEUDONN~ (Chem. Zeit., 10,1067). -This simple and, when carefully conducted, accurate method for estimating tannin is based on reading very small differences of density with a very delicate hydrometer. The hydrometer indicates 1" BaumG, and is divided into hundredths ; with this the solution, or extract of the substance to be examined, made with distilled water, is tested st 22", both before and after treatment with powdered skin, the difference in the hydrometric readings is due to tannin.A table is given showing the quantity of tannin corresponding with solutions of densities varying from 1.5 to 105 of the centesimal Rhurnt5 degrees at 22". The standard solutions used in constructing the table con-188 ABSTRACTS OF CHEMICAL PAPERS. tained 0.1 to 10 grams of tannin dissolved in 500 C.C. of water. The ordinary solutions are prepared by boiling and pressing the material four times ; they are made up to a definitevolume and to a gravity of 1" B. or less, then a measured quantity is shaken with powdered skin, and the next day is filtered, pressed, &c. It is important to use dry and assayed powdered skin as well as good instruments.D. A. L. Peptones in the Blood and Urine. By GEORGES (J. Pharrn. [ 5 ] , 13, 353-354) .-All the methods hithedo proposed for the detection of peptones in urine are more or less defective. The authorgives the preference to the two following :- I. This has been recently employed by Wassermann for the detec- tion of peptones in the blood. The blood is received in strong alcollol ; the clot thrown on a filter is washed first with cold then with boiling water ; the aqueous solution is concentrated to about double the volume of the blood taken, and then added t o the alcoholic solution; sodium acetate and ferric chloride are now added to the liquid. After filtration and cooling, the last traces of albumin are removed by adding potassium ferrocyanide and acetic acid, filtered, the excess of ferrocyanide precipitated by copper.acetate, filtered, excess of copper removed by hydrogen sulphide ; filtered again, and heated on the wafer-bath to expel hydrogen sulphide and to cmcen- trate the liquid. This method gives good remlts, especially if care be taken to neutralise, or even to add a slight excess of alkali on adding the sodium acetate and ferric chloride. It also serves very well for the investigation of peptones in urine, commencing by boiling to precipitate albumin coagulable by heat, and terminating as above. 11. The double iodide of potassium and mercury precipitates albumin and the peptones, and Tanret has shown that the albumi- nous precipitate is insoluble in boiling acetic acid, whilst the peptone precipitate dissolves completely.Employing these reactions, Georges has established a much more rapid method as follows :--Precipitate by heat all the coagulable albumin ; treat the urine with acetic acid and the double iodide, wash the precipitate on a filter with ca!d water charged with acetic acid t o the same extent as the wine ; wash again with the same acidified water boiling, keeping the washings apart. The clear liquid obtained gives a precipitate on cooling i f the least trace of peptonic precipitate has been dissolved. It is only necessary t o neutralise in order to obtain a solution to which the double iodide test can be applied. J. T.AEALYTICAL CHEMISTRY. 179A n a1 y t i c a 1 C h e m i s t r y.Apparatus for Gas Analysis. By 0. PETTERSSON (Zeit.anal.C'hem., 25, 479-484) .-The principle on which the measurements aremade is similar to that employed for air analysis (this vol., p. 180). Thestandard volume of air is, however, contained in ft special bulb con-nected with the eudiometer through the differential manometer. Thegas is introduced by a side tube from a bell-glass inverted in amercury trough. The absorptions take place in Orsat tubes connectedwith the eudiometer by stopcocks. There are also wires for explo-sions. M. J. S.Universal Spectroscope for Qualitative and QuantitativeChemical Analysis. By G. KRUSS (Bey., 19, Y739--2746).-Amodified form of Bunsen and Kirchhoffs spectroscope is describedwith sketches.New Volumetric Method for Determining Fluorine. By F.OETTEL (Zeit.anal. Chem., 25, 5u5--511).--The fluorine is measureda s silicon fluoride in a special form of eudiometer. The decomposi-tion vessel is tt stoppered flask with the neck above the stopperenlarged into a cup for holding mercury. A tube branching from theneck is ground into the top of the eudiometer, the joint being alsocovered with mercury. The eudiometer is connected at its lower endwith a mercury tube like that of the nitrometer. The graduationbegins 10 C.C. below the t'op of the eudiometer, and 10 C.C. of sul-phuric acid are introduced above the mercury. To obtain sulphuricacid suitable for the decomposition, ordinary acid is heated withsublimed sulphur until it begins to fume, then poured off from the fusedsulphur and evaporated to two-thirds of its volume.The fluoride(which if decomposable by cold acid may be enclosed in a tube sealedby n drop of fused acid potassium sulphate) is placed in the flask withignited quartz-powder. AEter reading the mercury level and tempera-ture, 50 C.C. of acid is added and the stopper inserted. The acid isslowly heated to boiling, whilst the pressure is kept below that of theatmosphere, to prevent leakage. When decomposition is complete,the whole is allowed to cool and the volume of the gas read off. Acorrection of 1.4 C.C. is added for the solubility of silicon fluoride insulphuric acid. The results are equal in accuracy to those obtainedby Fresenius' method, and the whole determination requires onlythree hours, of which two are occupied by the cooling.M. J. S180 ABSTRACTS OF CHEMICAL PAPERS.Air Analysis on a BTew Principle. By 0. PETTERSSON (Zeit.anal. C'hem., 25, 467-478).-11he principle of this method of deter-mining the moisture and carbonic anhydride in atmospheric air con-sists in performing all the operations in a closed system, in which theinfluence of barometric variations and changes of temperature iseliminated by adjusting the pressure of the gas undergoing measure-ment to equality with that of a constant quantity in one part of theapparatns.The apparatus consists of a pipette with its lower tube graduated,and connected with an adjustable mercury reservoir by a flexible tube.There is a stopcock at its upper end for the introduction of the air foranalysis.Below this stopcock are branched in the upper tubes(furnished with Atopcocks) two rather larger pipettes filled respec-tively with phosphoric anhydride and strongly dried soda-lime. Thelower tubes of these two pipettes are connected (by stopcock tubes)with the two ends of a sensitive differential manometer, which is ahorizontal tube slightly curved and containing as index a drop ofcoloured sulphuric acid or high-boiling petroleum. The pipettes areall immersed in the same vessel of water. The whole apparatushaving been filled with the air for analysis, the mercury having beenadjusted to the zero of the graduated stem, and equality of pressurehaving been established by opening for a moment all the stopcocks,the measured volume of air is compressed into the phosphoric anhy-dride pipette by admitting mercury until it fills the measuring tube.In30 minutes all the moisture will have been absorbed. The dried airis re-expanded into the measuring tube ; the stopcocks to the mano-meter are opened, and the level of the mercury is adjusted till thepressure is again equal in all the pipettes. Since the qumtity of gasin the soda-lime tube has remained unaltered it serve8 as a standardvolume, although external pressure and temperature may have varied,and the reading of the mercury in the graduated tube at once givesthe volume of the aqueous vapour absorbed. The same process isrepeated with the soda-lime pipette, in which the carbonic anhydride isabsorbed, and now the air in the phosphoric anhydride pipette isemployed as the standard volume.M. J. S.Assay of Iron Pyrites for Sulphur Available for SulphuricAcid Manufacture. By J. C. WELCH ( A d y s t , 11, 209--213).-1none method, the pyrites is mixed with calcium h-jdroxide and heated ina tube in a current of oxygen; the cont'ents of the tube are dissolvedin hydrochloric acid and boiling water, and precipitated with bariumchloride ; the presence of lime and iron in solution is perhaps objec-tionable. The results are only approximate. In the second method,which answers very well indeed, the pyrites is heated in a current ofoxygen, the issuing gases are passed through bromine dissolved inhydrochloric acid and water, and the liquid is then boiled and precipi-tated with barium chloride.The secoud method is better than themethod depending on heating with fumiug nitric acid, even in thew e of lead sulphide. D. A. LANALTTlCAL CHEMISTRY. 181Volumetric Determination of Sulphuric Acid. By H.WILSING (Beit. anal. Chcm., 25, 560-561).-A measured excess ofbarium chlorlde is added to the neutral solution, and the excess isthen determined by titration with sodium carbonate, using phenol-phthalei’n as indicator. The liquid is to be boiled while titrating.Substances precipitable by soda must first be removed.Volumetric Determination of Sulphates. By H. QUANTIN(Chem. News, 54, 233--234).-The solution of the sulphate underexamination is well mixed with a hydrochloric acid solution of bariumchromate to precipitate the sulphuric acid ; itl is then neutralised withammonia to remove the excess of barium chromate. The filtrate,containing chromate equivalent to the original sulphate, is acidifidwith sulphuric acid and titrated with ferrous sulphate, using potas-sium ferricyanide as indicator.Various necessary precautions arenoted. D. A. L.M. J. S.Determination of Nitric Acid by Absorption of Nitric Oxidein Standard Potassium Permanganate Solution. By H. N.MOKSE and A. F. LINN (Arner. Chem. J., 8, 27&280).--The nitricacid is reduced by fei-rous chloride and hydrochloric acid in a currentof carbonic anhydride. As ordinary marble contains air that cannotbe removed by boiling with water, the author uses a saturated solu-tioii of sodium hydrogen carbonate containing a quantity of the samesalt in suspension.The nitric oxide and carbonic anhydride passthrough an empty tube and a set of potash bulbs, the latter contain-ing a strong solution of potassium carbonate to arrest all acid vapours.The washed gases are absorbed in two, long, slanting tubes containinga measured quantity of potassium permanganate. When the absorptionis complete, the tubes are emptied and the contents decolorised bydilute sulphuric acid and a measured quantity of oxalic acid, the excessbeing titrated back with standard permanganate solution ; the tubesare cleaned by rinsing with a portion of the sulphuric and oxalicacids. The method yields very accurate and concordant results,Lawrence Smith’s Plan for Estimating Alkalis in Silicates.By P.HOLLAND (Chenz. News, 54, 242-243).-The author’s resultsindicate, firstly, that when carefully performed as directed, practicallyall the alkali is extracted at one operation ; secondly, that the form ofcrucible recommended by Smith minimises the loss of salts by vola-tilisation. D A. L.H. B.Analysis of Silicates. By W. M. HUTCBINGS (Chem. Neu7s, 54,173-1 74).-The following method is recommended for mineral deter-minations in silicates. Alkalis are determined by flame colorations,metallic oxides by blowpipe tests, alkaline earths, alumina, and theirapproximate quantitative relation to one another and to iron bythe following method :-A small quantity of the finely-powderedmineral is gently fused with seven times its weight of ammoniumfluoride, the fluorides obtained are mixed with sodium carbonate andmed in small qnantiiies at a, time in a, platinum-wire loop befor182 ABSTRACTS OF CHEMICAL PAPERS.very hot flame, the beads are powdered and treated with water,alumina passes into solution, whilst iron and the alkaline earthsremain undissolved.A mixture of cuprous iodide and sulphur in con-nection with the aluminium plate forms a very delicate test for smallquantities of bismuth and lead. Both this mixture and Turner's fluxkeep good for many years. Glycerol is of more general use for boricacid testing than Turner's flux ; in presence of copper for example.D. A. L.Separation of Zinc'from Iron, Cobalt, and Nickel. By P. v.BERG (Zeit. anal. C'hern., 25, 512-519) .-Hampe has published(Chem.Zeit., 9, 543) a process for precipitating zinc from a solutioncontaining the above metals, by converting them into formates andtreating with hydrogen sulphide. He, however, found a large quan-tity of free formic acid necessary to completely prevent the simul-taneous precipitation of the other metals. The author shows thatby diluting the solution until it contains only about 0.1 per cent. ofzinc oxide, a much smaller quantity of formic acid (1 per cent. of1.2 sp. p.) ensnres a practically complete separation, except in thecase of cobalt, which requires a double precipitation.Monochloracetic acid is still more efficient, a single precipitationbeing sufficient even with cobalt. To the dilute solution, heated to50-60", as much ammonia is added as is equivalent to the zincpresent, then a small excess (about 2.6 grams to 450 c.c.) of mono-chloracetic acid ; hydrogen sulphide is t'hen passed slowly throughthe liquid.In either case, filtration must be commenced immediately thehydrogen sulphide is i n excess, and the precipitate must not beallowed t o dry on the sides of the beaker.It is washed with watercontaining hydrogen sulphide and a little of the organic acid. Thetest analyses communicated are satisfactory, but the conditions werenot varied. M. J. S.Aluminium Sulphate containing Aluminium Hydroxide andFree Sulphuric Acid. By H. HAGER (Arch. Pharna. [3], 24, 852).-If the neutral sulphate contains any hydroxide, the crystnllised saltgives a more or less turbid solution with 2 parts of distilled water.To detect free sulphuric acid, Jorissen's test is applied thus:-Acouple of drops of gurjun balsam is warmed with 3 C.C.of aceticacid. About 0.23 gram of the powdered aluminium sulphate is addedand warmed gently. I n the absence of free sulphuric acid, a whitishor yellowish mixture is formed; in the presence of free acid, a bluecoloration appears within a few minutes.Determination of Aluminium in Presence of a Large Pro-portion of Iron. By R. T. THOMSON (Chem. News, 54, 252-253).-The methods depending on boiling with a caustic alkali and subsequentprecipitlation, or on direct precipitnkion by sodium thiosulphate, werefound tto be ineffectual, therefore the following methoda of treatmentare recommended for getting rid of the great bulk of the iron ; the firstworks best except when much manganese is present, therefore undersuch circumstances the secoiid method should be used.1st method :J. I'ANALYTICAL CHEMISTRY. 183Reduce the iron to the ferrous state by means of a cnrrent of sul-phurous anhydride, and boil off the excess, when cool add phosphoricacid or ammonium or sodium phosphate, in excess of that required toprecipitate all the alumina, then ammonia until a faint permanentcloudiness is formed, finally excess of ammonium acetate. Shouldthe precipitate contain much iron (it always retains a little), itis washed, redissolved in hydrochloric acid, and again treated withsulphurous anhydride, &c. 2nd method: Add ammonia to theI-educed iron solution until a slight cloudiness forms, then excess ofammonium acetate, boil, and if the precipitate contains much ironrepeat the reduction and precipitation.In either case, when asakisfactory precipitate is obtained, it is dissolved in hydrochloricacid, boiled with a little nitric acid, nearly neutralised with causticsoda, then boiled with large excess of the last reagent. The aluminais then precipitated as phosphate, the precipitate being washed witha hot 1 per cent. solution of ammonium nitrate, containing about0.1 gram per litre of ammonium dibydrogen phosphate, and isweighed as Al,P,O,. Test results are very satisfactory. The presenceof titanium does not interfere with the process.Silica in the Estimation of Manganese in Pig-iron, andEstimation of Phosphorus in Pig-iron and Steel. By ,L..M.DEANE (Chem. News, 54, 174-175). - When samples of pig-ironcontaining more than 2 per cent. of silicon are analysed by theordinary method, an appreciable amount of silica escapes separation,and is finally precipitated with the manganese. The ignited oxide ofmanganese should therefore be treated with hydrochloric acid, andthe silica mixed with it determined in the usual way. For theestimation of phosphorus, the substance is dissolved in nitric acid,evaporated to dryness, redissolved in hydrochloric acid, and againevaporated to dryness. The residue is dissolved in hydrochloric acid,the silica separated, the solution evaporated nearly to dryness, a fewdrops of nitric acid added, and the heating continued until all nitrousfumes have escaped. The cold solution is mixed with cold water, andthe phosphoric acid precipitated and weighed as ammonium phos-phoniolybdate.D. A. L.By L. BLUM(Zeit. anaZ. Chem., 25, 519-520). - From a, solution containingnickel, cobalt, zinc, manganous and ferric chlorides, with tartaric acidand excess of ammonia, potassium ferrocyanide throws down all themetals except the iron. A clear filtrate can be obtained after boil-ing, but the precipitate cannot be washed. A solution containing0.00004 gram of manganese and 0.01 gram of ferric chloride per C.C.gives a distinct precipitate.Detection of Stannic Sulphide in Presence of AntimoniousSulphide. By A. GRIFFITH (Analyst, 11, 166165).-When a solu-tion containing antimonious sulphide is shaken with ether, andallowed to remain at rest, the sulphide rises to the surfzice with theether ; stannic sulphide does not behgve in this manner.Therefore,when a solution containing both these sulphides is shaken with ether inD. A. L.Direct Separation of Manganese from Iron.M. J. S184 ABSTRACTS OF CHEMICAL PAPERS.sufficient quantity, the antimonious sulphide rises to the surface aridexposes the otherwise obscured stannic sulphide. The test does notwork with stannous salts. D. A. L.Production and Measurement of Gold and other MinuteMetallic Spheres to Determine their Weight. By G. A. Goz-DORF (Chenz. News, 54, 231-232) .--The minutle quantity of puregold obtained in the assay of very poor ores, &c., is dried on thealuminium plate and taken up by a red-hot boric acid bead ina platinum-wire loop; when heated before the blowpipe the goldis obtained as an almost perfect sphere.The boric acid is dissolvedoff, and the minute sphere of gold measured under the microscope,A sphere 0.024 mm. diameter = 0*000002178 of a grain of gold hasbeen examined. The modes of calculating are explained. Silverspheres may be obtained and measured in a similar manner; butfor copper, lead, and other metals, the boric acid is replaced bysodium carbonate, a s the former would dissolve a perceptible amouutof these metals. D. A. L.Estimation of Carbon in the Organic Constituents of Water.By A. HERZFELD (Ber., 19, 2618--2621).-The method is a modifica-tion of that proposed by Degener.The substance is boiled withchromic acid in a flask provided with a reflux condenser, the upperend of which is connected with a chloride of calcium tube. In themiddle of the calcium chloride is a layer of powdered antimony,which absorbs any chlorine evolved from the substance. The car-bonic anhydride is estimated in an improved form of Rose’s apparatus.Estimation of Nitrates in Water by Means of Aluminium.By S. HARVEY (Analyst, 11, 181--186).--The author bas adopted thefollowing plan, after considerable experience with the method :-70 C.C. of the water is mixed in a bottle with 30 C.C. of 10 per cent.aqueous soda, a strip of aluminium foil, about 0.75 gram, is put in,the bottle is closed with a stopper carrying an open tube filled withglass beads, and the whole placed under a bell-jar until the reaction(which is aided by warmth) is complete, The contents and wash-ings are made up to a definite volume, and, if possible, Nessleriseddirectly, otherwise they must be distilled, &c.In cases where freeammonia has to be expelled from the original water, the 70 C.C. isonly made slightly alkalirie n t first, the 30 C.C. of soda being addedsubsequently. After keeping some time, a reduction in the quantityof ammonia is observed in waters which have not been previouslyboiled, this is presumedly due to a re-oxidation. Accurate results areobtained. Cane-sugar, or salts of iron, calcium, or magnesium, donot affect the result.N. H. M.Certain sources of error are indicated.D.A. L.Estimation of Glycerol in Wines. By M. BARTH (Chent. Centr.,1886, 504-S05>.-10U C.C. of wine is concentrated to about 10 c.c.,1 gram of powdered quartz and about 3-4 C.C. of 40 per cent. milkof lime added, and the whole evaporated to dryness. ‘the glycerol iANALYTICAL CHEMISTRY. 185then extracted with alcobol and finally with ether, the alcohol andether evaporated on the water-bath, and the glycerol weighed.Assay of Carbolic Soap. By A. H. ALLEN (Analyst., 11, 103-106). -In the method recommended, the hydrocarbons are removedloy agitating the soap, dissolved in soda and water, with ether, andthe fatty acids are precipitated by means of brine. An aliquot partof the resulting solution is acidified with sulphuric acid and titratedwith bromine-water until the solution is permanently tinged of a faintyellow colour ; the bromine-water is standardised immediately beforeor after use by a solution of phenol or cresol.The remainder of thesolution may be used for preparing a larger quantity of the bromine-derivative for qualitative purposes.Estimation of Invert Sugar. By A. HERZFELD (Chem. Centr.,1836, 603).-In the method described by the author (Chem. Centr.,85, 604), the time taken in the preliminary heating of the liquidinfluences the result obtained. The tables given were constructedfrom experiments wherein this preliminary heating occupied fourminutes.The author recommends the following precautions :-An asbestosplate with a circular opening of 6.5 cm.diameter is placed on thewire gauze, and the flask placed on that, the Bnnsen burner beingplaced at such a height that the flame plays over the whole of theexposed part of the flask, and heats the liquid to boiling in from34 to 44 minutes. With these precautions, the results are very con-stant. L. T. T.L. T. T.D. A. L.Titration with Fehling's Solution. By E. BECKMANN (Zed.anal. Chem., 25, 529-53O).-Mang persons find a difficulty in recog-nising the point at which the blue colour disappears. This seems tobe due to an optical illusion which causes the colourless liquid toappear complementary in colour t o the yellowish-red cuprous oxide.It may to some extent be obviated by adding a drop of zinc chloride,which promotes the separation of the cuprous oxide, hut the safestway is to filter and test for copper, which is easily done by placingtwo thicknesses of filter-paper together, touching one side with theturbid fluid and testing the liquid which soaks through to the other.With diabetic urine, however, it is still necessary to rely on the dis-appearance of the blue colour.By C.0. CURTMAN (J. Phnrm.[ 5 ] , 14, 523-524).-To 4 C.C. of liquid (wine, beer, &c.) is added2 C.C. of methyl alcohol, or failing this, the same amount of ethylalcohol, and then, with care, 2 C.C. of pure sulphuric acid. Aftermixing, the liquid is heated for about two minutes, allowed to cool foreight or ten minutes, then heated just to boiling, when, if salicylicacid is present, a distinct odour of oil of wintergreen is perceptible.If only traces of acid be present, i t may be necessary to allow theliquid to stand, and to heat a third time especially if methyl alcoholhas been replaced by ethyl alcohol.Altbough other ethereal salts areM. J. S.Detection of Salicylic Acid1-8 B ABSTRACTS OF CHEMICAL PAPERS.formed in contact with beer and wine, besides methyl salicylats, theodour of the latter is the most characteristic and the most easilyperceived. I n examining condensed milk, fats, or other solids andsemi-solids, the sample is digested i n dilute alcohol at 20-30" forsome hours, with frequent agitation. After filtration and concentra-tion, methyl alcohol and sulphuric acid are added as before described ;0.001 part of salicylic acid in a food, &c., can be thus detected.Specific Gravity and some other Characters of Waxes andAllied Substances. By A.H. ALLEN ( A d y s t , 11, 223-228).-Methods are described for obtaining fragments of wax, &c., free fromair bubbles, for specific gravity determinations ; also a method of takinggravities of waxes, &c. (heated by a suitable arrangement to 98-99"),by means of a Westphal balance and glass-rod plummet. Theobserred gravities indicate that waxes are denser than fats or glyceridesin the solid state, but that the reverse is the case with the meltedsubstances. Sperm and bottle-nose oil are shown to be different incomposition from spermaceti. Evidence is adduced in support of theglyceride as opposed to the wax-like character of Japan wax (see alsonext Abstract).The relation of high gravity to high melting pointi n paraffin is noted.J. T.D. A. L.Saponification of Fixed Oils. By A. H. ALLEN (Analyst, 11,145--147).-The author has collected, grouped, and tabulated resultsobtained by various investigators in the examination of a large varietyof fatty substances by Kcettstorfer's saponification method. Oils con-sisting of olein mixed with comparatively small quantities of stearinor palmitin, whether of animal or vegetable origin, neutralise aboutthe same quantity of potash-from 18-93 to 19.66 per cent. Oils fromcruciferous plants require 17.02 to 17.9 per cent. of potash to neu-tralise them. Vegetable dr.yine(. oils require 18.7 to 19.6 per cent.These numbers are not characteristic, but show that linoleic acidmust have a higher atomic weight than is generally supposed.Withmarine animal oils, also, the numbers obtained are not Characteristic,varying from 18.51 in cod-liver oil to 21-88 in porpoise oil, which con-tains much valeric acid: marine waxes, however, require only from12-30 to 14.74, much less than the marine oils. The butter classcontains-butter-fat requiring 22.15 to 23-24. cocoa-nut oil 24.62 to26.84, palm-nut oil 22.00 to 24.76 per cent. of potash. The variousmixtures of palmitin, stearin, and olein require from 19 to 20 per cent.of potash for their neutralisation. Beeswax requires 9.2 to 9.7;Chinese wax 6.5 ; castor-oil 17.6 to 18.15 ; Japan wax 21.01 to 22.25.Adams' Method for Milk Analysis.By A. R. ALLEN andW. CHATTAWAY (Analyst, 11, 71-73) ; and W. THOMSON (ibid.,-73-75 ; compare also A bstr., 1886, 583) .-Allen rolls up a piece of stringwith the paper to keep the folds of paper from touching one another ;hence ensuring exposure of a more extensive surface. He also ties a,cap of filter-paper over the bottom of the coil. With this modifiedcod, suspended by a loop in the string, 5 C.C. of milk may be r u n directfrom a pipette on to the coil without fear of loss, and then the objec-D. A. LANALYTICAL CHEMXSTRY. 187tionable two weighings may be dispensed with. Thomson recommendsdistributing the 5 C.C. of milk on an extended strip of filter-paper,drying quickly, coiling and then extracting the fat in usual manner.D.A. L.Separation of Morphine and Strychnine from Fatty Matters.By FOCKE (J. Pharwt. [ 5 ] , 13, 360--361).-According to the aiithor,the following method gives good results. Exhaust the suspectedmatter with hot alcohol charged with tartaric acid. Filter aftercooling, and evaporate on the water-bath. Take up the residue with10 times its weight of witer and add an excess of baryta-water.After some hours, add a slight excess of sulphuric acid, allow toremain for some time, filter and remove excess of acid by means ofbarium chloride. Filter and evaporate again so as to completelyexpel the hydrochloric acid of the barium salt. The residue is takenup with absolute alcohol, and the solution is evaporated to dryness onthe water-bath.The new residue, which is slightly acid, is dissolvedin water and extracted with etber, which removes the fatty mattertaken up by the water. The aqueous solution, after being madealkaline, is again treated with ether, the ethereal solution evaporated,and the residue treated with water acidified with hydrochloric acid,which only dissolves the alkaloids.BySAYUELSON (Chem. Zeit., 10, 998).-When mixed with an aqueoussolution of sodium nitrate, white wine remains clear, but the colourbecomes darker. In genuine red wines, a precipitate forms and thesupernatant liquid becomes yellow, sometimes only after some time ;this is not the case with artificially coloured wines. I n a mixtureof red and white wines, the amount of precipitate formed is inverselyproportional to the quantity of white wine present.White winescoloured red with bilberry, mallow, red poppy, or orseille colouringmatter do not gix-e any precipitate. Red wines mixed with colouredwhite wines yield, in addition to the precipitate, the following reactions :with bilberry or mallow colours, a violet liquid ; with orseille, a cherry-red liquid ; with red poppy, a bright red liquid. The addition of ciderto white wine can be detected by sodium nitrate, as cider is coloureddark-brown by this reagent and after some time gives a slight precipi-tate. D. A. L.J. T.Detection of Artificial Colouring in Red Wine (Claret).Estimation of Tannin. By H. DIEUDONN~ (Chem. Zeit., 10,1067).-This simple and, when carefully conducted, accurate method forestimating tannin is based on reading very small differences of densitywith a very delicate hydrometer.The hydrometer indicates 1" BaumG,and is divided into hundredths ; with this the solution, or extractof the substance to be examined, made with distilled water, is testedst 22", both before and after treatment with powdered skin, thedifference in the hydrometric readings is due to tannin. A table isgiven showing the quantity of tannin corresponding with solutions ofdensities varying from 1.5 to 105 of the centesimal Rhurnt5 degreesat 22". The standard solutions used in constructing the table con188 ABSTRACTS OF CHEMICAL PAPERS.tained 0.1 to 10 grams of tannin dissolved in 500 C.C. of water. Theordinary solutions are prepared by boiling and pressing the materialfour times ; they are made up to a definitevolume and to a gravity of1" B. or less, then a measured quantity is shaken with powdered skin,and the next day is filtered, pressed, &c. It is important to use dryand assayed powdered skin as well as good instruments.D. A. L.Peptones in the Blood and Urine. By GEORGES (J. Pharrn. [ 5 ] ,13, 353-354) .-All the methods hithedo proposed for the detectionof peptones in urine are more or less defective. The authorgives thepreference to the two following :-I. This has been recently employed by Wassermann for the detec-tion of peptones in the blood. The blood is received in strongalcollol ; the clot thrown on a filter is washed first with cold then withboiling water ; the aqueous solution is concentrated to about doublethe volume of the blood taken, and then added t o the alcoholicsolution; sodium acetate and ferric chloride are now added to theliquid. After filtration and cooling, the last traces of albumin areremoved by adding potassium ferrocyanide and acetic acid, filtered,the excess of ferrocyanide precipitated by copper. acetate, filtered,excess of copper removed by hydrogen sulphide ; filtered again, andheated on the wafer-bath to expel hydrogen sulphide and to cmcen-trate the liquid. This method gives good remlts, especially if carebe taken to neutralise, or even to add a slight excess of alkali onadding the sodium acetate and ferric chloride. It also serves verywell for the investigation of peptones in urine, commencing byboiling to precipitate albumin coagulable by heat, and terminatingas above.11. The double iodide of potassium and mercury precipitatesalbumin and the peptones, and Tanret has shown that the albumi-nous precipitate is insoluble in boiling acetic acid, whilst the peptoneprecipitate dissolves completely. Employing these reactions, Georgeshas established a much more rapid method as follows :--Precipitateby heat all the coagulable albumin ; treat the urine with acetic acidand the double iodide, wash the precipitate on a filter with ca!d watercharged with acetic acid t o the same extent as the wine ; wash againwith the same acidified water boiling, keeping the washings apart.The clear liquid obtained gives a precipitate on cooling i f the leasttrace of peptonic precipitate has been dissolved. It is only necessaryt o neutralise in order to obtain a solution to which the double iodidetest can be applied. J. T

ISSN:0368-1769    

DOI:10.1039/CA8875200179

出版商:RSC    

年代:1887

数据来源: RSC

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189 General and Physical Chemistry. Actinornetry. By E. DUCLATJX (Compt. rend., 103, 1010-1 012). -0xalic acid in aqueous solution is converted into carbonic anhy- dride and water by the action of light in presence of oxygen, and this decomposition is not due to any rise of temperature resulting from absorption of the sun’s radiation, but is brought about by the visible and ultra-violet rays. In order to secure sufficient contact with the oxygen of the air, the solution is placed in flat vessels and the same volume of liquid is always employed ; also, in order to eliminate the some what considerable influence of the concentration of the solution, a, dilute solution, containing 3 grams of oxalic acid per litre, is employed. The amount of change is determined by titratinq with lime-water.I f the solution of oxalic acid has been kept for about two months in the dark, it is found to be much more sensitive to the action of light than a freshly prepared solution-a fact which indi- cates that the two liquids have not the same molecular constitut,ion. The change is analogous to the ripening of collodion. The same degree of sensitiveness can be imparted to a freshly prepared solution by exposing it to sunlight for a few hours, and if a concentrated solu- tion is treated in this way and is then diluted to the strength given, the increased sensitivenew is transmitted to the dilute solutions-a fact which indicates that the alteration takes place in the molecules of the acid and not in those of the water. The total quantity of acid decomposed when the same quantity of liquid is exposed during the whole day is much greater than the sum of the quantities decomposed when a fresh portion of solution is exposed during each hour, the difference varying from day to day.There is therefore a period of quiescence similar to that which is observed in many photographic and chemical reactions, and which Bunsen and Roscoe have termed photochemical induction in the case of hydrogen and chlorine. Fluorescences of Manganese and Bismuth. By L. DE BOIS- BAUDRAN (Compt. rend., 103, 1064-1068).-A mixture of 100 parts of yttrium sulphate with 2 parts of manganese snlphate shows a yellowish-green fluorescence, the spectrum of which consists of a broad band which begins at about 6500, attains its maximum bril- liancy at 5640, and fades away gradually at 489@-&0.With 4 per cent. of manganese sulphate, the fluorescence is more intense. but its character is not altered. The fluorescence differs from that of calcium, and is not due to the presence of traces of this element. A mixture of 100 parts of yttrium sulphate with 2 parts of bismuth sulphate gives a red fluorescence, with a spectrum consisting of a band which begins at 6840, attains its maximum brilliancy at 6420-6400, and fades away at 5790-5770. This fluorescence is not due to the pre- sence of magnesium. C. H. B. VOL. LII. 0190 ABSTRACTS OF CHEMICAL PAPERS. Calcium sulphate mixed with small quantities of both bismuth and manganese sulphates gives a fluorescence which is yellow at hhe centre, and pale-green further from the electrodes. In the spectrum, the orange-red band of the calcium-bismut h fluorescence is very distinct.If the tube is heated, the fluorescence becomes rose-yellow, the red band is scarcely affected, and the brilliancy of the green is diminished. At a higher temperature, the fluorescence diminishes and again becomes green with a bluer shade than originally, and the red band is almost extinguished. In all cases, the fluorescence is much less brilliant than with calcium and inanganese sulphates free from bismuth. A mixture of magnesium suiphate with both manganese and bismuth gives a fluorescence due to the superposition of the mag- nesium-manganese and the magnesium-bismuth fluorescences. Cadmium sulpbate with small quantities of both manganese and bismuth gives the cadmium-manganese fluorescence, which is some- what less brilliant than in the absence of bismuth, Strontium sul- phate, on the other hand, under similar conditions, gives the strontium- bismuth fluorescence, the intensity of which is somewhat diminished by the presence of manganese.A mixture of calcium oxide with small quantities of manganese and bismuth oxides gives the calcinm-manganese fluorescence with somewhat diminished intensity. A mixture of zinc and calcium sulphates, in varying proportions, with small quantities of manganese, gives a, fluorescence in which the calcium-manganese fluorescence is muoh more prominent than that due to zinc-manganese. With only 5 per cent. of calcium sulphate, the effect of its presence is readily observed, and it is quite distinct with even 2 per cent.if the tube is heated. Effect of Manganese on the Phosphorescence of Calcium Carbonate. By E. BECQUEREL (Compt. rend., 103, 1098-1101).- The most highly phosphorescent crystals of Iceland spar, which show an orange phosphorescence, contain a somewhat high proportion of manganese, probably in the form of carbonate, with mere traces of iron. The less strongly phosphorescent varieties contain very little manganese. Calcium carbonate, precipitated from a solution of calcium chloride containing 4 per cent. of manganese chloride, gives alniost identical results. Calcium carbonate, formed on the surface of such a solution when exposed in an atmosphere charged with the vapour of am- monium carbonate, does n o t show the same phenomenon.These results explain the author’s earlier observation, that calcinm carbonate precipitated from calcium chloride prepared from Iceland spar, always gives an orange phosphorescence, whilst that prepared from aragonite shows a green phosphorescence. Further experiments are necessary to determine whether manganese is the sole cause of the phenomenon. The phosphorescence of Iceland spar is affected by lithium, bis- muth, and antimony, and by various metallic sulphides. C. H. B. C. H. B.GENERAL AND PHYSICAL CHEMISTRY. 191 Red Fluorescence of Alumina. By L. DE BOISBAUDRAN (Compt. rend., 103, 1107).-Pure calcined alumina shows no red fluorescence when subjected to the action of the silent discharge in a vacuum, but the red fluorescence described by Becquerel (“ La Lumiere”) is shown brilliantly if the alumina contains a small quantity of chromic oxide, and is visible even with so small a proportion as 0.001 per cent?.Alumina with 1 per cent. of manganese oxide shows a green fluorescence ; with 1 per cent. of bismuth oxide, a lilac fluorescence in the cold, which becomes blue on heating. Magnesia with 1 per cent. of chromic oxide shows a red fluorescence, whilst the fluorescence of lime containing chromic oxide differs very slightly from that of pure lime. C. H. B. Phosphorescence of Alumina. By E. BECQUEREL (Coinpt. rend., 103, 1224-12 27) .-The alumina prepared by Boisbaudran (pre- ceding Abstract) does actually show a feeble red phosphorescence, but after being heated to a very high temperature in a platinum crucible for 15 minutes, it shows the red phofiphorescence brilliantly.It would seem, therefore, that Boisbaudran had not sufficiently dehy- drated his product. The author has repeated his earlier experiments, and confirms his former conclusion that pure alumina shows some phosphorescence, which is often greenish in colour, but if strongly heated it shows a brilliant red phosphorescence, the intensity of which is increased by the presence of small quantities of chromium and certain other sub- stances. He points out that the exact character of a phosphorescence or fluorescence will depend on the agent by which the substance is excited and the conditions under which excitation takes place. C. H. B. Molecular Refraction of Liquid Organic Compounds of High Dispersive Power.By J. W. BRUHL (AnnaZen, 235, 1- 106 ; see also Ber., 19, 2746).-1n previous papers (Abstr., 1880, 293, 295, 685, 781 ; 1882, 15; 1882, 263, 445, 82‘7, 829), the author has shown that the mode of union of atoms in n compound, inde- pendently of their mere number, has a special influence in raising the moleculgr refractive power. The present paper embodies a number of new and confirmatory observations, together with discus- sions of the validity of the several expressions for molecular refrac- tive power, and of the possible connection between dispersion and refractive index or chemical constitution. Numerous references to the work of other physicists are given. The methods of investiga- tion have been previously described. The first part of the paper contains an account of the prepayation and purification of 21 unsaturated compounds specially examined, together with determinations of their densities, refractive indices for the lines a, D, 6, and v, their molecular refractive powers according to Dale and Gladstone’s formula ( p a - 1).;, and the more recent or “new ’’ formula tk’). g, &c. The constants for these and pa2 + 2 0 2192 ABSTRACTS OF CHEMICAL PAPERS. for 21 other unsaturated compounds previously examined are arranqed in four tables, from which subsidiary tables are constructed to illus- trate special points. Gladstone and Dale's constant was found to be correct within moderate limits of temperature, and since it was applied chiefly to the saturated and feebly dispersive compounds o€ the fatty series, comparable results were obtained.More recently, H. A. Lorenz (Ann. Phys. Chem. [2], 9, 641) and L. Lorenz (ibid., 11, 70) have proved by independent theoretical methods that the relation between the velocity of propagation of light and the density of the medium is contained in the formula - - - - constant, when n = refractive index, d = density. This constant was proved by these authors, and by Nasini and Bernheimer, t o vary much less with the temperature than the old one. Landolt, also (Abstr., 1882, 909), by its aid has recalculated the molecular refractive powers of many compounds examined by various authors, and found not only that all the earlier established relations are equally well expressed, but that a closer aqreement between theory and observation is attained by its use.There still remain, however, serious discrepancies between theory and experiment, especial€y in the case of substances of high dispersive power. The question then presented itself: Is there any relation between dispersion and mean refractive index on the one hand, or chemical constitution on the other ? Dispersion may be measured either as py - pa, or by the constant B in Cauchy's equation- ma - 1 (n2 + 2jd - B C P = A + X s + Q - + - * . (using only constants A and B), in which p = refractive index for wave-length X, A = refractive index for infinite wave-length. In the saturated compounds of the fatty series, B is small (0.3 t o 0.5) ; but in the unsaturated compounds tabulated in this paper B is very great, in the case of cinnamaldehydereaching the enormous value 2.5.Calculating the constants A and B from observations of and ,q, the author has applied Cauchy's equation to calculating ,uD for the last- named substances, and he shows by a tabular statement that theory and experiment agree well for cornpounds of low dispersion, but that very serious discrepancies arise when the dispersive power is high. Cauchy's equation is therefore untrustworthy in these cases. No definite relation can be traced between dispersion and mean refrac- tive index. (See also following Abstract.) Neither does any con- nection exist between dispersion and chemical constitution. This B is shown by selected examples, in which - (dispersion at 20" for d: unit density) is seen to have very different values for compounds of analogoils constitution, nearly equal density and equal refractive index; whilst, on the other hand, the dispersion may be the same for substances of very different chemical structure.Enquiry is next made into the validity of the old and new formula.QENERAL AND PHYSICAL CHEMISTRY. 193 P N a 2 - 1 P pa2 i- 2 ’ d Tables are given of the values of (pa - 1)2 and - - for the 42 substances, both experimental and calculated by the aid of the following table of atomic refractive powers :- -----I__ Singly-linked carbon ............. Hydrogen ...................... Singly-linked oxygen ............ Aldehydic oxygen ................ Chlorine ........................ Bromine ........................ Iodine. ......................... Singly-linked nitrogen ...........Equivalent of ethylene grouping.. .. Equivalent of acetylene grouping.. . Ca . 5-00 1-30 2 -80 3 ‘40 9.87 15.39 24.69 5’75 2.30 1.90 ?-a . -- 4 -86 1-29 2.71 3.29 9.63 14 ‘81 23 -35 5-35 2 -00 1 ‘80 r’a . -- 2 -48 1 *04 1.58 2.34 6 ‘02 8 *95 13.99 3 *02 1 *78 1 *97 C‘A. -- 2 -43 1 ‘02 1.56 2-29 5 *89 8 -70 13 *36 2 -b7 1 -59 1.86 In this table ra and rA are the equivalents for the refractive index of a (red hydrogen line), and A, index for infinite wave-length, using the old (Gladstone’s) formula : rlcr and T ’ ~ the similar equivalents for the new (Lorenz). This table has been calculated in part by the author, in part by Landolt. From this table, it is seen that when the molecular refractive power is calculated by the old formula, the differences between theory and experiment in most cases exceed the possible limits of experimental error, and are especially great for substances of high dispersive power.Since all the differences are positive, it is evident that dispersion here tends to raise the molecular refractive power. When the latter is calculated by the new formula, the differences, although still positive, are both relatively and absolutely smaller. The disagreement is, however, well marked in the ca5e of highly dispersive compounds. To show the disturbing influence of dispersion more dearly, tbe author in a new table arranges the various substances in the order of ascending values of B (dispersion-coefficient), placing opposite each the differences between the observed and calculated refractions according to the old and new formula.When B is small, the discrepancies are relatively about the same for both; but as B increases, there is a rapidly growing inequality between them, the advantage being always with the new formula. The t w o formulae are therefore of nearly equal value (as Landolt supposed them always to be) only for feebly dispersive substances. Yet even here the new gives the more concordant results, as the author shows by a new table, including only unsaturated but feebly dispersive com- pounds. In the author’s opinion, the defects of the new formula are mainly, but not altogether, traceable to dispersion. The general connection between them has been proved above ; but it is pointed out that no ayithmetical relation exists between the discrepancies and the disper- sion-coefficieut.194 ABSTRACTS OF UHEMICAL PAPERS.Although as a rule the dispersion is high in compounds con- taining many C=C’ groups, some unsaturated compounds of low dispersive power exist. Certain striking examples are mentioned, for which the new formula nevertheless gives good results. These show also that there is no connectmion between dispersive power and chemical cons ti t u t i on. Some little space is devoted to refuting Gladstone’s theory (Abstr., 1882, 133), adopted by Nasini, namely, that the atomic refraction of carbon-atoms, which are united only to other unsaturated atoms, is higher than that of Unsaturated atoms, which are not so united. Examples are given of compounds containing atoms of this kind, for which theory and experiment give concordant results.Moreover, there is no connection between dispersion and such atoms, as proved by the high dispersive power of many substances (aldehyde, fur- furaldehyde, &c.) from which they are absent. The highly important relationship of molecular refractive power to unsaturated carbon groups is next discussed. This has been denied by Nasini and others. (See also Thomsen, following Abstract.) The author yehearses the older arguments on which his views rest, and quotes three series of substances containing 1,2, and 3 ethylene (CZC) groupings respectively. For these the mean excesses of observed molecular refractive power over that calculated for the empirical formulae alone, are 1.79, 3.47, and 5.38 respectively. A fourth table shows the empirical refractive powers for a series of seven substances, each containing 4 C=C groupings.I n this, the discrepancies range from 4 x 1.73 for the feebly dispersive ally1 pbenoxide, to 4 x 2.03 for the highly dispersive cinnamic alcohol. It is remarkable that when hydrogen is removed from a hydro- carbon, so as to form a ring of singly-linked carbon-atoms, there is no undue increase in refractive power. For example, in citrene, pitrene, and tetrahydroterpene, which according to Wallach contain 2, 1, and 0 C=C groupings, whilst all three contain rings, the excess of observed over empirical molecular refractive power amounts to 2 x 1.78, 1 x 1.78 and 0. I n a note, it is pointed out that these considerations speak strongly in favour of KekulB’s benzene formula, as opposed to the prismatic formulae of Ladenburg and others. Thornsen’s thermochemical researches (Abstr., 1880, 785; 1882, 721) lead to exactly opposite conclusions.The final conclusion of this chapter i s : that ethylene groups are effective in raising the molecular refractive power ; and that where the increase is greater that can be thus accounted for, it is attributable to dispersion. A question of practical importance is : how far may the molecular refractive power according to the new formula be safely applied to determining chemical structure ? This is attacked by making n comparison between the observed and calculated (taking structuw into account) powers for various substances, and the number of C=C groupings in their molecules. The value of this grouping according to Landolt =1.78; or rather the mean value, since it is not the same for all series.Many of the slighter discrepancies in the tableGENERAL AND PH YSTCAL CHEMISTRY. 195 may be explained by this variability, the presence of impurities, or uncertainty as to chemical constitution. But of the 42 cases quoted, in only eight does the discrepancy amount to more than the value of an ethylene group ; and all these are of substances of high dispersive power. Of the remainder, in only three does the dimrepancy equal one-half of 1.78. In some cases even of highly dispersive bodies the difference is less than this. It is not possible to assign an exact limit beyond which dispersion becomes of importance ; but, generaily, con- clusions as to chemical structure are insecure when the dispersion equals that of cinnamic alcohol (PUS - pa = 0.0248 ; py - pa = 0.0412 ; B = 1.38).I n such a case efforts should be made to prepare less dispersive derivatives of the substance in question, which is very frequently possible. I n anot,her chapter, the value of the acetylene, CEC, grouping is discussed. A strong point in favour of the new formula is that here its value is greater than that of the ethylene grouping, whereas for the old formula it is less. But old and new values are to some extent variable with the dispersion. A fresh study of five compounds (three propargyl- derivatives, heptidene, and acetenylbenzene) lends to the slightly increased mean value (see table above) 2.18. This and the value of the ethylene grouping agree remarkably well with those calcu- lated by the author from Mascart’s determinations of pD for gaseous ethylene and acetylene (Compt.rend., 86, 1182). I n Section 111, the question is discussed to what extent are the discrepancies between theory and experiment removed by substituting for pa in the new formula, the refractive index A for infinite wave- length calculated from Cauchy’s formula, using firstly two, and secondly three, constants, An elaborate study of the results so obtained leads to the following general conclusions. When A is calculated from Cauchy’s equation with two constants (A and B), the molecular refractive powers, although in better agree- ment with experiment, seldom differ much from, and always in the same sense as, those calculated from pa.For feebly dispersive sub- Rtances, in fact, little is gained by the substitution ; but for compounds of high dispersive power the advantage is usually, but not always, very decided. The values of A deduced from Cauchy’s equation with two and with three terms are about the same when the disperson is low. But for highly dispersive substsLilces the values of A from the three-termed formula are always the greater ; hence the molecular refractive powers calculated from them diverge still more from the observed powers. Here, in fact, the uses of A and of pa lead to about the same re8 u l t s. The author’s conclusion is that Cauchy’s formula is purely empirical, and without any physical signigcance. (See also next Abstract.) CH. B. Experimental Examination of the Older and More Recent Dispersion-formulae.By J. W. BRCHL (Ber., 19, 282l).-The author has shown (preceding Abstract) that in calculating refractive power, the difficulty introduced by dispersion cannot be removed by196 ABSTRACTS OF CHEMICAL PAPERS. substituting for n (the refractive index for any particular wave- length) its value for a wave-length supposed infinite, deduced from Cauchy’s well-known equation. In view of the great importance of the subject in its chemical aspect, the author here presents a critical inquiry into the trusfworthiness of the various formula connecting refractive index with wave-length, which have been proposed from time to time. B C X2 x4 Cauchy’s original formula, n = A + - + - + . . . . ., as well as later modifications of it,, lead to the conclusion that the refractive index n diminishes oonstantly as the wave-length increases, reaching a definite minimum value when X becomes infinite, a, conclusion which is manifestly unfirue in the case of substances showing abnormal dis- persion. Of the more modern theories discussed, which embrace the phenomena of abnormal dispersion, only one, that of Lommel, implies a limiting value of a greater than unity.Others either do not give such a limiting value (Ketteler’s), or give it only under special con- ditions (Helmholtz’s). I n 1879, Mouton proved the untrustworthiness of Cauchy’s formula in calculating the dispersion of the ultra-red rays of the spectrum of a specimen of heavy flint glass, when the constants A, B, C, were de- duced from the observed values of ?L for the seven principal Fraun- hofer lines.The differem- of hhe observed from the calculated values of n ranged from 0.0023 for h, = 8.8 to 0.0137 for X = 21.4, amounts which greatly exceed possible experimental errors. Very similar differences existed between the observed valnes of n for the ultra-red rays of the ordinary and extraordinary spectra of quartz, and the values calculated by Briot’s equation - = a + b - + c- + . . . . . 1 w? n4 n2 x2 x d which gives a limiting value of n = di for h = 03. The con- stants here were calculated from some measurements by Mascart for the lines C, G, 0. The results of these experiments are arranged by the author in tabular form, and prove that Cauchy’s formula fails when used €or calculating by extrapolation the refractive index for ultra-red rays, and d fortiori for rays of infinite wave-length.The same is true of Christoffel’s modification of Cauchy’s equation. All, however, are available for interpolation. It might be supposed that the failure of Cauchy’s formula in these cases was due to the narrow range of observations from which the constants were determined. The author has therefore made a com- parison, based on a series of measurements by Langley, between the observed and calculated values of 12 from the beginning of the ultra- violet to far beyond the red in the spectrum of flint-glass. The constants (A = 1.3504, B = 1.334171, C = -6.982411) were de- duced from the values of n for X = 3.97 (H1), X = 7.6, and X = 18.1 (ultra-red). The tabulated results are remarkable ; in fact Cauchy’s formula is here as valueless for interpolation as it was before for extrapolation.The interpolated values in no case agree with the observed values, inGENERAL AND PHYSICAL CHEMISTRY. 19‘7 one case differing by so much as 0.0045, whilst the observed values of .n for X = 23-56 (1.5478) and for h = 28.0 (1.5435) are considerably smaller than the calculated minimurn, A = 1.5504 for X = m.. The constant C, too, being negative, it can be shown .~ that n should reach a maximum value (= 1.6141) when X = dr! = 3-23; whilst the observed index for X = 3.44 was 1.6266, thatis, greater than this theoretical maximum. The author next directs attention to Helmholtz’s formula- x4 X2 - A;;; rta - 1 = Q .r - PXa, a in which P, Q, and XG depend on the nature of the medium.When P > Q, the refractive index must diminish as A increases, until becomes negative, that is, until total reflection occurs. When P = Q, .n reaches a minimum value for m; but when P < Q, this limiting value corresponds with a finite wave-length. A value of n independent of dispersion can only exist, then, when P = Q, in which case Helm- holtz’s formula reduces to Lommel’s. Ketteler’s still more recent formula- gives = 1, when h = m, that is, the limiting value of V L would be unity for all substances, and consequently there could be no index of refraction independent of dispersion. The author’s investigations have now shown that for calculations by interpolation Helmholtz’s and Ketteler’s equations give equally good results in the case of media of low dispersive power.No choice between them is possible. But when applied to highly dispersive media, Helmholtz‘s formula is inferior not only to Ketteler’s (which contains an additional constant), but also to Cauchy’s. Taking a series of measurements of‘ n, for oil of cassia (Baden-Powell), the constants for each formula were determined from observations extend- ing to the extreme limits of the visible spectrum. Calculating the values of n for intermediate wave-lengths, the best results were usually obtained by Ketteler’s formula. But with constants deter- mined from lines between C and G, Cauchy’s formula proved most trustworthy, especially for extrapolation. These conclusions are clearly set forth in a tabular statement. An important result of this investigation is that Q in Helmholtz’s equation is always found > P, which at once disposes of Lommel’s theory.The refractive index should therefore be a minimum for some wave-length not infinite. According to the way in which the constants were determined, this minimum was either 1.59 for X = 8.535, or 1.6002 for X = 7397; whereas for the line A, n, was observed = 1.5963, or less than the theoretical minimum. In the foregoicg comparisons, the constants were always determined for lines within the limits of the visible spectrum. With constanta198 ABSTRACTS OF CHEMIOAL PAPERS. determined over a much wider range, Wlillner has faund Helmholtz’s formula, and Ketteler his own formula, to give excellent results in the case of feebly dispersive subslances, although, as the author points out, the two are fundamentally different, and cannot both be correct.From the author’s calculations, it appears that both are equally in- sufficient when applied to highly dispersive media. In proof, a table is given of the differences between the observed values of n for the ordi- nary and extraordinary spectra of calcspar, and the values calculated by Helmholtz’s and Ketteler’s equations respectively. The observed values are by Mnscart for lines from A t o R, and by Sarasin for the ul tra-violet (cadmium) spectrum. The constants were determined for lines over the whole spectrum. The results show that for the extraordinary spectrum, in which the dispersion is low, Helmholtz’s formula is satisfactory, Ketteler’s some- what better.But when applied to the ordinary spectrum, in which the dispersion is 24 times greater, the discrepancies are very serious, extending in the case of Helmholtz’s formula to the third place of decimals. From his investigations, the author draws the following important conclusions :-That all the formule connecting wave-length and re- frangibility hitherto proposed are of purely empirical character, and applicable only to media of low dispersive power : that at present it is not certain that the refractive index reaches a limiting value, unity or otherwise, either for X = cm or for any other wave-length; and, finally, that in investigations bearing on chemical constitution and refractive puwer, dispersion must either be taken into account,, or be eliminated in some empirical way.Ketteler’s equation proved somewhat better. CH. B. Supposed Influence of Multiple Bonds of Union on the Molecular Refraction of the Hydrocarbons. By JULIUS THOMSEN (Ber., 19, 2837).-In 1862-664, Landolt (Ann. Phys. Cjzern., 117, 122, and 123) proved beyond doubt that a connection exists between mole- cular refractive power and chemical composition, by showing that in any homologous series the refractive power increases from member to member by a constant amount, and is independent of isomerism and metamerism. Since then Briihl (Abstr., 1880, 295, 781 ; 1882, 44.5, and preceding Abstract) has endeavoured, with apparent success, to establish a, rela- tion between molecular constitution and refractive power, by showing that the refractive power of a compound, although independent of the number of single bonds of union between carbon-atoms in its mole- cule, is decidedly influenced by double and treble bonds. The fol- lowing considerations, however, make such an influence at least doubtful :- Briihl’s results are summed up in the formula- n .c + 2m.h + aV, + /3V2 + YV, = R . . . . in which R is the molecular refraction of a hydrocarbon CfiH2m, c and h the refractions of a carbon and hydrogen atom respectively, a, /3, and ‘y the numbers of single, double, and treble bonds of union, andGE,WRAL AND PHYSICAL CHEMISTHT. 199 V,. VL, and V3 the increments of refractive power due to them re- spectively. Briihl now puts V1 = 0 ; but this assumption may be avoided, and V, eliminated as an independent constant by combining equation [l] with the necessarily true relttt,ion 2n - wb - a - 2p - 3cy = 0. Multiplying the latter by V1, and adding, we get- and finally substituting x, y, p , and q for the constant quantities within brackets, we get- n .x + m . y + p . p + p i . q = R, , . . . . . [41 which is of the same form as [l], and identical with it when V, = 0, but in which R is not necessarily independent of the number of single bonds of union between carbon-atoms. In either case, x + y = c + 2h + V, represents the increase in refractive power for each addition of CH,. Experimentally, J: + y has been found to vary from 4.85 in the benzene series to 4.525 in the naphthalene-group. No values of .z and y can therefore exist which will in all cases satisfy equation [4], and this must also be true of the constants p and q.The following example illustrates this :- Taking the experimental value oE the refraction of two molecules of benzene, 51.86 = 12c + 1212 + 6V, + 6V2, and of one molecule of naphthalene, 43.93 = 1 0 ~ + 8h + 6V1 + 5V2 and subtracting, we have 2c + 4h + V., = 7.93. From this and the relation G + Sh + Vl = 4.85 or 4.525 we find Vz - 2V1 = constant p in equation [4] -- 1.77 or - 1.12. Now Bruhl (preceding Abstract) has found the following values for the constants of equation [4) :- - x = 2.48, y = 2.08, p = 1.78, q = 1.97 . . . . [51 The above calculation shows the negative influence of p to be as great as Bruhl assumes it to be positive. Again the difference between the molecular refractions of naphtha- lene and benzene, calculated with Briihl’s constants = 42.02 - 26-46 = 5.56, whereas the actual difference = 8.00. Briihl attributes the discrepancy to the greater dispersive power of naphthalene. The author rather attributes it to the incorrectness of Bruhl’s hypothesis, which he proceeds to show is unnecessary.Assaming either that double and treble bonds of union have no in- fluence on molecular refraction, or that Vz = 2V1, V, = 3VI, equa- tion [3] reduces to R = nx + my. The author has now determined the constants x and y from the observed moleculm refractions of a, series of five hydrocarbons of t h e general formula CBHZm, containing 1, 2, 3, and 4 double bonds of union, and thus arrives a t the equation R = n. . 4.014 + rn . 0.840. A table is then given showing the molecular refractions of these five hydrocarbons and of three others, containing from 0 to 5 double bonds, calculated by the author’s formula and by equation [4] with Bruhl’s constants ; and the agree- ment with experiment is seen t o be much better in the former case (mean error = 0.37) than in the latter (mean error = 0.8).200 ABSTRAOTS OF CHEMICAL PAPERS.The author therefore concludes that the mode of union of carbon- atoms has no influence on molecular refraction. I n the author’s formula, the values of x and y can only be re- garded as approximate. However, the range of variation is not great. A table is given of the values of x calculated for 22 hydro- carbons, roughly classified according to the number of double bonds in their molecules.Throughout y is taken = 0.84. In no case does the value of x differ much from the mean value given above. For one group only, of which hexahydronaphthalene may be considered typical, it falls as low as 3.75; but even here x + y = 4.59 is Thornsen’s Supposed Explanation of Molecular-refraction Relations. By J. W. BRGHL (Ber., 19, 3103-3108).-A partial reply to Thomsen (ibid., 19, 2837, see previons Ahtract). The author points out that the constant y in Thomscn’s formula for mole- cular refraction, R = fix + my, has been calculated from observa- tions on a series of hydrocarbons of the formula CBH2,,&, in which the increments of refractive power for each addition of Hz are very variable, sometimes positive, sometinies negative, a variability which can only be attributed to chemical constitution.Like other empirical formula, Thomsen’s is no doubt applicable to the observations from which i t was deduced, and possibly to others besides. But in many cases (quoted by the author) it is seriously at fault, whilst the author’s formula applies to all hydrocarbons except those having a high dispersive power, to which the author attributes a special in- fluence. Referring to his previous work (see preceding Abstracts) for a full discussion of the question, he here contents himself with quoting examples of isomeric compounds whose molecular refractive powers differ more or less. I n all the compounds selected, the dispersive power is low. Inspection of the table shows that when isomerides are equallysaturated, that is, contain the same numberof doubly or trebly bound atoms (isovaleric acid, propylic acetate, methylic butyrate), their molecular refractive powers differ very slightly ; but when the saturation is unequal (ally1 ethyl ether and valeral, cymene and hexahydronaphthalene) the differences are considerable, and beyond the possible limits of experimental error.The influence of saturation on refractive power cannot therefore be ignored. Absolute Electrodynamometer. By H. PELLAT (Con@. rend., 103, 1189--1190).-A description of a new electrodynarnometric balance. New Apparatus for Electrochemical Investigations. By N. v. KLOEUKOFF (J. pr. Chem. [a], 34, 539-547).--8 description, with plates, of a “ universal commutator ” which fulfils tbe following con- ditions :- That with a given large number of circuits in which the measure- ment of the strength of the currents has to be determined with one and the same measuring instrument, the making and breaking contact with the latter can be easily and quickly effected. within the observed limits of variation, CH.B. CH. B.0-907" 907-1100" Silver { Tin ,. 232*7-1110" 0-660" f 660-720" Iron.. 4 I 720-1@ooo [ 1050-1200° r 0-230" Nickel 4 230-400" I 400-1150" 0-890" 890 -1150" Cobalt = 0.05785 + 0*0000044t2 + 0~000000006t3. = 0.0578 + 0.0000088t + 0*000000018~2. r q; = omo7$8t + 17.20. \elt = 0.0748. = 14.375 + 0.06 12931s - 0*0000104741t2 + 0~0000000103~8t3. yr = 0.0612931 - 0*0000209482t + 0~0000000310344ta. 0.1 1012t + 0*0000253333t2 f 0.000000054666t3. 0.1101'2 + 0.00005066665 + 0*000000163998t2. 0.578035 + 0*00143598t2 + 0.000001195t3.0.57803 + 0.002871965 + 0*000003585t2. qi = yt = 9; = 0.218t - 39. yt = 0.218. nit = 0019887. { qi = 0.19887t - 23.44. 0.10836t + 0.00002833t2. { $ 0.10836 + 0.00004466t. t 0.183493t - 0*000282S2 + 0.00000046666t3. 0.183493 - 0.000564t + 0*000001339998t2. 0.099t -+ 0*00003Y75t2 + 6.55. yYt = yYt = 0.099 + 0.000061755. - 0.105845 + 0-0000228667t' + 0*0000000219427t3. = 0.10584 + 0.0000457334t + 0~0000000658281~2. 0.124t + 0*00004t2 - 14.8. yt = = 0.124 + 0.00008t.202 ABSTRACTS OF CEEMICAL PAPERS. the absorption of oxygen by the silver, and it was found that under these conditions the metal melts at 907", a temperature much lower than that given by previous observers. Molten tin differs from all ordinary liquids in that its specific heat changes very slowly.Experiments with gas-carbon of which the vessels used to hold some of the metals were made, confirm Weber's statement that at high temperatures the specific heats of the different varieties of carbon are identical. The variations in the specific heats of the magnetic metals, iron, nickel and cobalt, show that they exist in several allotropic modifica- tions. It is worthy of note that the changes take place at very different temperatures in the three cases. Experiments which are not yet completed, show that these changes of state &re intimately con- nected with the magnetic properties of the three metals. The author's results confirm Berthelot's criticisim of the law of Duloiig and Petit. This law amounts simply to a statement that there is a certain interval of temperature (between 0" and *looo) in which the values of the products of the specific heats of the elements into their combiniug wecghts are approximately equal, c.H. R. Themnochemistry of Bibasic Phosphates and their Con- geners. By A. JOLY (Cowpt. rend., 103, 1197--1199).-The heats of formation of the bibasic phosphates from the dissolved acids and dissolved oxides were determined both directly and iudirectly. Cttl. Calcium hydrogen phosphate, CaHP04, cryst. ........ + 26 9 Barium hydrogen phosphate, BaHP04, gelat.. ......... + 26-6 Barium hydrogen arsenate, BaHAs04, gelat. .......... + 27.8 Strontium hydrogen phosphate, SrHP04, cryst.. ....... + 25.2 Manganese hydrogen phosphate, MnHP04, gelat. ...... + 22.73 Manganese tetrahydrogen phosphate, MnH,( PO,),, gelat.+ 24.3 Barium hydrogen hypophosphate, BaH,(PO,),, cryst.. .. + 35.2 Barium hypophosphate, BaPO,, cryst. ................ + 2b.2 9 , 9 9 9' ,, cryst.. ......... + 27.8 9 , 9 , ,, ,, cryst.. ........... + 28.4 The differences between the heats of formation of the collojidal and cry stallised varieties is sufficient to show that the reactions involved in their formation are of a complex character. Ammonium Magnesium Phosphate. By BERTHELOT (COWL@. rend., 103, 966--970).-Tlie heat of formation of magnesium ammo- nium phosphate was determined by measuring the thermal dis- turbance which takes place when a solution of a magnesium salt is mixed with sodium phosphate and afterwards with ammonia. The numbers thus obtained for the heat of formation of the crystallised double phosphate were +40.7; +41*0; +40-6; +41*9.The last value is probably the most accurate, since the ammonia was added to the crystalline magnesium hydrogen phosphate, and the latter was converted directly into the crystalline double salt. A series of experiments in which a mixture of ammonia and sodium C. H. B.GENERAL AKD PHYSICAL CHEMISTRY. 203 phosphate was added to the magnesium salt showed that the difference between the heats of formation of the zolloidal and crystal- line varieties of the double phosphate is greater than +12.4. These experiments gave a higher value than the first series for the heat of formation of this compound, and the combined results of both series give for the heat of formation of ammonium magnesium phosphate, colloidal, +29.3 cal.; cryst,alline, + 41.9 cal. These values agree closely with the corresponding values for colloidal and crystalline trim agnesium phosphate. When magnesium hydrogen phosphate is in the colloidal condition, the displacement of the third atom of hydrogen by magnesium develops only +3*7 cal., whilst the same substitution in the crystal- line phosphate develops + 14.4 cal. Similar phenomena are observed with calcium phosphate. I n like manner, the action of ammonia on colloidal magnesium hydrogen phosphate develops only +4.1 cal., whilst its action on the crystallised salt develops +14.6 cal., a quantity higher than that developed by magnesium, and equal to that developed by sodium or potassium. It follows that ammonium in union with magnesium forms a base, the energy of which is com- parable with the energy of sodium and potassium, as already ob- served in the case of the chlorides and snlphates.(This ~ o l . , p. 96.j It also follows that the action of ammonia on trimagnesium phos- phate will produce only a very slight thermal disturbance. Trimagnesium phosphate is rapidly altered by ammonia with pro- duction of ammonium magnesium phosphate, not because the heats of formation of the two phosphates for the colloidal condition are rery different, but because the double salt more rapidly passes into the crystalline condition and thus develops heat. This result illustrates the fact that the more or less rapid formation of salts in the colloi'dal or crystalline condition depends on the order in which the reacting substances are brought together.Ammonia also acts on crystallised trimagnesium phosphate with development of + 0.42 cal., but the reaction is not complete without the addition of ammonium chloride. When this salt is added, there is a slight additioual development of heat owing to the formation of a small quantity of magnesium chloride ; this fact explains the effect produced by the presence of ammonium chloride when magnesium salts are precipitated by sodium phosphate. This effect is only exerted in presence of a t least three equivalents of base. Ammonium chloride alone has 00 action on magnesium phosphate. These facts explain the difficulty which is experienced in displac- ing ammonia from ammonium magnesium phosphate by means of magnesia or lime.Lime teiids to produce collojidal calcium phos- phate, the heat of formation of which is less than that of the double phosphate. The lieaf of formation of crystallised trimagnesium phosphate is also somewhat less than that of the double compound. That decomposition takes place at all is due to the combined effect of the slight dissociation of the ammonium compound in the presence of water, especially if heated, and the volatilisation of the ammonia, which is thus removed from the sphere of action, the mwneqium taking its place. C. H. B.204 ABSTRACTS OF CHEMICAL PAPERS. Saturation of Arsenic Acid by Magnesia: Formation of Ammonium Magnesium Arsenate. Ry C. BLAREZ (C'omp. rend., 103, 1133--1135).-The developments of heat accompanying the dis- placement of successive atoms of hydrogen by magnesium are +14*866 cal.; +11.464 cal. ; f F 0 3 cal., giving for the total heat of neutralisation, + 28-36 cal. The heat developed by the neutralisation of arsenic acid by mape- sium and ammonium is +37*645 cal., from which it follows that the displacement of the third atom of hydrogen by ammonium develops +11.30 cal. C. H. B. Heat of Formation of Potassium Methoxide and Ethoxide. By DE FORCRAND (Compt. rend., 103, 1263-1266).-Potassium meth- oxide is obtained by dissolving potassium in excess of anhydrous methyl alcohol and heating the solution in a current of pure dry hydrogen at 200". Complex alcoholates similar to those formed by sodium are at first formed. The heat of solution at 12" is +11*74 cal.CH?*OH liq. + +K,O solid = CH3-OK solid + 4H20 solid.. .......................... CH3*OH liq. + KHO solid = CH3*OK solid + CH,*OR solid + H,O liq. = CHS-OH liq. + CH3-OH liq. + K solid = CHs*OK solid + H CH,*OH solid + rtCH3*OH liy. = CH3*OK Potassium ethoxide is obtained in a precisely similar manner. A small quantity of crystals of the compound EtRO + 3EtOH was obtained. Heat of solution of the ethoxide at 12-15" = +14.70 cal. develops + 24-79 cal. ............................ H,O solid 9 , + 4-30 9 ) KHO solid.. ,? - 2.87 ,, gas .................................. j, + 38-17 ,, diss. in rtCH3*OH liq. .................. ,, + 12-76 ,, .......................... C2H,*OH liq. + &KzO solid = C,H,*OK solid + QH,O solid.. ........................ C,H,*OH liq. + KHO solid = C,H,*OK solid C,H,*OK solid + H,O liq.= C,H,*OHliq. + C,H,*OH liq. + K solid = CzH5*OK solid + C2H,-OK solid + rtC2H6*OH liq. = C2H,*OK The values for the potassium compounds agree very closely with those obtained previously for the sodium compounds, and the values are practically the same with both ethyl and methyl alcohol. More- over the values corresponding with the action of potassium and potassium hydroxide on the two alcohols agree closely with those corresponding with their action on water. In the case of sodium the differences between the heat developed develops + 22.28 cal. .......................... + H,O solid ,, + 1-79 7, KHO solid.. 9 , - 0.36 ,, H gas ................................ ,, + 35-66 , 9 diss. in rzCzH5*OH liq.. .................. ), + 13-59 ,, ..........................GENERAL AND PHYSICAL CHEMISTRY. 205 by its action on the two alcohols respectively, and on water, are much greater than the corresponding differences in the case of potassium, and the absolute values of the quantities are higher with sodium, a result which is due to the fact that the tendency to form polyalcoholic nlcoholates is much greater in the ease of sodium.Moreover, the heats of formation of the hydrates of potassium hydroxide are much greater than those of the corresponding sodium compounds. It follows that the alcoholates of potassium ethoxide or methoxide dissolved in the alcohols are practically in the same condition as potassium hydroxide dissolved in water, whilst the dissociation of sodium hydroxide in water is much greater than that of sodium methoxide and ethoxide in the alcohols. C.H. B. Heats of Neutralisation of Glyceric and Camphoric Acids. By H. GAL and E. WERNER (Corn@. rend., 103, 1199-1200).- Glyceric Acid, OH*CH,*CH(OH)*COOH.-Heats of neutralisation by the first and second equivalent of potassium hydroxide respectively +11*334 cnl. and +12.127 cal. ; total +23*461 cal. The addi- tion of a, third equivalent of alkali causes no further thermal dis- turbance. Camphoric Acid, C8H14(C00H)2.-Heats of neutralisation by the first, second, and Ghi1-d equivalents of sodium hydroxide respectively, +13%28 cal. ; +13.253 cal. ; +O.O cal. ; total +27.081 cal. These results confirm the former conclusion that the total heat of neutralisation of hydroxy-acids is lower than that of acids into which the hydroxyl-group has not been introduced.C. H. B. Heats of Neutralisation of Malic and Citric Acids and their Pyrogenic Derivatives. By H. GAL and E. W-ERNER (Compt. rend., 103, 1019-1022). Heat of Heat of solution neutrdisation. at about ZOO. Maleic acid ........ 13.310 x 2 - 4.438 Fumaric acid ...... 13.299 x 2 - 5.901 Citraconic acid.. .... 13.511 x 2 - 2.i93 Mesaconic acid.. .... 13.633 x 2 - 5.943 Itaconic acid.. ...... 12.837 x 2 - 5.923 Malic acid.. ........ 12.4 x 2 Citric acid.. ........ 12.8 x 3 The heat developed by neutralisation is practically the same for each acid function of the same acid, In all cases, with the exception of itaconic acid, the heat of neutrali- sation of the pyrogenic derivatives is about 2 cal.greater than that of the generating acid, a relation similar to that already observed in the case of monobasic acids and the corresponding hydroxy-acids (this vol., p. 96). The pyrogenic acids derived from malic acid by the loss of HzO, and from citric acid by the loss of CO, + H,O, no longer contain the hydroxyl-group. C. H. B. VOL. LII. P206 ABSTRACTS OF CHEMICAL PAPERS. Heat of Neutralisation of Meconic and Mellitic Acids. By H. GAL and E. WERNER (Compt. rend., 103, 1141--1142).-The heat developed by the action of successive equivalents of sodium hydroxide on meconic acid, OH*C4(COOH)s is + 14.074 cal.; +13*611 cal. ; +8.369 cd. ; +1.328 cal. = 37.382 cal. The heat developed by the action of sodium hydroxide on mellitic acid, C,(COOH),, is $15.040 cal.; pt15.516 cal.; +15*294 cal.; +13.713 cal.; $. 12.793 cal, ; + 21.678 cal. = 84.034 cal, The heat of neutralisation of meconic acid is less than that of tnellitic acid, probably because the former is a hydroxy-acid. In both cases the heat of neutralisation diminishes as neutralisation becomes more camplete. The values far mellitic acid show that if neutral sodium mellitate is evaporated with excess of hydrochloric acid, it will lase part of the base and yield an acid salt, and the same acid salt will be obtained, when mellitic acid is heated with a solution of an alkaline chloride, The values obtained for mellitic acid are analogous to those found for phosphoric, sulphuric, and other acids in which several hydroxyl-groups are united with the same radicle.The numbers for the six acid functions of mellitic acid differ more widely than would have been expected from the symmetrical constitu- By 0, W. A, HAHLBAUM (Bey.. 19, 2860--2862).-An improvement on Andree’s form (Ann, Phys. Chem, [2], 4, 164), Influence of Change of Atmospheric Pressure on Boiling Point, By (3. W. A. KAHLBAUM (Ber., 19, 3098--3101).-With the exception of Broch’s “ Temperatures d’kbullition de l’eau pure ” (Trnv. et Mim. Bureazt I n t e r n a t . 3es Po& e t Mesh, I., A., 43 (1881)), calculated from Repault’s observations (Mein. Acad. Xci., 21 (1847)), accurate determihations of boiling point at regular intervals of pres- sure haTe not been made. Thc author has made such a series of measurements for ether (sp. gr. 0.720), The ether was boiled ih a platinum vessel, the heating being as uniform as possible; and to avoid possible change of the xero point of the thermometer, the latter was wrapped in wadding and transferred to a vessel of boiling ether after each observation.It was thus maintained at about the Bame temperature for a period of four months. The author strongly recommender this device. By graphic interpolation, the boiling points were calculated for each mm. of pressure from 721 to 750, and are given in tabular form. Only relative, not absolute, accuracy is claimed for them. A comparison of thiR table with Broch’s shows that within the ordinary limits of variation of atmospheric pressure, the curves of boiling point for water and ether are practically parallel. Assuming this to be true for other liquids whose boiling point may exceed 100” by as much as that of ether falls below it, the author gives a table of corrections of observed boiling point for each mm.pressure, for liquids boiling between 30” and 170°, of which the following is a condensed form- tion generally assigned to this acid. c. H, €3. Temperature Regulator.GENERAL AND PHYSICAL CHEMISTRY. 207 Between 720-730 mm. = + 0.038" ,, 730-740 ,, = + 0.037 ,, 740-750 ,, = + 0.037 750-760 mm. = + 0.037" 760--7iO ,, = -0.036 - 770-780 ,, - -0.036 Vapour-tensions of Ethereal Solutions. By E. RAOULT (Compt. rend., 103, 1125--1127).-The author has carefully measured the vapour-tensions of ethereal solutions of several organic compounds at different temperatures. Between 0" and 25", the difference between the vspour-tension of the ethereal solution and that of the ether is exactly proportional to the vapour-tension of pure ether at the particular temperature.For solutions containing from 1 t o 5 molrs. of the substance in 5000 grams of ether, the difference between the vapour-tension of the solution and that of pure ether is proportional to the amount of solid in solu- tion. The relative diminution of the vapour-tension caused by the sohtion of 1 gram of the substance in LOO grams of ether depends on the nature of the substance. The molecular reduction of the vapour- tension 7c is obtained by the formula k = S+f x 3, in whichf is the vapour-tension of ether, f tbe vapour-tension of the solution, M the molecular weight of the substance, and P theamount dissolved in 100 grams of ether.It is found that if a gram-molecule of any compound whatever is dissolved in 100 grams of ether, the vapour- tension of the ether is diminished by a constant, fraction of its normal value. For all temperatures between 0" and 25", the value of this fraction is 0-71. f P C. H. B. Apparatus for Measuring the Tension of Vapours. By G. W. A. KAHLBAUM (Ber., 19, 2954--2958).-The essential point in this apparatus is the maintenance of a uniform temperature by the circulation of a curnent of water heated in a vessel exterior to the Dissociation of Salts containing Water of Crystallisation. By W. M~LLER-ERZBACH (Ber., 19, 2874-2876).-A continuation of the author's experiments (Abstr., 1885, 952 ; 1886, 10) in which the relative vaponr-tensions of the water in the salts and of pure water are compared.The following salts are examined : CaN,O, + 4H,O, jacket. w. P. w. P 2208 ABSTRACTS OF CHEMICAL PAPERS. relative tension = 0.06--0.07: CaNZO6 + 3Hz0, relative tension = 0*10-0.11 ; after the loss of 1 mol. HzO, this fell to 0.04. The salt obtained by dissolving the latter in a fourth molecular proportion of water had a relative tension = 0.27-0.36 ; after 2 mols. H,O had been removed, the tension fell to 0.08-0.07, and reached 0.04 before the last traces of water were removed. The author regards this variation in the tension required to separate the different proportions of the water from the solution as affording good evidence of the existence of a molecular compound in the liquid. With SrNzOg + 4Hz0, the relative tension at 12.g was 0.61 ; ZnN20G + 6Hz0, relative tension = 0.18 at 12*1", after the loss of 2Hz0 this fell to 0.025, and became imperceptible when a salt containing 3 mols.HzO was left. BaHZO2 + 8Hz0 lost 1 mol. HzO with a relative tension = 0.88-0.92, 5 more mols. H,O were lost when it fell to 0.18-0.22, and a diminution to 0.10 to 0.12 accompanied the separation of a seventh mol. H,O; 1 mol. HzO remaining combined with the salt. SrH,O, + 8Bz0 lost 1 mol. H,O with a relative tension = 0.73 at 17*6', and a further 6 mols. HzO with a relative tension = 0.27 at 18*5", 1 mol. H,O remaining combined with the hydroxide. w. P. w. Dissociation of Copper Sulphate. By W. MZLLER-EEZBACH (Rer., 19, 2877-2879).-1n this paper, it is pointed out that H.Lescmur, working with a different method and at higher temperatures, has arrived at results (this vol., p. 100) which agree exactly with those previously obtained by the author (Abstr., 1886, 10). Lescoeur, in his criticisms on the author's earlier experiments (Abstr., 1884, 952), has overlooked these more recently published experiments on the dissociation of copper sulphate. w. P. w. The Relation between the Efflorescence and Deliquescence of Salts and the Maximum Vapour-tensions of their Saturated Solutions. By H. LESC~UR (Cornpt. rend., 103, 1260--1263).-The presence of a few tenths of a per cent. of water over and above that which is actually combined with the salt, is sufbcient to give the maximum vapour-tension of its saturated solution. In order that a salt may be deliquescent, the maximum vapour-tension of its satu- rated solution must be lower than that of the aqueous vapour in the atmosphere.The following table gives the vapour-tensions of the saturated solutions, and may be termed the scale of deliquescence at 20':- Potassium nitrate . . . . 15 mm. Potassium chloride . . 13.55 mm. Sodium acetate (cryst.) 12.4 ,, Iodic acid . . . . . . . . . . . 11.6 ,, Strontium chloride. . . . 11.5 ,, Sodium nitrate . . . . . . 11.15 ,, Sodium chromate . . . . 10.6 ,, Calcium nitrate . . . . . . 9.3 ,, Ammonium nitrate . . 5.1 ,, Strontium bromide. . Potassium carbonate Magnesium chloride Calcium chloride . . . Potassium acetate . . Arsenic anhydride. . Sodium hydroxide.. Potassium hydroxideGENERAL AND PHYSICAL CHEMISTRY.209 On the other hand, if the vapour-tension of a hydrated salt is greater than that of the aqueous vapour in the air, the salt will be efflorescent. The following table furnishes a scale of efflorescence at 20':- Sodium arsenate, NhHhs04 + 12H,O ........ 16.0 mm, .. sulphate, N%SOa + 1OHzO.. .......... 13.9 1, ,, phosphate, Na2HP04 + 12Hz0.. ...... 13-5 ,, .. phosphate, N%HP(34 + 7H20 ........ 9.0 .. Ciipric sillphate, CuS04 + 5H20.. ............ 6.0 .. Strontium hydroxide, SrHZOz + 8Hz0 ........ 5% .. Nickel chloride, NiCI, + 6HzO .............. 4.6 ,, Sodium arsenate, NazHAsOk + 7Hz0.. ........ 4 6 .. Barium hydroxide, BaHzO2 + 8Hz0 .......... 4.2 ,, Boric acid, H3B03, about .................... 2.0 ,, Stroutium bromide, SrBr, + 6H20, about.. .... 1.8 .... acetate, NaC,H,OZ + 3H,O .......... 12.4 ,, .. carbonate, Na2C03 + 10HzO .......... 12.1 .. .. chloride, SrC1, + 6H,O ............ 5.6 3 , Oxalic acid, H2C204- + 2Hz0, about.. .......... 1.3 .. C. H. B. Density of Weak Aqueous Solutions of Certain Salts. By J. G. MCGREGOR (Chem. News, 55, 3--6).-Experiments have been made to decide:-1. Whether or not there are solutions of salts, given volumes of which are less than the volumes of the water they contain. 2. How the density of very weak solutions varies with their strength. Anhydrous copper sulphate has already been shown to form weak solutions exhibiting the first property. Experiments with zinc sulphate, magnesium sulphate, and calcium chloride now show that these salts do not behave in this manner, but that the solutions they form are always of greater volume than the water they contain.The strength of the solutions examined, varied in the case of zinc sulphate from 0.186 to 2.695 per cent. of the salt; of magnesiiim sulphate from 0.191 to 1.132 ; of calcium chloride from 0.191 to 1.320 per cent. With regard to the density of the solutions: with the zinc and magnesium salt, the increase in density is nearly in direct proportion to the percentage of salt in solution, whereas with calcium chloride the rate of increase of density with concentration diminishes as the percentage of salt in solution increases. The mode of experimenting is fully described and the results are tabulated. D. A. L. Cohesion and Slibmersion Figures. By C. TOMLINSON (Chenz. News, 55, 1-2).-Re€erring to a paper by Ackroyd on this subject. (Abstr., 1886,971), the author recalls the work of Rogers and his own work in the same direction.In 1864, he published papers on " Sub- mersion Figures " produced by a large variety of liquids, and diagrams were given illustrating the formation and structure of these liquid " rolling rings," and also of ai3rial " rolling rings." Reference is also made to other work on the same subject, to the modes of exhi- biting vortex rings a t the lecture table, and to the author's researches210 ABSTRACTS OF CHEMICAL PAPERS. on the action of nuclei and porous bodies in liberating vapour from boiling lisquids. D. A. L. Weight of Drops and their Relation to the Constants of Capillarity and the Capillary Meniscus Angle. By J.TRAUBE ( J . pr. Chenz. [a], 34, 515-538; compare this vol.? p. 10l).--From the results obtained with water and with solutions of alcohol of dif- ferent strengths, the author concludes that the weight of drops and their capillary constants decrease with the increasing curvature of the surface of formation of the drops; this decrease does not, however, begin before a certain degree of curvature, which is different for different liquids. The decrease of the weight of drops in the case of different liquids is not proportional to the increase of curvature, but appears to be the greater the smaller the capillary constants of the liquid. He also finds that the edge-angle of the meniscus of drops of different liquids is equal or proportional to the meniscus angle of the same liquid in capillary tubes.The author also made a series of determinations with solutions of alcohols and acids of different strengths, observing in each case the time which was necesswy for the formafion of a drop from a capillary tube and also the time necessary for the formation of a drop plus the curved surface of its meniscus; by working out the proportion between these, he found that the ratio of the time of formation between the curved surface of the dropmeniscus and the drop increases with the increasing radius of the tube ; and that the drop- meniscus in general increases in proportion to the drop with increasing concentration of the solution ; that is, with decreasing cohesion. The difference in the quotient - decreases with increasing concentration (T, = time of formation of the drop-meniscus, Tt = that of the drop) ; therefore, curves constructed with the concentrations (as abscissae) and these quotients are concave.With compounds of an homologous series, and equal concentration, the drop-meniscus increases wiih the molecular weight of the dissolved substance. The determination of the size of the drop-meniscus was made in order to see if any con- clusion regarding the meniscus angle could be drawn from their respective sizes. The results showed that-1. The volume of the drop-meniscus and the top meniscus angle, whieh the tangential planes, formed by the last particles of the curved surface of the drop- meniscus, form with the horizontal tube wall, decreases with in- creasing concentration of the solution, like the meniscus angle in capillary tubes.2. For substances of an homologous series, in solu- tions of equal strength, the volume of the drop-meniscus decreases with the increasing molecular weight of the dissolved substance, as do also the top edge of the angle of the drop-meniscus, and the meniscus in capillary tubes. In conclusion, the author considers that Laplace’s hypothesis, according to which the meniscus angle for wetting liquids is equal to 0, cannot be maintained in view of the results obtained by the direct measurement of the capillary meniscus at different temperatures, and by the measurement of drops ; moreover, one of the most important T W T’tINORGANIC CHEMISTRY. 211 theories of capillarity can only be maintained if the finiteness of the meniscus angle is accepted.Wilhelmy's important law of the constawy of the meniscus angle cannot be accepted in its universality, since the size of this angle appears to depend on the temperature of the liquid and the curvature of the walls of the tube. Noreover, the meniscus angle, which the surface of a drop forms with a horizontal glass surface, is not, as Quincke supposes, e ual to tha$ which is enclosed by the meniscus complement of the other. Volatilisatios of Dissolved Substances during the Evapora- tion of the Solvent, By P. M. DELACHARLONNY (Compt. rend., 103, 1128--1129).-Concentrated solutions of sulphuric acid, sodium hydroxide, sodium carbonate, and ferric sulphate were heated at 65- 70" in vessels closed by inverted funnels. In a few hours, the fact that some of the dissolved substance had been carried off in the vapour of the solvent was easily recognised by means of suitable test-papers which had been placed in $he apex of each funnel.Even a t the ordinary temperature, the papers had distinctly changed after four or five days. Acid solutions of alum and of ferrous sulphate at the ordinary tem- perature gare similar results. There is no evidence of the actual carrying off of solid particles ; the colour of the test-papers was unihrm, and not in streaks or patches. C. H. B. The Periodiac Law, By W. SPRING (Bar., 19, 3092-3093).-A question of priority with regard to Emerson Reynolds's illustration of this law (Ckem. News, 54, l), G. H. M. surface in tubes wit 1 a, vertical partition. The one is perhaps the189General and Physical Chemistry.Actinornetry.By E. DUCLATJX (Compt. rend., 103, 1010-1 012).-0xalic acid in aqueous solution is converted into carbonic anhy-dride and water by the action of light in presence of oxygen, and thisdecomposition is not due to any rise of temperature resulting fromabsorption of the sun’s radiation, but is brought about by the visibleand ultra-violet rays. In order to secure sufficient contact with theoxygen of the air, the solution is placed in flat vessels and the samevolume of liquid is always employed ; also, in order to eliminate thesome what considerable influence of the concentration of the solution,a, dilute solution, containing 3 grams of oxalic acid per litre, isemployed. The amount of change is determined by titratinq withlime-water.I f the solution of oxalic acid has been kept for abouttwo months in the dark, it is found to be much more sensitive to theaction of light than a freshly prepared solution-a fact which indi-cates that the two liquids have not the same molecular constitut,ion.The change is analogous to the ripening of collodion. The samedegree of sensitiveness can be imparted to a freshly prepared solutionby exposing it to sunlight for a few hours, and if a concentrated solu-tion is treated in this way and is then diluted to the strength given,the increased sensitivenew is transmitted to the dilute solutions-afact which indicates that the alteration takes place in the moleculesof the acid and not in those of the water.The total quantity of acid decomposed when the same quantity ofliquid is exposed during the whole day is much greater than the sumof the quantities decomposed when a fresh portion of solution isexposed during each hour, the difference varying from day to day.There is therefore a period of quiescence similar to that which isobserved in many photographic and chemical reactions, and whichBunsen and Roscoe have termed photochemical induction in the caseof hydrogen and chlorine.Fluorescences of Manganese and Bismuth.By L. DE BOIS-BAUDRAN (Compt. rend., 103, 1064-1068).-A mixture of 100 partsof yttrium sulphate with 2 parts of manganese snlphate shows ayellowish-green fluorescence, the spectrum of which consists of abroad band which begins at about 6500, attains its maximum bril-liancy at 5640, and fades away gradually at 489@-&0.With 4 percent. of manganese sulphate, the fluorescence is more intense. but itscharacter is not altered. The fluorescence differs from that of calcium,and is not due to the presence of traces of this element. A mixtureof 100 parts of yttrium sulphate with 2 parts of bismuth sulphategives a red fluorescence, with a spectrum consisting of a band whichbegins at 6840, attains its maximum brilliancy at 6420-6400, andfades away at 5790-5770. This fluorescence is not due to the pre-sence of magnesium.C. H. B.VOL. LII. 190 ABSTRACTS OF CHEMICAL PAPERS.Calcium sulphate mixed with small quantities of both bismuth andmanganese sulphates gives a fluorescence which is yellow at hhecentre, and pale-green further from the electrodes.In the spectrum,the orange-red band of the calcium-bismut h fluorescence is verydistinct. If the tube is heated, the fluorescence becomes rose-yellow,the red band is scarcely affected, and the brilliancy of the green isdiminished. At a higher temperature, the fluorescence diminishesand again becomes green with a bluer shade than originally, and thered band is almost extinguished. In all cases, the fluorescence is muchless brilliant than with calcium and inanganese sulphates free frombismuth.A mixture of magnesium suiphate with both manganese andbismuth gives a fluorescence due to the superposition of the mag-nesium-manganese and the magnesium-bismuth fluorescences.Cadmium sulpbate with small quantities of both manganese andbismuth gives the cadmium-manganese fluorescence, which is some-what less brilliant than in the absence of bismuth, Strontium sul-phate, on the other hand, under similar conditions, gives the strontium-bismuth fluorescence, the intensity of which is somewhat diminishedby the presence of manganese.A mixture of calcium oxide with small quantities of manganeseand bismuth oxides gives the calcinm-manganese fluorescence withsomewhat diminished intensity.A mixture of zinc and calcium sulphates, in varying proportions,with small quantities of manganese, gives a, fluorescence in whichthe calcium-manganese fluorescence is muoh more prominent thanthat due to zinc-manganese.With only 5 per cent.of calciumsulphate, the effect of its presence is readily observed, and it is quitedistinct with even 2 per cent. if the tube is heated.Effect of Manganese on the Phosphorescence of CalciumCarbonate. By E. BECQUEREL (Compt. rend., 103, 1098-1101).-The most highly phosphorescent crystals of Iceland spar, which showan orange phosphorescence, contain a somewhat high proportionof manganese, probably in the form of carbonate, with mere traces ofiron. The less strongly phosphorescent varieties contain very littlemanganese.Calcium carbonate, precipitated from a solution of calcium chloridecontaining 4 per cent. of manganese chloride, gives alniost identicalresults. Calcium carbonate, formed on the surface of such a solutionwhen exposed in an atmosphere charged with the vapour of am-monium carbonate, does n o t show the same phenomenon.These results explain the author’s earlier observation, that calcinmcarbonate precipitated from calcium chloride prepared from Icelandspar, always gives an orange phosphorescence, whilst that preparedfrom aragonite shows a green phosphorescence.Further experimentsare necessary to determine whether manganese is the sole cause of thephenomenon.The phosphorescence of Iceland spar is affected by lithium, bis-muth, and antimony, and by various metallic sulphides.C. H. B.C. H. BGENERAL AND PHYSICAL CHEMISTRY. 191Red Fluorescence of Alumina. By L. DE BOISBAUDRAN (Compt.rend., 103, 1107).-Pure calcined alumina shows no red fluorescencewhen subjected to the action of the silent discharge in a vacuum, butthe red fluorescence described by Becquerel (“ La Lumiere”) isshown brilliantly if the alumina contains a small quantity of chromicoxide, and is visible even with so small a proportion as 0.001 per cent?.Alumina with 1 per cent.of manganese oxide shows a greenfluorescence ; with 1 per cent. of bismuth oxide, a lilac fluorescence inthe cold, which becomes blue on heating. Magnesia with 1 per cent.of chromic oxide shows a red fluorescence, whilst the fluorescence oflime containing chromic oxide differs very slightly from that of purelime. C. H. B.Phosphorescence of Alumina. By E. BECQUEREL (Coinpt. rend.,103, 1224-12 27) .-The alumina prepared by Boisbaudran (pre-ceding Abstract) does actually show a feeble red phosphorescence, butafter being heated to a very high temperature in a platinum cruciblefor 15 minutes, it shows the red phofiphorescence brilliantly.Itwould seem, therefore, that Boisbaudran had not sufficiently dehy-drated his product.The author has repeated his earlier experiments, and confirms hisformer conclusion that pure alumina shows some phosphorescence,which is often greenish in colour, but if strongly heated it shows abrilliant red phosphorescence, the intensity of which is increased bythe presence of small quantities of chromium and certain other sub-stances. He points out that the exact character of a phosphorescenceor fluorescence will depend on the agent by which the substance isexcited and the conditions under which excitation takes place.C.H. B.Molecular Refraction of Liquid Organic Compounds ofHigh Dispersive Power. By J. W. BRUHL (AnnaZen, 235, 1-106 ; see also Ber., 19, 2746).-1n previous papers (Abstr., 1880,293, 295, 685, 781 ; 1882, 15; 1882, 263, 445, 82‘7, 829), the authorhas shown that the mode of union of atoms in n compound, inde-pendently of their mere number, has a special influence in raisingthe moleculgr refractive power. The present paper embodies anumber of new and confirmatory observations, together with discus-sions of the validity of the several expressions for molecular refrac-tive power, and of the possible connection between dispersion andrefractive index or chemical constitution. Numerous references tothe work of other physicists are given.The methods of investiga-tion have been previously described.The first part of the paper contains an account of the prepayationand purification of 21 unsaturated compounds specially examined,together with determinations of their densities, refractive indices forthe lines a, D, 6, and v, their molecular refractive powers accordingto Dale and Gladstone’s formula ( p a - 1). ;, and the more recentor “new ’’ formula tk’). g, &c. The constants for these andpa2 + 20 192 ABSTRACTS OF CHEMICAL PAPERS.for 21 other unsaturated compounds previously examined are arranqedin four tables, from which subsidiary tables are constructed to illus-trate special points.Gladstone and Dale's constant was found to be correct withinmoderate limits of temperature, and since it was applied chiefly tothe saturated and feebly dispersive compounds o€ the fatty series,comparable results were obtained.More recently, H. A. Lorenz(Ann. Phys. Chem. [2], 9, 641) and L. Lorenz (ibid., 11, 70) haveproved by independent theoretical methods that the relation betweenthe velocity of propagation of light and the density of the medium iscontained in the formula - - - - constant, when n = refractiveindex, d = density. This constant was proved by these authors, andby Nasini and Bernheimer, t o vary much less with the temperaturethan the old one. Landolt, also (Abstr., 1882, 909), by its aid hasrecalculated the molecular refractive powers of many compoundsexamined by various authors, and found not only that all the earlierestablished relations are equally well expressed, but that a closeraqreement between theory and observation is attained by its use.There still remain, however, serious discrepancies between theoryand experiment, especial€y in the case of substances of high dispersivepower.The question then presented itself: Is there any relation betweendispersion and mean refractive index on the one hand, or chemicalconstitution on the other ?Dispersion may be measured either as py - pa, or by the constantB in Cauchy's equation-ma - 1(n2 + 2jd -B CP = A + X s + Q - + - * .(using only constants A and B), in which p = refractive index forwave-length X, A = refractive index for infinite wave-length.Inthe saturated compounds of the fatty series, B is small (0.3 t o 0.5) ;but in the unsaturated compounds tabulated in this paper B is verygreat, in the case of cinnamaldehydereaching the enormous value 2.5.Calculating the constants A and B from observations of and ,q, theauthor has applied Cauchy's equation to calculating ,uD for the last-named substances, and he shows by a tabular statement that theoryand experiment agree well for cornpounds of low dispersion, but thatvery serious discrepancies arise when the dispersive power is high.Cauchy's equation is therefore untrustworthy in these cases. Nodefinite relation can be traced between dispersion and mean refrac-tive index. (See also following Abstract.) Neither does any con-nection exist between dispersion and chemical constitution.ThisB is shown by selected examples, in which - (dispersion at 20" ford:unit density) is seen to have very different values for compounds ofanalogoils constitution, nearly equal density and equal refractiveindex; whilst, on the other hand, the dispersion may be the samefor substances of very different chemical structure.Enquiry is next made into the validity of the old and new formulaQENERAL AND PHYSICAL CHEMISTRY. 193P N a 2 - 1 Ppa2 i- 2 ’ dTables are given of the values of (pa - 1)2 and - - for the42 substances, both experimental and calculated by the aid of thefollowing table of atomic refractive powers :------I__Singly-linked carbon .............Hydrogen ......................Singly-linked oxygen ............Aldehydic oxygen ................Chlorine ........................Bromine ........................Iodine..........................Singly-linked nitrogen ...........Equivalent of ethylene grouping.. ..Equivalent of acetylene grouping.. .Ca .5-001-302 -803 ‘409.8715.3924.695’752.301.90?-a .--4 -861-292.713.299.6314 ‘8123 -355-352 -001 ‘80r’a .--2 -481 *041.582.346 ‘028 *9513.993 *021 *781 *97C‘A. --2 -431 ‘021.562-295 *898 -7013 *362 -b71 -591.86In this table ra and rA are the equivalents for the refractive indexof a (red hydrogen line), and A, index for infinite wave-length, usingthe old (Gladstone’s) formula : rlcr and T ’ ~ the similar equivalents forthe new (Lorenz).This table has been calculated in part by theauthor, in part by Landolt.From this table, it is seen that when the molecular refractive poweris calculated by the old formula, the differences between theory andexperiment in most cases exceed the possible limits of experimentalerror, and are especially great for substances of high dispersive power.Since all the differences are positive, it is evident that dispersion heretends to raise the molecular refractive power. When the latter iscalculated by the new formula, the differences, although still positive,are both relatively and absolutely smaller. The disagreement is,however, well marked in the ca5e of highly dispersive compounds.To show the disturbing influence of dispersion more dearly, tbeauthor in a new table arranges the various substances in the order ofascending values of B (dispersion-coefficient), placing opposite eachthe differences between the observed and calculated refractionsaccording to the old and new formula.When B is small, thediscrepancies are relatively about the same for both; but as Bincreases, there is a rapidly growing inequality between them, theadvantage being always with the new formula. The t w o formulaeare therefore of nearly equal value (as Landolt supposed them alwaysto be) only for feebly dispersive substances. Yet even here thenew gives the more concordant results, as the author shows by anew table, including only unsaturated but feebly dispersive com-pounds.In the author’s opinion, the defects of the new formula are mainly,but not altogether, traceable to dispersion.The general connectionbetween them has been proved above ; but it is pointed out that noayithmetical relation exists between the discrepancies and the disper-sion-coefficieut194 ABSTRACTS OF UHEMICAL PAPERS.Although as a rule the dispersion is high in compounds con-taining many C=C’ groups, some unsaturated compounds of lowdispersive power exist. Certain striking examples are mentioned, forwhich the new formula nevertheless gives good results. These showalso that there is no connectmion between dispersive power andchemical cons ti t u t i on.Some little space is devoted to refuting Gladstone’s theory (Abstr.,1882, 133), adopted by Nasini, namely, that the atomic refraction ofcarbon-atoms, which are united only to other unsaturated atoms,is higher than that of Unsaturated atoms, which are not so united.Examples are given of compounds containing atoms of this kind, forwhich theory and experiment give concordant results.Moreover,there is no connection between dispersion and such atoms, as provedby the high dispersive power of many substances (aldehyde, fur-furaldehyde, &c.) from which they are absent.The highly important relationship of molecular refractive powerto unsaturated carbon groups is next discussed. This has beendenied by Nasini and others. (See also Thomsen, followingAbstract.) The author yehearses the older arguments on which hisviews rest, and quotes three series of substances containing 1,2, and 3ethylene (CZC) groupings respectively.For these the meanexcesses of observed molecular refractive power over that calculatedfor the empirical formulae alone, are 1.79, 3.47, and 5.38 respectively.A fourth table shows the empirical refractive powers for a series ofseven substances, each containing 4 C=C groupings. I n this, thediscrepancies range from 4 x 1.73 for the feebly dispersive ally1pbenoxide, to 4 x 2.03 for the highly dispersive cinnamic alcohol.It is remarkable that when hydrogen is removed from a hydro-carbon, so as to form a ring of singly-linked carbon-atoms, there isno undue increase in refractive power. For example, in citrene, pitrene,and tetrahydroterpene, which according to Wallach contain 2, 1,and 0 C=C groupings, whilst all three contain rings, the excess ofobserved over empirical molecular refractive power amounts to2 x 1.78, 1 x 1.78 and 0.I n a note, it is pointed out that these considerations speak stronglyin favour of KekulB’s benzene formula, as opposed to the prismaticformulae of Ladenburg and others.Thornsen’s thermochemicalresearches (Abstr., 1880, 785; 1882, 721) lead to exactly oppositeconclusions.The final conclusion of this chapter i s : that ethylene groups areeffective in raising the molecular refractive power ; and that wherethe increase is greater that can be thus accounted for, it is attributableto dispersion.A question of practical importance is : how far may the molecularrefractive power according to the new formula be safely appliedto determining chemical structure ? This is attacked by makingn comparison between the observed and calculated (taking structuwinto account) powers for various substances, and the number of C=Cgroupings in their molecules.The value of this grouping accordingto Landolt =1.78; or rather the mean value, since it is not thesame for all series. Many of the slighter discrepancies in the tablGENERAL AND PH YSTCAL CHEMISTRY. 195may be explained by this variability, the presence of impurities, oruncertainty as to chemical constitution. But of the 42 cases quoted,in only eight does the discrepancy amount to more than the value ofan ethylene group ; and all these are of substances of high dispersivepower. Of the remainder, in only three does the dimrepancy equalone-half of 1.78.In some cases even of highly dispersive bodies thedifference is less than this. It is not possible to assign an exact limitbeyond which dispersion becomes of importance ; but, generaily, con-clusions as to chemical structure are insecure when the dispersionequals that of cinnamic alcohol (PUS - pa = 0.0248 ; py - pa = 0.0412 ;B = 1.38). I n such a case efforts should be made to prepare lessdispersive derivatives of the substance in question, which is veryfrequently possible.I n anot,her chapter, the value of the acetylene, CEC, grouping isdiscussed. A strong point in favour of the new formula is that hereits value is greater than that of the ethylene grouping, whereas forthe old formula it is less.But old and new values are to some extentvariable with the dispersion. A fresh study of five compounds (threepropargyl- derivatives, heptidene, and acetenylbenzene) lends to theslightly increased mean value (see table above) 2.18. This and thevalue of the ethylene grouping agree remarkably well with those calcu-lated by the author from Mascart’s determinations of pD for gaseousethylene and acetylene (Compt. rend., 86, 1182).I n Section 111, the question is discussed to what extent are thediscrepancies between theory and experiment removed by substitutingfor pa in the new formula, the refractive index A for infinite wave-length calculated from Cauchy’s formula, using firstly two, andsecondly three, constants, An elaborate study of the results soobtained leads to the following general conclusions.When A is calculated from Cauchy’s equation with two constants(A and B), the molecular refractive powers, although in better agree-ment with experiment, seldom differ much from, and always in thesame sense as, those calculated from pa.For feebly dispersive sub-Rtances, in fact, little is gained by the substitution ; but for compoundsof high dispersive power the advantage is usually, but not always, verydecided.The values of A deduced from Cauchy’s equation with two and withthree terms are about the same when the disperson is low. But forhighly dispersive substsLilces the values of A from the three-termedformula are always the greater ; hence the molecular refractivepowers calculated from them diverge still more from the observedpowers. Here, in fact, the uses of A and of pa lead to about the samere8 u l t s.The author’s conclusion is that Cauchy’s formula is purelyempirical, and without any physical signigcance.(See also nextAbstract.) CH. B.Experimental Examination of the Older and More RecentDispersion-formulae. By J. W. BRCHL (Ber., 19, 282l).-Theauthor has shown (preceding Abstract) that in calculating refractivepower, the difficulty introduced by dispersion cannot be removed b196 ABSTRACTS OF CHEMICAL PAPERS.substituting for n (the refractive index for any particular wave-length) its value for a wave-length supposed infinite, deduced fromCauchy’s well-known equation.In view of the great importance ofthe subject in its chemical aspect, the author here presents a criticalinquiry into the trusfworthiness of the various formula connectingrefractive index with wave-length, which have been proposed fromtime to time.B CX2 x4 Cauchy’s original formula, n = A + - + - + . . . . ., as well aslater modifications of it,, lead to the conclusion that the refractiveindex n diminishes oonstantly as the wave-length increases, reachinga definite minimum value when X becomes infinite, a, conclusion whichis manifestly unfirue in the case of substances showing abnormal dis-persion. Of the more modern theories discussed, which embrace thephenomena of abnormal dispersion, only one, that of Lommel, impliesa limiting value of a greater than unity.Others either do not givesuch a limiting value (Ketteler’s), or give it only under special con-ditions (Helmholtz’s).I n 1879, Mouton proved the untrustworthiness of Cauchy’s formulain calculating the dispersion of the ultra-red rays of the spectrum ofa specimen of heavy flint glass, when the constants A, B, C, were de-duced from the observed values of ?L for the seven principal Fraun-hofer lines. The differem- of hhe observed from the calculated valuesof n ranged from 0.0023 for h, = 8.8 to 0.0137 for X = 21.4, amountswhich greatly exceed possible experimental errors. Very similardifferences existed between the observed valnes of n for the ultra-redrays of the ordinary and extraordinary spectra of quartz, and thevalues calculated by Briot’s equation - = a + b - + c- + .. . . . 1 w? n4n2 x2 x dwhich gives a limiting value of n = di for h = 03. The con-stants here were calculated from some measurements by Mascart forthe lines C, G, 0. The results of these experiments are arranged bythe author in tabular form, and prove that Cauchy’s formula failswhen used €or calculating by extrapolation the refractive index forultra-red rays, and d fortiori for rays of infinite wave-length. Thesame is true of Christoffel’s modification of Cauchy’s equation. All,however, are available for interpolation.It might be supposed that the failure of Cauchy’s formula in thesecases was due to the narrow range of observations from which theconstants were determined.The author has therefore made a com-parison, based on a series of measurements by Langley, between theobserved and calculated values of 12 from the beginning of the ultra-violet to far beyond the red in the spectrum of flint-glass. Theconstants (A = 1.3504, B = 1.334171, C = -6.982411) were de-duced from the values of n for X = 3.97 (H1), X = 7.6, and X = 18.1(ultra-red).The tabulated results are remarkable ; in fact Cauchy’s formula ishere as valueless for interpolation as it was before for extrapolation.The interpolated values in no case agree with the observed values, iGENERAL AND PHYSICAL CHEMISTRY. 19‘7one case differing by so much as 0.0045, whilst the observed values of.n for X = 23-56 (1.5478) and for h = 28.0 (1.5435) are considerablysmaller than the calculated minimurn, A = 1.5504 for X = m..Theconstant C, too, being negative, it can be shown .~ that n should reach amaximum value (= 1.6141) when X = dr! = 3-23; whilstthe observed index for X = 3.44 was 1.6266, thatis, greater than thistheoretical maximum.The author next directs attention to Helmholtz’s formula-x4X2 - A;;;rta - 1 = Q .r - PXa,ain which P, Q, and XG depend on the nature of the medium. WhenP > Q, the refractive index must diminish as A increases, untilbecomes negative, that is, until total reflection occurs. When P = Q,.n reaches a minimum value for m; but when P < Q, this limitingvalue corresponds with a finite wave-length. A value of n independentof dispersion can only exist, then, when P = Q, in which case Helm-holtz’s formula reduces to Lommel’s.Ketteler’s still more recent formula-gives = 1, when h = m, that is, the limiting value of V L would beunity for all substances, and consequently there could be no index ofrefraction independent of dispersion.The author’s investigations have now shown that for calculations byinterpolation Helmholtz’s and Ketteler’s equations give equally goodresults in the case of media of low dispersive power.No choicebetween them is possible. But when applied to highly dispersivemedia, Helmholtz‘s formula is inferior not only to Ketteler’s (whichcontains an additional constant), but also to Cauchy’s. Takinga series of measurements of‘ n, for oil of cassia (Baden-Powell), theconstants for each formula were determined from observations extend-ing to the extreme limits of the visible spectrum.Calculating thevalues of n for intermediate wave-lengths, the best results wereusually obtained by Ketteler’s formula. But with constants deter-mined from lines between C and G, Cauchy’s formula proved mosttrustworthy, especially for extrapolation. These conclusions areclearly set forth in a tabular statement.An important result of this investigation is that Q in Helmholtz’sequation is always found > P, which at once disposes of Lommel’stheory. The refractive index should therefore be a minimum forsome wave-length not infinite. According to the way in which theconstants were determined, this minimum was either 1.59 for X= 8.535, or 1.6002 for X = 7397; whereas for the line A, n, wasobserved = 1.5963, or less than the theoretical minimum.In the foregoicg comparisons, the constants were always determinedfor lines within the limits of the visible spectrum.With constant198 ABSTRACTS OF CHEMIOAL PAPERS.determined over a much wider range, Wlillner has faund Helmholtz’sformula, and Ketteler his own formula, to give excellent results in thecase of feebly dispersive subslances, although, as the author points out,the two are fundamentally different, and cannot both be correct.From the author’s calculations, it appears that both are equally in-sufficient when applied to highly dispersive media. In proof, a table isgiven of the differences between the observed values of n for the ordi-nary and extraordinary spectra of calcspar, and the values calculatedby Helmholtz’s and Ketteler’s equations respectively.The observedvalues are by Mnscart for lines from A t o R, and by Sarasin for theul tra-violet (cadmium) spectrum. The constants were determined forlines over the whole spectrum.The results show that for the extraordinary spectrum, in which thedispersion is low, Helmholtz’s formula is satisfactory, Ketteler’s some-what better. But when applied to the ordinary spectrum, in whichthe dispersion is 24 times greater, the discrepancies are very serious,extending in the case of Helmholtz’s formula to the third place ofdecimals.From his investigations, the author draws the following importantconclusions :-That all the formule connecting wave-length and re-frangibility hitherto proposed are of purely empirical character, andapplicable only to media of low dispersive power : that at present it isnot certain that the refractive index reaches a limiting value, unity orotherwise, either for X = cm or for any other wave-length; and,finally, that in investigations bearing on chemical constitution andrefractive puwer, dispersion must either be taken into account,, or beeliminated in some empirical way.Ketteler’s equation proved somewhat better.CH.B.Supposed Influence of Multiple Bonds of Union on theMolecular Refraction of the Hydrocarbons. By JULIUS THOMSEN(Ber., 19, 2837).-In 1862-664, Landolt (Ann. Phys. Cjzern., 117, 122,and 123) proved beyond doubt that a connection exists between mole-cular refractive power and chemical composition, by showing that inany homologous series the refractive power increases from member tomember by a constant amount, and is independent of isomerism andmetamerism.Since then Briihl (Abstr., 1880, 295, 781 ; 1882, 44.5, and precedingAbstract) has endeavoured, with apparent success, to establish a, rela-tion between molecular constitution and refractive power, by showingthat the refractive power of a compound, although independent of thenumber of single bonds of union between carbon-atoms in its mole-cule, is decidedly influenced by double and treble bonds.The fol-lowing considerations, however, make such an influence at leastdoubtful :-Briihl’s results are summed up in the formula-n . c + 2m.h + aV, + /3V2 + YV, = R .. . .in which R is the molecular refraction of a hydrocarbon CfiH2m, c andh the refractions of a carbon and hydrogen atom respectively, a, /3,and ‘y the numbers of single, double, and treble bonds of union, anGE,WRAL AND PHYSICAL CHEMISTHT. 199V,. VL, and V3 the increments of refractive power due to them re-spectively.Briihl now puts V1 = 0 ; but this assumption may be avoided, andV, eliminated as an independent constant by combining equation [l]with the necessarily true relttt,ion 2n - wb - a - 2p - 3cy = 0.Multiplying the latter by V1, and adding, we get-and finally substituting x, y, p , and q for the constant quantitieswithin brackets, we get-n . x + m .y + p . p + p i . q = R, , . . . . . [41which is of the same form as [l], and identical with it when V, = 0,but in which R is not necessarily independent of the number of singlebonds of union between carbon-atoms. In either case, x + y = c + 2h + V, represents the increase in refractive power for each addition ofCH,. Experimentally, J: + y has been found to vary from 4.85 in thebenzene series to 4.525 in the naphthalene-group. No values of .z andy can therefore exist which will in all cases satisfy equation [4], andthis must also be true of the constants p and q. The followingexample illustrates this :-Taking the experimental value oE the refraction of two moleculesof benzene, 51.86 = 12c + 1212 + 6V, + 6V2, and of one molecule ofnaphthalene, 43.93 = 1 0 ~ + 8h + 6V1 + 5V2 and subtracting, wehave 2c + 4h + V., = 7.93.From this and the relation G + Sh +Vl = 4.85 or 4.525 we find Vz - 2V1 = constant p in equation [4]-- 1.77 or - 1.12.Now Bruhl (preceding Abstract) has found the following values forthe constants of equation [4) :--x = 2.48, y = 2.08, p = 1.78, q = 1.97 . . . . [51The above calculation shows the negative influence of p to be asgreat as Bruhl assumes it to be positive.Again the difference between the molecular refractions of naphtha-lene and benzene, calculated with Briihl’s constants = 42.02 - 26-46= 5.56, whereas the actual difference = 8.00. Briihl attributes thediscrepancy to the greater dispersive power of naphthalene. Theauthor rather attributes it to the incorrectness of Bruhl’s hypothesis,which he proceeds to show is unnecessary.Assaming either that double and treble bonds of union have no in-fluence on molecular refraction, or that Vz = 2V1, V, = 3VI, equa-tion [3] reduces to R = nx + my.The author has now determinedthe constants x and y from the observed moleculm refractions of a,series of five hydrocarbons of t h e general formula CBHZm, containing1, 2, 3, and 4 double bonds of union, and thus arrives a t the equationR = n. . 4.014 + rn . 0.840. A table is then given showing themolecular refractions of these five hydrocarbons and of three others,containing from 0 to 5 double bonds, calculated by the author’sformula and by equation [4] with Bruhl’s constants ; and the agree-ment with experiment is seen t o be much better in the former case(mean error = 0.37) than in the latter (mean error = 0.8)200 ABSTRAOTS OF CHEMICAL PAPERS.The author therefore concludes that the mode of union of carbon-atoms has no influence on molecular refraction.I n the author’s formula, the values of x and y can only be re-garded as approximate.However, the range of variation is notgreat. A table is given of the values of x calculated for 22 hydro-carbons, roughly classified according to the number of double bondsin their molecules. Throughout y is taken = 0.84. In no case doesthe value of x differ much from the mean value given above. Forone group only, of which hexahydronaphthalene may be consideredtypical, it falls as low as 3.75; but even here x + y = 4.59 isThornsen’s Supposed Explanation of Molecular-refractionRelations. By J.W. BRGHL (Ber., 19, 3103-3108).-A partialreply to Thomsen (ibid., 19, 2837, see previons Ahtract). Theauthor points out that the constant y in Thomscn’s formula for mole-cular refraction, R = fix + my, has been calculated from observa-tions on a series of hydrocarbons of the formula CBH2,,&, in which theincrements of refractive power for each addition of Hz are veryvariable, sometimes positive, sometinies negative, a variability whichcan only be attributed to chemical constitution. Like other empiricalformula, Thomsen’s is no doubt applicable to the observations fromwhich i t was deduced, and possibly to others besides. But in manycases (quoted by the author) it is seriously at fault, whilst theauthor’s formula applies to all hydrocarbons except those having ahigh dispersive power, to which the author attributes a special in-fluence.Referring to his previous work (see preceding Abstracts) for a fulldiscussion of the question, he here contents himself with quotingexamples of isomeric compounds whose molecular refractive powersdiffer more or less.I n all the compounds selected, the dispersivepower is low. Inspection of the table shows that when isomerides areequallysaturated, that is, contain the same numberof doubly or treblybound atoms (isovaleric acid, propylic acetate, methylic butyrate),their molecular refractive powers differ very slightly ; but when thesaturation is unequal (ally1 ethyl ether and valeral, cymene andhexahydronaphthalene) the differences are considerable, and beyondthe possible limits of experimental error.The influence of saturationon refractive power cannot therefore be ignored.Absolute Electrodynamometer. By H. PELLAT (Con@. rend.,103, 1189--1190).-A description of a new electrodynarnometricbalance.New Apparatus for Electrochemical Investigations. By N.v. KLOEUKOFF (J. pr. Chem. [a], 34, 539-547).--8 description, withplates, of a “ universal commutator ” which fulfils tbe following con-ditions :-That with a given large number of circuits in which the measure-ment of the strength of the currents has to be determined with oneand the same measuring instrument, the making and breaking contactwith the latter can be easily and quickly effected.within the observed limits of variation, CH. B.CH.B0-907"907-1100"Silver {Tin ,. 232*7-1110"0-660" f 660-720"Iron.. 4I 720-1@ooo[ 1050-1200°r 0-230"Nickel 4 230-400" I 400-1150"0-890"890 -1150"Cobalt= 0.05785 + 0*0000044t2 + 0~000000006t3.= 0.0578 + 0.0000088t + 0*000000018~ r q; = omo7$8t + 17.20.\elt = 0.0748.= 14.375 + 0.06 12931s - 0*0000104741t2yr = 0.0612931 - 0*0000209482t + 0~0000000310344ta.0.1 1012t + 0*0000253333t2 f 0.000000054666t3.0.1101'2 + 0.00005066665 + 0*000000163998t2.0.578035 + 0*00143598t2 + 0.000001195t3.0.57803 + 0.002871965 + 0*000003585t2.qi =yt =9; = 0.218t - 39.yt = 0.218.nit = 0019887.{ qi = 0.19887t - 23.44.0.10836t + 0.00002833t2.{ $ 0.10836 + 0.00004466t.t0.183493t - 0*000282S2 + 0.00000046666t3.0.183493 - 0.000564t + 0*000001339998t2.0.099t -+ 0*00003Y75t2 + 6.55.yYt =yYt = 0.099 + 0.000061755.- 0.105845 + 0-0000228667t' + 0*0000000219427t3.= 0.10584 + 0.0000457334t + 0~0000000658281~0.124t + 0*00004t2 - 14.8.yt = = 0.124 + 0.00008t202 ABSTRACTS OF CEEMICAL PAPERS.the absorption of oxygen by the silver, and it was found that underthese conditions the metal melts at 907", a temperature much lowerthan that given by previous observers.Molten tin differs from all ordinary liquids in that its specific heatchanges very slowly.Experiments with gas-carbon of which the vessels used to holdsome of the metals were made, confirm Weber's statement that athigh temperatures the specific heats of the different varieties of carbonare identical.The variations in the specific heats of the magnetic metals, iron,nickel and cobalt, show that they exist in several allotropic modifica-tions.It is worthy of note that the changes take place at verydifferent temperatures in the three cases. Experiments which are notyet completed, show that these changes of state &re intimately con-nected with the magnetic properties of the three metals.The author's results confirm Berthelot's criticisim of the law ofDuloiig and Petit. This law amounts simply to a statement thatthere is a certain interval of temperature (between 0" and *looo) inwhich the values of the products of the specific heats of the elementsinto their combiniug wecghts are approximately equal, c.H. R.Themnochemistry of Bibasic Phosphates and their Con-geners. By A. JOLY (Cowpt. rend., 103, 1197--1199).-The heatsof formation of the bibasic phosphates from the dissolved acids anddissolved oxides were determined both directly and iudirectly.Cttl.Calcium hydrogen phosphate, CaHP04, cryst. ........ + 26 9Barium hydrogen phosphate, BaHP04, gelat.. ......... + 26-6Barium hydrogen arsenate, BaHAs04, gelat. .......... + 27.8Strontium hydrogen phosphate, SrHP04, cryst.. ....... + 25.2Manganese hydrogen phosphate, MnHP04, gelat. ...... + 22.73Manganese tetrahydrogen phosphate, MnH,( PO,),, gelat. + 24.3Barium hydrogen hypophosphate, BaH,(PO,),, cryst.. .. + 35.2Barium hypophosphate, BaPO,, cryst................. + 2b.29 , 9 9 9' ,, cryst.. ......... + 27.89 , 9 , ,, ,, cryst.. ........... + 28.4The differences between the heats of formation of the collojidal andcry stallised varieties is sufficient to show that the reactions involvedin their formation are of a complex character.Ammonium Magnesium Phosphate. By BERTHELOT (COWL@.rend., 103, 966--970).-Tlie heat of formation of magnesium ammo-nium phosphate was determined by measuring the thermal dis-turbance which takes place when a solution of a magnesium salt ismixed with sodium phosphate and afterwards with ammonia. Thenumbers thus obtained for the heat of formation of the crystalliseddouble phosphate were +40.7; +41*0; +40-6; +41*9. Thelast value is probably the most accurate, since the ammonia wasadded to the crystalline magnesium hydrogen phosphate, and thelatter was converted directly into the crystalline double salt.Aseries of experiments in which a mixture of ammonia and sodiumC. H. BGENERAL AKD PHYSICAL CHEMISTRY. 203phosphate was added to the magnesium salt showed that thedifference between the heats of formation of the zolloidal and crystal-line varieties of the double phosphate is greater than +12.4. Theseexperiments gave a higher value than the first series for the heat offormation of this compound, and the combined results of both seriesgive for the heat of formation of ammonium magnesium phosphate,colloidal, +29.3 cal. ; cryst,alline, + 41.9 cal. These values agreeclosely with the corresponding values for colloidal and crystallinetrim agnesium phosphate.When magnesium hydrogen phosphate is in the colloidal condition,the displacement of the third atom of hydrogen by magnesiumdevelops only +3*7 cal., whilst the same substitution in the crystal-line phosphate develops + 14.4 cal.Similar phenomena are observedwith calcium phosphate. I n like manner, the action of ammonia oncolloidal magnesium hydrogen phosphate develops only +4.1 cal.,whilst its action on the crystallised salt develops +14.6 cal., aquantity higher than that developed by magnesium, and equal tothat developed by sodium or potassium. It follows that ammoniumin union with magnesium forms a base, the energy of which is com-parable with the energy of sodium and potassium, as already ob-served in the case of the chlorides and snlphates.(This ~ o l . , p. 96.jIt also follows that the action of ammonia on trimagnesium phos-phate will produce only a very slight thermal disturbance.Trimagnesium phosphate is rapidly altered by ammonia with pro-duction of ammonium magnesium phosphate, not because the heatsof formation of the two phosphates for the colloidal condition are rerydifferent, but because the double salt more rapidly passes into thecrystalline condition and thus develops heat. This result illustratesthe fact that the more or less rapid formation of salts in the colloi'dalor crystalline condition depends on the order in which the reactingsubstances are brought together. Ammonia also acts on crystallisedtrimagnesium phosphate with development of + 0.42 cal., but thereaction is not complete without the addition of ammonium chloride.When this salt is added, there is a slight additioual development ofheat owing to the formation of a small quantity of magnesiumchloride ; this fact explains the effect produced by the presence ofammonium chloride when magnesium salts are precipitated bysodium phosphate.This effect is only exerted in presence of a t leastthree equivalents of base. Ammonium chloride alone has 00 actionon magnesium phosphate.These facts explain the difficulty which is experienced in displac-ing ammonia from ammonium magnesium phosphate by means ofmagnesia or lime. Lime teiids to produce collojidal calcium phos-phate, the heat of formation of which is less than that of the doublephosphate.The lieaf of formation of crystallised trimagnesiumphosphate is also somewhat less than that of the double compound.That decomposition takes place at all is due to the combined effect ofthe slight dissociation of the ammonium compound in the presence ofwater, especially if heated, and the volatilisation of the ammonia,which is thus removed from the sphere of action, the mwneqiumtaking its place. C. H. B204 ABSTRACTS OF CHEMICAL PAPERS.Saturation of Arsenic Acid by Magnesia: Formation ofAmmonium Magnesium Arsenate. Ry C. BLAREZ (C'omp. rend.,103, 1133--1135).-The developments of heat accompanying the dis-placement of successive atoms of hydrogen by magnesium are+14*866 cal. ; +11.464 cal.; f F 0 3 cal., giving for the total heat ofneutralisation, + 28-36 cal.The heat developed by the neutralisation of arsenic acid by mape-sium and ammonium is +37*645 cal., from which it follows that thedisplacement of the third atom of hydrogen by ammonium develops+11.30 cal. C. H. B.Heat of Formation of Potassium Methoxide and Ethoxide.By DE FORCRAND (Compt. rend., 103, 1263-1266).-Potassium meth-oxide is obtained by dissolving potassium in excess of anhydrousmethyl alcohol and heating the solution in a current of pure dryhydrogen at 200". Complex alcoholates similar to those formed bysodium are at first formed. The heat of solution at 12" is +11*74cal.CH?*OH liq. + +K,O solid = CH3-OK solid +4H20 solid.. ..........................CH3*OH liq.+ KHO solid = CH3*OK solid +CH,*OR solid + H,O liq. = CHS-OH liq. +CH3-OH liq. + K solid = CHs*OK solid + HCH,*OH solid + rtCH3*OH liy. = CH3*OKPotassium ethoxide is obtained in a precisely similar manner. Asmall quantity of crystals of the compound EtRO + 3EtOH wasobtained. Heat of solution of the ethoxide at 12-15" = +14.70 cal.develops + 24-79 cal............................. H,O solid 9 , + 4-30 9 )KHO solid.. ,? - 2.87 ,,gas .................................. j, + 38-17 ,,diss. in rtCH3*OH liq. .................. ,, + 12-76 ,,..........................C2H,*OH liq. + &KzO solid = C,H,*OK solid + QH,O solid.. ........................C,H,*OH liq. + KHO solid = C,H,*OK solidC,H,*OK solid + H,O liq.= C,H,*OHliq. +C,H,*OH liq. + K solid = CzH5*OK solid +C2H,-OK solid + rtC2H6*OH liq. = C2H,*OKThe values for the potassium compounds agree very closely withthose obtained previously for the sodium compounds, and the valuesare practically the same with both ethyl and methyl alcohol. More-over the values corresponding with the action of potassium andpotassium hydroxide on the two alcohols agree closely with thosecorresponding with their action on water.In the case of sodium the differences between the heat developeddevelops + 22.28 cal........................... + H,O solid ,, + 1-79 7,KHO solid.. 9 , - 0.36 ,,H gas ................................ ,, + 35-66 , 9diss. in rzCzH5*OH liq.. .................. ), + 13-59 ,,.........................GENERAL AND PHYSICAL CHEMISTRY.205by its action on the two alcohols respectively, and on water, are muchgreater than the corresponding differences in the case of potassium,and the absolute values of the quantities are higher with sodium, aresult which is due to the fact that the tendency to form polyalcoholicnlcoholates is much greater in the ease of sodium. Moreover, theheats of formation of the hydrates of potassium hydroxide are muchgreater than those of the corresponding sodium compounds.It follows that the alcoholates of potassium ethoxide or methoxidedissolved in the alcohols are practically in the same condition aspotassium hydroxide dissolved in water, whilst the dissociation ofsodium hydroxide in water is much greater than that of sodiummethoxide and ethoxide in the alcohols.C. H. B.Heats of Neutralisation of Glyceric and Camphoric Acids.By H. GAL and E. WERNER (Corn@. rend., 103, 1199-1200).-Glyceric Acid, OH*CH,*CH(OH)*COOH.-Heats of neutralisation bythe first and second equivalent of potassium hydroxide respectively+11*334 cnl. and +12.127 cal. ; total +23*461 cal. The addi-tion of a, third equivalent of alkali causes no further thermal dis-turbance.Camphoric Acid, C8H14(C00H)2.-Heats of neutralisation by thefirst, second, and Ghi1-d equivalents of sodium hydroxide respectively,+13%28 cal. ; +13.253 cal. ; +O.O cal. ; total +27.081 cal.These results confirm the former conclusion that the total heat ofneutralisation of hydroxy-acids is lower than that of acids into whichthe hydroxyl-group has not been introduced.C. H. B.Heats of Neutralisation of Malic and Citric Acids and theirPyrogenic Derivatives. By H. GAL and E. W-ERNER (Compt. rend.,103, 1019-1022).Heat of Heat of solutionneutrdisation. at about ZOO.Maleic acid ........ 13.310 x 2 - 4.438Fumaric acid ...... 13.299 x 2 - 5.901Citraconic acid.. .... 13.511 x 2 - 2.i93Mesaconic acid.. .... 13.633 x 2 - 5.943Itaconic acid.. ...... 12.837 x 2 - 5.923Malic acid.. ........ 12.4 x 2Citric acid.. ........ 12.8 x 3The heat developed by neutralisation is practically the same foreach acid function of the same acid,In all cases, with the exception of itaconic acid, the heat of neutrali-sation of the pyrogenic derivatives is about 2 cal.greater than thatof the generating acid, a relation similar to that already observed inthe case of monobasic acids and the corresponding hydroxy-acids(this vol., p. 96). The pyrogenic acids derived from malic acid bythe loss of HzO, and from citric acid by the loss of CO, + H,O, nolonger contain the hydroxyl-group. C. H. B.VOL. LII. 206 ABSTRACTS OF CHEMICAL PAPERS.Heat of Neutralisation of Meconic and Mellitic Acids.By H. GAL and E. WERNER (Compt. rend., 103, 1141--1142).-Theheat developed by the action of successive equivalents of sodiumhydroxide on meconic acid, OH*C4(COOH)s is + 14.074 cal.;+13*611 cal. ; +8.369 cd. ; +1.328 cal. = 37.382 cal.The heat developed by the action of sodium hydroxide on melliticacid, C,(COOH),, is $15.040 cal.; pt15.516 cal.; +15*294 cal.;+13.713 cal.; $. 12.793 cal, ; + 21.678 cal. = 84.034 cal,The heat of neutralisation of meconic acid is less than that oftnellitic acid, probably because the former is a hydroxy-acid. In bothcases the heat of neutralisation diminishes as neutralisation becomesmore camplete. The values far mellitic acid show that if neutralsodium mellitate is evaporated with excess of hydrochloric acid, itwill lase part of the base and yield an acid salt, and the same acid saltwill be obtained, when mellitic acid is heated with a solution ofan alkaline chloride, The values obtained for mellitic acid areanalogous to those found for phosphoric, sulphuric, and other acids inwhich several hydroxyl-groups are united with the same radicle.The numbers for the six acid functions of mellitic acid differ morewidely than would have been expected from the symmetrical constitu-By 0, W.A, HAHLBAUM (Bey.. 19,2860--2862).-An improvement on Andree’s form (Ann, Phys.Chem, [2], 4, 164),Influence of Change of Atmospheric Pressure on BoilingPoint, By (3. W. A. KAHLBAUM (Ber., 19, 3098--3101).-With theexception of Broch’s “ Temperatures d’kbullition de l’eau pure ”(Trnv. et Mim. Bureazt I n t e r n a t . 3es Po& e t Mesh, I., A., 43 (1881)),calculated from Repault’s observations (Mein. Acad. Xci., 21 (1847)),accurate determihations of boiling point at regular intervals of pres-sure haTe not been made.Thc author has made such a series of measurements for ether(sp.gr. 0.720), The ether was boiled ih a platinum vessel, the heatingbeing as uniform as possible; and to avoid possible change of thexero point of the thermometer, the latter was wrapped in wadding andtransferred to a vessel of boiling ether after each observation. Itwas thus maintained at about the Bame temperature for a period offour months. The author strongly recommender this device. Bygraphic interpolation, the boiling points were calculated for each mm.of pressure from 721 to 750, and are given in tabular form. Onlyrelative, not absolute, accuracy is claimed for them.A comparison of thiR table with Broch’s shows that within theordinary limits of variation of atmospheric pressure, the curves ofboiling point for water and ether are practically parallel.Assumingthis to be true for other liquids whose boiling point may exceed 100”by as much as that of ether falls below it, the author gives a table ofcorrections of observed boiling point for each mm. pressure, for liquidsboiling between 30” and 170°, of which the following is a condensedform-tion generally assigned to this acid. c. H, €3.Temperature RegulatorGENERAL AND PHYSICAL CHEMISTRY. 207Between 720-730 mm. = + 0.038",, 730-740 ,, = + 0.037,, 740-750 ,, = + 0.037750-760 mm. = + 0.037"760--7iO ,, = -0.036 - 770-780 ,, - -0.036Vapour-tensions of Ethereal Solutions. By E. RAOULT (Compt.rend., 103, 1125--1127).-The author has carefully measured thevapour-tensions of ethereal solutions of several organic compounds atdifferent temperatures.Between 0" and 25", the difference between the vspour-tension ofthe ethereal solution and that of the ether is exactly proportional tothe vapour-tension of pure ether at the particular temperature.Forsolutions containing from 1 t o 5 molrs. of the substance in 5000 gramsof ether, the difference between the vapour-tension of the solutionand that of pure ether is proportional to the amount of solid in solu-tion. The relative diminution of the vapour-tension caused by thesohtion of 1 gram of the substance in LOO grams of ether depends onthe nature of the substance. The molecular reduction of the vapour-tension 7c is obtained by the formula k = S+f x 3, in whichf isthe vapour-tension of ether, f tbe vapour-tension of the solution,M the molecular weight of the substance, and P theamount dissolvedin 100 grams of ether.It is found that if a gram-molecule of anycompound whatever is dissolved in 100 grams of ether, the vapour-tension of the ether is diminished by a constant, fraction of its normalvalue. For all temperatures between 0" and 25", the value of thisfraction is 0-71.f PC. H. B.Apparatus for Measuring the Tension of Vapours. ByG. W. A. KAHLBAUM (Ber., 19, 2954--2958).-The essential point inthis apparatus is the maintenance of a uniform temperature by thecirculation of a curnent of water heated in a vessel exterior to theDissociation of Salts containing Water of Crystallisation.By W. M~LLER-ERZBACH (Ber., 19, 2874-2876).-A continuation ofthe author's experiments (Abstr., 1885, 952 ; 1886, 10) in which therelative vaponr-tensions of the water in the salts and of pure waterare compared.The following salts are examined : CaN,O, + 4H,O,jacket. w. P. w.P 208 ABSTRACTS OF CHEMICAL PAPERS.relative tension = 0.06--0.07: CaNZO6 + 3Hz0, relative tension= 0*10-0.11 ; after the loss of 1 mol. HzO, this fell to 0.04. Thesalt obtained by dissolving the latter in a fourth molecular proportionof water had a relative tension = 0.27-0.36 ; after 2 mols. H,O hadbeen removed, the tension fell to 0.08-0.07, and reached 0.04 beforethe last traces of water were removed. The author regards thisvariation in the tension required to separate the different proportionsof the water from the solution as affording good evidence of theexistence of a molecular compound in the liquid.With SrNzOg +4Hz0, the relative tension at 12.g was 0.61 ; ZnN20G + 6Hz0, relativetension = 0.18 at 12*1", after the loss of 2Hz0 this fell to 0.025, andbecame imperceptible when a salt containing 3 mols. HzO was left.BaHZO2 + 8Hz0 lost 1 mol. HzO with a relative tension = 0.88-0.92,5 more mols. H,O were lost when it fell to 0.18-0.22, and adiminution to 0.10 to 0.12 accompanied the separation of a seventhmol. H,O; 1 mol. HzO remaining combined with the salt.SrH,O, + 8Bz0 lost 1 mol. H,O with a relative tension = 0.73 at17*6', and a further 6 mols. HzO with a relative tension = 0.27 at18*5", 1 mol. H,O remaining combined with the hydroxide. w. P. w.Dissociation of Copper Sulphate.By W. MZLLER-EEZBACH(Rer., 19, 2877-2879).-1n this paper, it is pointed out that H.Lescmur, working with a different method and at higher temperatures,has arrived at results (this vol., p. 100) which agree exactly with thosepreviously obtained by the author (Abstr., 1886, 10). Lescoeur, inhis criticisms on the author's earlier experiments (Abstr., 1884, 952),has overlooked these more recently published experiments on thedissociation of copper sulphate. w. P. w.The Relation between the Efflorescence and Deliquescenceof Salts and the Maximum Vapour-tensions of their SaturatedSolutions. By H. LESC~UR (Cornpt. rend., 103, 1260--1263).-Thepresence of a few tenths of a per cent. of water over and above thatwhich is actually combined with the salt, is sufbcient to give themaximum vapour-tension of its saturated solution.In order thata salt may be deliquescent, the maximum vapour-tension of its satu-rated solution must be lower than that of the aqueous vapour in theatmosphere. The following table gives the vapour-tensions of thesaturated solutions, and may be termed the scale of deliquescenceat 20':-Potassium nitrate . . . . 15 mm.Potassium chloride . . 13.55 mm.Sodium acetate (cryst.) 12.4 ,,Iodic acid . . . . . . . . . . . 11.6 ,,Strontium chloride. . . . 11.5 ,,Sodium nitrate . . . . . . 11.15 ,,Sodium chromate . . . . 10.6 ,,Calcium nitrate . . . . . . 9.3 ,,Ammonium nitrate . . 5.1 ,,Strontium bromide. .Potassium carbonateMagnesium chlorideCalcium chloride .. .Potassium acetate . .Arsenic anhydride. .Sodium hydroxide..Potassium hydroxidGENERAL AND PHYSICAL CHEMISTRY. 209On the other hand, if the vapour-tension of a hydrated salt isgreater than that of the aqueous vapour in the air, the salt will beefflorescent. The following table furnishes a scale of efflorescenceat 20':-Sodium arsenate, NhHhs04 + 12H,O ........ 16.0 mm, .. sulphate, N%SOa + 1OHzO.. .......... 13.9 1, ,, phosphate, Na2HP04 + 12Hz0.. ...... 13-5 ,,.. phosphate, N%HP(34 + 7H20 ........ 9.0 .. Ciipric sillphate, CuS04 + 5H20.. ............ 6.0 .. Strontium hydroxide, SrHZOz + 8Hz0 ........ 5% ..Nickel chloride, NiCI, + 6HzO .............. 4.6 ,,Sodium arsenate, NazHAsOk + 7Hz0.. ........ 4 6 .. Barium hydroxide, BaHzO2 + 8Hz0 ..........4.2 ,,Boric acid, H3B03, about .................... 2.0 ,,Stroutium bromide, SrBr, + 6H20, about.. .... 1.8 .... acetate, NaC,H,OZ + 3H,O .......... 12.4 ,, .. carbonate, Na2C03 + 10HzO .......... 12.1 .... chloride, SrC1, + 6H,O ............ 5.6 3 ,Oxalic acid, H2C204- + 2Hz0, about.. .......... 1.3 .. C. H. B.Density of Weak Aqueous Solutions of Certain Salts. ByJ. G. MCGREGOR (Chem. News, 55, 3--6).-Experiments have beenmade to decide:-1. Whether or not there are solutions of salts,given volumes of which are less than the volumes of the waterthey contain. 2. How the density of very weak solutions varies withtheir strength. Anhydrous copper sulphate has already been shownto form weak solutions exhibiting the first property.Experimentswith zinc sulphate, magnesium sulphate, and calcium chloride now showthat these salts do not behave in this manner, but that the solutionsthey form are always of greater volume than the water they contain.The strength of the solutions examined, varied in the case of zincsulphate from 0.186 to 2.695 per cent. of the salt; of magnesiiimsulphate from 0.191 to 1.132 ; of calcium chloride from 0.191 to 1.320per cent. With regard to the density of the solutions: with thezinc and magnesium salt, the increase in density is nearly in directproportion to the percentage of salt in solution, whereas with calciumchloride the rate of increase of density with concentration diminishes asthe percentage of salt in solution increases.The mode of experimentingis fully described and the results are tabulated. D. A. L.Cohesion and Slibmersion Figures. By C. TOMLINSON (Chenz.News, 55, 1-2).-Re€erring to a paper by Ackroyd on this subject.(Abstr., 1886,971), the author recalls the work of Rogers and his ownwork in the same direction. In 1864, he published papers on " Sub-mersion Figures " produced by a large variety of liquids, and diagramswere given illustrating the formation and structure of these liquid" rolling rings," and also of ai3rial " rolling rings." Reference isalso made to other work on the same subject, to the modes of exhi-biting vortex rings a t the lecture table, and to the author's researche210 ABSTRACTS OF CHEMICAL PAPERS.on the action of nuclei and porous bodies in liberating vapour fromboiling lisquids. D. A. L.Weight of Drops and their Relation to the Constants ofCapillarity and the Capillary Meniscus Angle. By J. TRAUBE( J . pr. Chenz. [a], 34, 515-538; compare this vol.? p. 10l).--Fromthe results obtained with water and with solutions of alcohol of dif-ferent strengths, the author concludes that the weight of drops andtheir capillary constants decrease with the increasing curvature of thesurface of formation of the drops; this decrease does not, however,begin before a certain degree of curvature, which is different fordifferent liquids. The decrease of the weight of drops in the case ofdifferent liquids is not proportional to the increase of curvature, butappears to be the greater the smaller the capillary constants of theliquid. He also finds that the edge-angle of the meniscus of drops ofdifferent liquids is equal or proportional to the meniscus angle of thesame liquid in capillary tubes.The author also made a series of determinations with solutions ofalcohols and acids of different strengths, observing in each case thetime which was necesswy for the formafion of a drop from a capillarytube and also the time necessary for the formation of a drop plus thecurved surface of its meniscus; by working out the proportionbetween these, he found that the ratio of the time of formationbetween the curved surface of the dropmeniscus and the dropincreases with the increasing radius of the tube ; and that the drop-meniscus in general increases in proportion to the drop with increasingconcentration of the solution ; that is, with decreasing cohesion. Thedifference in the quotient - decreases with increasing concentration(T, = time of formation of the drop-meniscus, Tt = that of the drop) ;therefore, curves constructed with the concentrations (as abscissae)and these quotients are concave. With compounds of an homologousseries, and equal concentration, the drop-meniscus increases wiih themolecular weight of the dissolved substance. The determination ofthe size of the drop-meniscus was made in order to see if any con-clusion regarding the meniscus angle could be drawn from theirrespective sizes. The results showed that-1. The volume of thedrop-meniscus and the top meniscus angle, whieh the tangentialplanes, formed by the last particles of the curved surface of the drop-meniscus, form with the horizontal tube wall, decreases with in-creasing concentration of the solution, like the meniscus angle incapillary tubes. 2. For substances of an homologous series, in solu-tions of equal strength, the volume of the drop-meniscus decreaseswith the increasing molecular weight of the dissolved substance, asdo also the top edge of the angle of the drop-meniscus, and themeniscus in capillary tubes.In conclusion, the author considers that Laplace’s hypothesis,according to which the meniscus angle for wetting liquids is equal to0, cannot be maintained in view of the results obtained by the directmeasurement of the capillary meniscus at different temperatures, andby the measurement of drops ; moreover, one of the most importantT WT’INORGANIC CHEMISTRY. 211theories of capillarity can only be maintained if the finiteness of themeniscus angle is accepted.Wilhelmy's important law of the constawy of the meniscus anglecannot be accepted in its universality, since the size of this angleappears to depend on the temperature of the liquid and the curvatureof the walls of the tube. Noreover, the meniscus angle, which thesurface of a drop forms with a horizontal glass surface, is not, asQuincke supposes, e ual to tha$ which is enclosed by the meniscuscomplement of the other.Volatilisatios of Dissolved Substances during the Evapora-tion of the Solvent, By P. M. DELACHARLONNY (Compt. rend., 103,1128--1129).-Concentrated solutions of sulphuric acid, sodiumhydroxide, sodium carbonate, and ferric sulphate were heated at 65-70" in vessels closed by inverted funnels. In a few hours, the fact thatsome of the dissolved substance had been carried off in the vapour ofthe solvent was easily recognised by means of suitable test-paperswhich had been placed in $he apex of each funnel. Even a t theordinary temperature, the papers had distinctly changed after four orfive days.Acid solutions of alum and of ferrous sulphate at the ordinary tem-perature gare similar results.There is no evidence of the actual carrying off of solid particles ;the colour of the test-papers was unihrm, and not in streaks orpatches. C. H. B.The Periodiac Law, By W. SPRING (Bar., 19, 3092-3093).-Aquestion of priority with regard to Emerson Reynolds's illustration ofthis law (Ckem. News, 54, l),G. H. M.surface in tubes wit 1 a, vertical partition. The one is perhaps th

ISSN:0368-1769    

DOI:10.1039/CA8875200189

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 211 I n o r g a ni c C h e m i s t r y. Formation of Active Oxygen in the Akmosphere, and its Connection with the Electric Phenomena of the Air and the Production of Storms, By C. WURSTER (Ber., 19, 3208-3217).- Observations made by the author lead him to conclude that ozone is formed in the air by the action of sunlight on clouds. When clouds are continually formed from above, they all become laden with ozone, whilst when they form from below only the upper layer will contain much ozone. I n the former wse, the accumulation of ozone causes the clouds to become strongly negatively electric, and so gives rise to thunderstorms. N. H. M. Formation of Active Oxygen in Paper. By C. WURSTER (Bey., 19, 3217--3218).-The yellow and brown colour acquired by some212 ABSTRACTS OF CHEMICAL PAPERS.papers is due to the action of active oxygen on the resin used in siz- i n g the paper, or in some cases on the woody matter present i n the paper. By means of dimethylparaphenylenediamine paper (this vol., p. 298), the presence and even the percentage amount of woody matter can be determined in a paper. When the moist dimethylpara- phenylenediamine paper is pressed between paper containing wood, it acquires a deep red colour. Ordinary sized paper merely turns it a delicate rose colour. N. H. M. Phosphorus Pentafluoride. By H. MOWAN (Compt. rend., 103, 1257-1260).-Perfectly dry phosphorus pentafluoride confined over mercury is not decomposed by the action of induction sparks 40 mm. in length, a result which agrees with Thurpe's earlier observation.With sparks 150-200 mm. in length, however, the gas is decomposed info phosphorus trifluoride and fluorine, the latter at once attacking the glass and the mercury. Phosphorus pentafluoyide yields no trihoride when heated to dull redness with an excess of phosphorus. In this respect, its behaviour differs from that of the pentachloride. It is not affected by sulphur vaponr at 440", nor by iodine vepour at 500". In presence of a minute trace of water, it attacks glass, with formation of silicon fluoride and phosphorus oxyfluoride, whilst the alkalis in the glass are converted into phosphates or fluorphosphates. In order to analyse the gas, a measured volume was absorbed in water in a platinum vessel, treated with nitric acid and molybdic solution, and the phosphorus finally weighed as magnesium pyrophos- phate.Another method consists in absorbing a measured volume in potassium hydroxide solution, which is mixed with some pure silica, evaporated to dryness, mixed with concentrated sulphuric acid, and heated until vapours of this acid begin to come off. The liquid is then diluted, made alkaline with ammonia, and the phosphorus pre- cipitated as magnesium ammonium phosph te. The results agree with the formula PF,; the first method is the most accurate. C. H. B. Compounds of Selenious and Arsenious Anhydrides with Sulphuric Anhydride : Isolation of Sulphuric Anhydride. By R. W EBER (Bey., 19, 3185--31YO).-When selenious anhydride is warmed with very carefully purified sulphuric anhydride, it dissolves therein, and if the excess of sulphuric anhydride is distilled off at 60 -70°, a crystalline compound, Se02,S03, is left.This substance is decomposed by a temperature of loo", sulphuric anhydride being evolved. In like manner, sulphuric anhydride dissolves arsenious anhydride. If the excefis of sulphuric anhydride is distilled off at 6U0, a compound of the formula As203,6S03 is left ; if the distillation is continued a t lOO", the regidue has the formula As203,3S03. These compounds are quite distinct from the compound As203,S03 discovered by Reich in 1863 in the Freiberg smelting works. The author states that the specimens of pure sulphuric anhydride previously obtained and described (this Journal, 1877, ii, 164) still Water decomposes it with great violence.INORGANIC CREMISTRY. 213 retain their original character, melting and resolidifying at 15".and showing no signs of forming allotropic modifications. He is still of opinion that the various modifications of sulphuric anhydride are all due to the presence of traces of moisture, He describes further pre- cautions for obtaining absolutely pure anhydride, and considers the best method to be to cohobate carefully purified sulphuric anhydride with phosphoric anhydride in a slight modification of the bent and sealed distilling tube previously described (Zoc. cit.). After continued cohobation, the sulphuric anhydride will remain liquid down to 15", even in contact with the phosphoric anhydride. Finally the sulphuric anhydride may be distilled over into the opposite end of the distilling tube, and this then sealed off without the air being able to come in contact with the inside of the tube.Phosphoric anhydrille forms a compound P205,3S03, which crystallises out from the excess of sul- phuric anhydride. This compound decomposes at the boiling point of sulphuric anhydride. L. T. T. Behaviour of Iodine with Realgar and Arsenic Iodosulphide. By R. SCHNEIDER ( J . pr. Chem. [2], 34, 505--514).-Arsenious iodo- subpiuhide, As13,AssS3, is prepared by heating together either a mixture of realgar ( 1 mol.) and iodine (2 atoms) with the least possible access of air, or a mixture of 3 parts arsenious iodide with 1.6 parts of arsenic trisulphide. It 'forms an amorphous, vitreous mass with conchoidal fracture, aud is of a dark red or reddish-brown colour.It is not acted on by the air at ordinary temperatures, When heated a t loo", it softens, and boils at a higher temperature without evolution of iodine vapour, but with partial decomposition in to arsenious iodide and sulphide. It is insoluble in hot and cold alcohol, ether, carbon bisul- phide, and chloroform. Hot water slowly decomposes it with forma- tion of hydriodic acid. Boiling hydrochloric acid slowly decomposes it with evolution of iodine. When boiled with concentrated sulphuric acid, it gives off iodine, sulphur and sulphurous anhydride. Potassium and ammonium hydroxides dissolve arsenious iodosulphide to a colour- less liquid, from which dilute acids precipitate arsenious sulphide, whilst the whole of the iodine and part of the arsenic remain in solution.When treated with an ammoniacal solution of silver nitrate, it is decomposed, forming silver iodide, sulphide, and arsenite. This reaction affords a means of determining the composition of the substance. When realgar is shaken with a solution of iodine in carbon bi- sulphide, and iodine is added in small quantities until the whole of the realgar is dissolved (1 mol. realgar requires 6 atoms iodine), and the solution then evaporated, arsenious iodide separates, partly in hexagonal plates and partly in rhombohedrons, mixed with long prisms of sulphur. Also, when a mixture of realgar (1 mol.) with iodine (6 atoms) is heated, and the resulting mass is dissolved in carbon bisulphide, arsenious iodide and sulphur are formed. Arsenic Pentasulphide.By L. W. MCCAY (Chem. News, 154, 287) .-When a solution of an alkaline arsenate strongly acidified with hydrochloric acid and saturated with hydrogen sulphide is G. H. M.214 ABSTRACTS OF CHEMICAL PAPERS. heated in a closed vessel at 100” for one hour, the arsenate is com- pletely converted into pentasulphide. It contains no trisulphide, and if due precautions have been taken to exclude air, no free sulphur. Pure arsenic pentasulphide is lemon-yellow in colour, does riot yield any sulphur to carbon bisulphide, and dissolves in ammonia without separation of sulphur. When the arnmoniacal soliition is agitated with silver nitrate and filtered, a clear filtrate is obtained, from which nitric acid precipitates silver arsenate. The formation of arsenic pentasulphide in this manner confirms Bunsen’s results, he having obtained it by the action of hydrogen sulphide on hot, solutions of arsenic compounds. Carbonic Anhydride in the Atmosphere.By R. BLOCHMANN (Annnlen, 237, 39--90).-The author gives an account of the various methods which have been used for the estimation of the carbonic anhydride in the atmosphere from the time of Saussure to the present day. It is pointed out that Pettenkofer’s method yields too high results ; the normal amount of carbonic anhydride in 10,000 volumes of air is 3, not 4 volumes. The author describes a modification of Pettenkofer’s method, which permits of the baryta-water being filtered through asbestos and titrnted without coming into contact with the air of the atmosphere, A double burette of special construc- tion is required.Drawings of the apparatus are given in the original. Bimetallic Phosphates. By A. JOLY (Compt. rend:., 103,1129- 1132) .-The action of disodium hydrogen phosphate on solutions of metallic salts varies with the conditions, and with the nature of the metal. I n some cases, with silver nitrate for instance, an amorphous precipitate of the trihasic phosphate is at once produced; in others, a, gelatinous monophosphak is at first precipitated, and t h i s gradually passes into a crystalhe diphosphate. I n the case of the alkaline earths and manganese, the first stage in the reaction is represented by the equation 4Na2HPOa + 4M”Cl2 = M,”(PO& + M”H4(POa)z + 8NaCI. The monophosphahes decompose in presence of water with a rapidity which depends on the nature of the metal and the concentration of the solution (Abstr., 1884, 556).In some cases, these is an intermediate reaction, the gelatinous monophosphate becoming crystalline. This is the final stage of the reaction if the conditions are such as to prevent the formation of a di- phosphate. The diphosphates decompose a t 100” into crystalline tribasic phosphates and the free acid, and a t the ordinary temperature the reverse change takes place to a greater or less extent. These facts indicate that the intermediate phosphates described by various authors are in reality mixtures. The precipitation of silver phosphate may be regarded as taking place in two stages, the first products being the trisilver phosphate and the monophosphate, the latter im- mediately decomposing into the tribasic salt and the free acid, which limits the extent of the reaction.The formation of disilver phosphate is impossible under these conditions, since this salt is immediately de- composed by water (this vol., p. 215). D. A. L. w. c. w.INORGANIC CHEMISTRY. 215 In the case of hypophosphoric acid, the precipitate is at first a gelatinous bibasic phosphate, which rapidly changes into a crystalline monobasic phosphate (Abstr., 1886, 200, 408, 593, 662). Silver Phosphates and Arsenates. By A. JOLY (Cmapt. rend., 103, 1071-1074).-Precipitated and amorphous silver phosphate dis- solve in phosphoric acid solution, the solubility increasing with the concentration of the acid and the temperature. If a liquid containing less than 38 parts of phosphoric anhydride to 100 parts of water is saturated with silver phosphate at 80" and allowed to cool, it deposits trisilver phosphate in pale-yellow, rhombic dodecahedrons modified by faces of the icositetrabedron.The mother-liquor deposits no more crystals on standing, but will dissolve a further quantity of amor- phous silver phosphate if heated, and thus the same fiolution of phos- phoric acid can be used for the crystallisation of an unlimited quantity of silver phosphate. If the solution contains 40 parts of phosphoric anhydride to 200 parts of water, it deposits disilver hydrogen phosphate, AgzHP04, in colourless crystals derived from a hexagonal prism. They generally form long prisms with rhombohedra1 terminations. I n contact with water or alcohol, they became yellow, and decompose into trisilver phosphate and phosphoric acid, but they are not aff'ected by ether.If the concentration of the phosphoric acid solution differs much from the strength given, the produet is a mixture of crystals very difficult to purify. When the crystals of disilver hydrogen phosphate are heated to 110-150°, they yield silver pyrophosphate, AgtPZO7, which can also be obtained by heating the syrupy solution of the silver phosphate to the same temperature. Hurhig and Geuther obtained the same com- pound by adding ether to the solution which had been heated. The pyrophosphate is not, however, formed in the wet way as these authors supposed, since under the given conditions of concentration, the fused acid salt, and not its solution, is decomposed.The experi- ment simply shows that disilver hydrogen phosphate yields the pjro- phosphate at a lower temperature than that ak which phosphoric acid is converted into pyrophosphoric acid, Silver arsenate is much less soluble than the phosphate in the free acid. If the solution contains less than 70 parts of arsenic anhydride to 100 parts of water, the solution saturated with amorphous silver arsenate at 80" deposits rery brilliant, black, opaque crystals of tri- silver arsenate, which are unmodified rhombic dodecahedra. A solution of arsenic acid of the composition H,AsO, + H,O, when saturated with silver arsenate, yields white monoclinic crystals of silver dihydrogen arsenate, a compound which is very readily pre- pared. I t is decomposed into trisilver arsenate and arsenic acid by a trace of water, and if heated t o 100" yields silver metarsenate i n the form of a white powder which absorbs water very slowly. Before losing water, the crystals of the acid salt become red, probably owing to the formation of arsenic acid and disilver hydrogen arsenate, AgzHAs04.In fact, if a solution from which silver dihydrogen arse- nate will crystallise is saturated with silver arsenate at a tempera- C. H. B.216 ABSTRACTS OF CHEMICAL PAPERS. ture a little below loo", it deposits orange-red hexagonal prisms with rhombohedra1 terminations. Their form agrees with that of disilver hydrogen phosphate, and indicates that they are disilver arsenate, but they could not be purified. When a syrupy solution of silver arsenate in arsenic acid is heated above loo", it yields a white granular powder similar in appearance to the compound Ag20,2As206, described by Hurtzig and Geuther.Solubility of Silver Chromate in Ammonium Nitrate, By R. P. CARPENTER (J. Xoc. Chem. Ind., 5, 286).-1t is found that on treating freshly precipitated silver chromate with B strong solution of ammonium nitrate, the solutioii instantly assumes a bright yellow colour in the cold. On warming, the rate of solution rapidly increases up to the boiling point; on cooling, the silver chromate crystallises out in needle-shaped crystals. In a paper by G. Riscaro (Chern. News, 53, 67) " On a Defect in the Volumetric Estimation of Chlorine by Mohr's Process," it was stated that " if nitrates, especially those of the alkalis and alkaline earths, are simultaneously present, the pre- cipitation of the red silver chromate often takes place too late," a circumstance which the author considers to be fully explained by the above experiments.The subjoined table gives the results of some experiments made to determine the relative solubility of silver chro- mate in the nitrates of potassium, sodium, ammonium, and magne- sium in cold and hot strong solutions :- One-tenth normal silver nitrate added. C. H. B. Grains of silver chromate 7-- 7 dissolved in hot 10". 100". solution. Pure water.. . . . . . . 0.05 C.C. 0.25 C.C. 0 064 Sodium nitrate . . . . 0.05 ,, 0.25 ,, 0,064 Potassium nitrate . . 0.10 ,, 0.75 ,, 0.192 Magnesium nitrate. . 0.35 ,, 1.00 ,, 0.256 50 grains of each of the above salts were dissolved in 100 C.C. of water, and the amount of decinormal silver nitrate solution taken to obtain the reaction with potassium chromate is given in the table.In the last three cases, the author has deducted the amount of silver chromate dissolved by the water alone, and has given the amourit due to the solvent action of the respective nitrates. From all these, the silver chromate crystallised out again on cooling. Tetracalcium Phosphate and Basic Converter Slag. By E. JENSCH (Ber., 19, 3093-3101).-1t has been generally assumed that the phosphoric acid in basic converter slag is present as tetracal- cium phosphate. The author has endeavoured t o prepare such a phosphate by heating tricalcium phosphate with calcium carbonate to a high temperature, He has failed to obtain a crystalline substance such as is frequently seen in the basic slag, but at the same time the properties of the tricalcium phosphate are so altered as to indicate some chemical change having occui*red.The following analyses of basic slag are quoted :-I. Mean results Ammonium nitrate. 0.07 ,, 1-23 ,, 0,320 D. B.INORGANIC CHEMISTRT. 217 for the slag of all German works (Hasenclever). 11. Mean of 12 analyses of slag from the steel works at Friedenshiitte. 111. Mean of four analyses of slag from Witkowitz. P205. CaO. MgO. IFeO. Fe,03. A1,03. MnO. S. SO3. SiO,. I. 17.25 48.29 4.89 9.44 3.78 2.04 3-91 0-49 0.2'2 7.96 11. 18.93 54.87 4-90 8-83 5.20 3-51 0.31 0.44 - 6.85 111, 16.86 49.45 1.26 9.88 5.96 2.17 2.93 0.61 0.10 10.08 The author considers that I1 may be regarded as consisting of- P20,,4Ca0.Mn,03,3Ca0. Fe20,,3Ca0. SiO,,BCaO. CaS. 48.78 1.20 30.77 19-59 0.99 With regard t o the statement frequently made, that a large propor- tion of the phosphorus is present in the form of iron phosphide, the author's results show that at most only 1.5 per cent. can be present in this form, and that even this is rendered soluble in the soil. A. J. G. The Determination of Water in the Hydrates of Strontium Oxide. By C. SCHEIBLER (Bey., 19, 2865-2868).-A controversial paper, in which the author rejects the deduction drawn by C. Heyer (this vol., p. l08), as evidence of the existence of a dihydrate of strontium oxide. It is also pointed out that Heyer's method for the determination of water in the dihydrate has only a limited value, since it is inapplicable to the monohydrates of the alkaline earths and to the dihydrate of barium oxide.w. P. w. Action of Carbonic Anhydride on the Dihydrate of Stron- tium Oxide. By R. FINKENER (Bey., 19, 2958-2963).--The author finds that well moistened stronbium hydroxide, kept for some time at 50" in an atmosphere of aqueous vapour having a tension of 16 mm., is converted into the dihydrate of strontium oxide. When exposed to a current of dry carbonic anhydride, the dihydrate is decomposed into the carbonate, but the product dried at 145" is deficient in carbonic anhydride and contains water. In opposition to Heyer's statement that carbonate alone is formed under these conditions, the author regards this fact as evidence that, in addition, a hydrated basic carbonate is also formed.The basic carbonate is %L neutral compound which, in an atmosphere of carbonic anhydride, slowly absorbs that gas. It does not lose its water completely at 120", but must be raised to incipient redness before complete dehydration occurs ; no evolution of carbonic anhydride occurs at this temperature, but the product on moistening with water is strongly alkaline. w. P. w. Estimation of Water in Strontia Dihydrate. By C. HEYER (Bey., 19, 3222--3224).-The author does not believe in the existence of a basic strontium carbonate, and ascribes the analytical results obtained by Finkener (preceding Abstract) to the use of too great an amount of substance (Finkener used over 5 grams), as not more than 0.5 gram should be used to ensure complete decomposition (compare this vol., p.108). N. E. M.218 ABSTRACTS OF CHEMICAL PAPERS. Vapour-density of Zinc. By J. MEXSCHING and V. MEPER (Bey., 19, 3295-3298) .-In their paper, the authors describe the method used by them in the determination of the vapour-density of zinc, and give details of the furnace employed, with which a constant tempera- ture of about 1400" was obtainable under the conditions of working. The porcelain experimental tube was filled with nitrogen carefully freed from every trace of oxygen by slow passage over red-hot copper turnings, and through chromous chloride and alkaline pyrogallate. Two experiments were made, one at a temperature lower than the maximum, the second a t the maximum temperature of the furnace, and the numbers obtained for the density were 2.41 and 2.36 respec- tively, compared with 2.25, the theoretical density of monatomic (Zn) zinc vapour.Experiments were also made with magnesium, but so far without success, since it has not been found possible t o volatilise Ammonio-mercuric Chromates. By C. HFNSGEN (Rec. Trav. Chim., 5, 187-198) .-On dissolving mercuric oxide in ammonium dichromate, Hirzel obtained a compound to which the formula (NHg2,0H2)2,4HgCr04, was ascribed, although based only on deter- minations of the mercury and chromium. I n this paper, it is shown that mercuric oxide dissolves readily in a saturated solution of am- monium dichromate ; golden, crystalline leaflets or needles separate out ; these are insoluble in water, alcohol, and ether, very soluble in hydrochloric acid, but only sparingly soluble in dilute nitric or sul- phuric acid.Analytical results showed the atomic ratio Hg : N : Cr = 1 : 2 : 2, and that three-fourths of the total nitrogen was in the form of ammonium and the remainder in an amido-group, results which point to the composition ( NHg2,H20),,Cr2073(NE€4)2Cr,07. These crystals when treated with excess of ammonia yield a canary-yellow powder, which no longer contains nitrogen in the form of ammonium, and to which the formula (NHgz,H20),Cr04 is ascribed. If mercury chromate be digested with a warm, concentrated solution of ammonium dichromate, a brown solution is obtained, from which, on pouring into an excess of cold water, a yellow powder is deposited ; the composi- tion of the substance is (NHg2,H,0),Cr04, the analogue of the selenate Water of Crystallisation of Alums.By E. MAUXEN~ (Compt. rend., 103, 1140-1 141 ).-Ordinary potassium-alum, containing according to the author 28-73 mols. H,O, was dried for several months over sulphuric acid almost completely free from water. It never shows any condition of equilibrium corresponding with the formation of a hydrate containing 24 mols. H,O. Towards the end of the operation, dehydration took place very slowly. The product contains 3.5 mols. H,O, and seems to have attained a condition of equilibrium. Chemical Composition of some Ancient Ceramics from Brandenburg. By E. JENSCH (Ber., 19, 28SO-2853) .-Fragments of urns from various ancient burying places were analysed. The following may be quoted as examples :-I.From the urn field between the metal in hydrogen. w. P. w. (NHg2, H,O)LSe04. v. H. v. C. H. B.INOlZGANIC OHE1\.IISTRT. 219 Reichersdorf and Kuppen, Jessnitz N/L. 11. Funfeichen, Fiirsten- berg a/O. The specimen I1 was taken from the sides, which were covered with a thin glaze, I and I11 were taken from the bottom of the urns. Specimen I1 was coarse-grained and porous. Dried at 105" the loss of weight varied between 0.6-5-3 mean 1.95 per cent., an additional loss of 1.5-9.4, mean 4*0,2 per cent., occurring when the temperature was raised to a red heat. 111. Platkow, GUSOW, in the Lebus district. SiO,. A1203. Fez03. FeO. CttO. MgO. Alkalis. I, 62.46 27.27 3.17 0.44 1.21 0.89 2.93 11. 61.32 36.57 1.07 0.33 0.18 0.24 0.13 111, 64.57 27-70 1.77 - 2.83 0.28 0.69 P206.803. MnO. Total. I. 0.01 0.1 1 0-23 98.73 11. - - - 99.84 111. 0.75 - 0.27 98.66 Owing to the unusual amount of phosphoric acid, analyses of five other fragments from the two urns containing the highest amount were made, with a result that a variation of 0.26-0.85 per cent., and 0-12-0*97 per cent. respectively were found, This is in all probability accounted for by imperfect admixture of bone-ash or some material rich in phosphorus with the red clay of the district which was most probably used in the manufacture of the urns. The clay accompanying t,he urn from Iiinderode had the composition SiO,,, 62-67 ; A1203, 29.34 ; FeO and FezO,, 3'56 ; CaO, 1.17 ; MgO, 0.53 ; Alkalis, 2.02. w. P. w. Heating and Cooling of Fused Steel.By OSMOND COW^^. rend., 103, 1135-1137) .-Iron containing 0.16 per cent. of carbon shows a feeble perturbation at 749" (this vol., p. 14), but the modifica- tion of the iran takes place mainly at a higher temperature. In the cooling of the fused metal, there are in fact three points at which the rate of cooling diminishes. Between 863 and 820", the maximum effect being observed between 845" and 839"; between 775" and 736", the maximum being between 763" and 749"; and between 693" and 669". The first change indicates the return of the iron from the 6 modifica- tion which is stable at high temperatures, t o the ordinary modification stable at the ordinary temperature, this return being retarded by the presence of the small quantityof carbon. The first diminution in the rate of cooling corresponds with a development of +3.8 cal.and the second with a development of +1*3 cal., the total 5#1 agreeing closely with Pionchon's determination + 5.3 cal. On reheating, the second and third perturbations become coincident. With steel containing 0.57 per cent. of carbon, the two perturbations at the highest temperatures become merged into one which takes place at 736-690", but is still quite distinct from recalescence. If the steel contains 1.25 per cent. of carbon, the temperature at which alteration takes place is still lower, and in fact coincides with recalescence at220 ABSTRACTS OF CHEMICAL PAPERS. 704". It is evident that during cooling the presence of the dissolved carbon retards the alteration of the iron the more completely the greater its quantity.Steel containing 0.16 per cent. of carbon shows the same perturba- tions in an atmosphere of hydrogen as in nitrogen. Steel containing 1.25 per cent. of carbon when cooled in hydrogen from 800" shows much enfeebled recalescence, a result probabiy due to the fact that hydrogen, as Forquignon has shown, has a strong attraction for the carbon i n steel, and thus diminishes the proportion of carbon which combines with the iron. In another experiment, however, cooling from 1100". no anomalies were observed. No noteworthy differences are observed in an atmosphere of coal-gas. C . H. B. Influence of Silicon on the Condition of Carbon in Cast- iron. By F. GAUTIER (Compt. rend., 103, 1137--1140).-The author has repeated Stead and Wood's experiments in which white' iron was converted into grey iron by melting with a certain proportion of iron rich in silicon.His results were precisely the same, and show that in presence of not less than 2 per cent. of silicon the combined carbon is almost completely changed into graphite. He points out that the reverse change takes place in the Bessemer process. About half the silicon is removed before the amount of carbon has appreciably diminished, and it is then found thah the iron has become white. The presence of manganese intederes with the conversion of com- bined carbon into graphite, owing to the tendency of the manganese to combine with carbon. Grey iron prepared indirectly in this way is more homogeneous and has greater tenacity than grey iron obtained in the ordinary way.C. H. B. A New Class of Cobaltic Salts. By I?. KEHRMANN (Bey., 19, 3101-3103) .-Potassium cobaltic oxalate, K6C02(C204), + 6Hz0, is obtained by mixing cobaltic hydroxide, potassium oxalate, oxalic acid, and water to a thick paste, and allowing the mixture to remain 14 to 21 days. After recrystallisation, &c., the salt is obtained in nearly black, well-formed, seemingly monosymmetric crystals, which in thin lamells show distinct dichroism (dark blue and emerald-green). When treated with cold saturated sodium chloride solution, the sodium potassium salt is obtained crystallising in beautiful pyramids. The barium salt crystallises in sparingly soluble, green needles. The solutions of these salts are stable in the cold, but quickly decompose on heating with evolution of carbonic anhydride and formation of cobaltous salts.Corresponding nickel compounds could not be ob- tained. A. J. GINORGANIC CHEMISTRY. 211I n o r g a ni c C h e m i s t r y.Formation of Active Oxygen in the Akmosphere, and itsConnection with the Electric Phenomena of the Air and theProduction of Storms, By C. WURSTER (Ber., 19, 3208-3217).-Observations made by the author lead him to conclude that ozone isformed in the air by the action of sunlight on clouds. When cloudsare continually formed from above, they all become laden with ozone,whilst when they form from below only the upper layer will containmuch ozone. I n the former wse, the accumulation of ozone causesthe clouds to become strongly negatively electric, and so gives rise tothunderstorms.N. H. M.Formation of Active Oxygen in Paper. By C. WURSTER (Bey.,19, 3217--3218).-The yellow and brown colour acquired by som212 ABSTRACTS OF CHEMICAL PAPERS.papers is due to the action of active oxygen on the resin used in siz-i n g the paper, or in some cases on the woody matter present i n thepaper. By means of dimethylparaphenylenediamine paper (this vol.,p. 298), the presence and even the percentage amount of woody mattercan be determined in a paper. When the moist dimethylpara-phenylenediamine paper is pressed between paper containing wood, itacquires a deep red colour. Ordinary sized paper merely turns it adelicate rose colour. N. H. M.Phosphorus Pentafluoride. By H. MOWAN (Compt. rend., 103,1257-1260).-Perfectly dry phosphorus pentafluoride confined overmercury is not decomposed by the action of induction sparks 40 mm.in length, a result which agrees with Thurpe's earlier observation.With sparks 150-200 mm.in length, however, the gas is decomposedinfo phosphorus trifluoride and fluorine, the latter at once attackingthe glass and the mercury.Phosphorus pentafluoyide yields no trihoride when heated to dullredness with an excess of phosphorus. In this respect, its behaviourdiffers from that of the pentachloride. It is not affected by sulphurvaponr at 440", nor by iodine vepour at 500". In presence ofa minute trace of water, it attacks glass, with formation of siliconfluoride and phosphorus oxyfluoride, whilst the alkalis in the glass areconverted into phosphates or fluorphosphates.In order to analyse the gas, a measured volume was absorbed inwater in a platinum vessel, treated with nitric acid and molybdicsolution, and the phosphorus finally weighed as magnesium pyrophos-phate. Another method consists in absorbing a measured volume inpotassium hydroxide solution, which is mixed with some pure silica,evaporated to dryness, mixed with concentrated sulphuric acid, andheated until vapours of this acid begin to come off.The liquid isthen diluted, made alkaline with ammonia, and the phosphorus pre-cipitated as magnesium ammonium phosph te.The results agree with the formula PF,; the first method is themost accurate. C. H. B.Compounds of Selenious and Arsenious Anhydrides withSulphuric Anhydride : Isolation of Sulphuric Anhydride.By R.W EBER (Bey., 19, 3185--31YO).-When selenious anhydride iswarmed with very carefully purified sulphuric anhydride, it dissolvestherein, and if the excess of sulphuric anhydride is distilled off at 60-70°, a crystalline compound, Se02,S03, is left. This substance isdecomposed by a temperature of loo", sulphuric anhydride beingevolved.In like manner, sulphuric anhydride dissolves arsenious anhydride.If the excefis of sulphuric anhydride is distilled off at 6U0, a compoundof the formula As203,6S03 is left ; if the distillation is continued a tlOO", the regidue has the formula As203,3S03. These compounds arequite distinct from the compound As203,S03 discovered by Reich in1863 in the Freiberg smelting works.The author states that the specimens of pure sulphuric anhydridepreviously obtained and described (this Journal, 1877, ii, 164) stillWater decomposes it with great violenceINORGANIC CREMISTRY.213retain their original character, melting and resolidifying at 15". andshowing no signs of forming allotropic modifications. He is still ofopinion that the various modifications of sulphuric anhydride are alldue to the presence of traces of moisture, He describes further pre-cautions for obtaining absolutely pure anhydride, and considers thebest method to be to cohobate carefully purified sulphuric anhydridewith phosphoric anhydride in a slight modification of the bent andsealed distilling tube previously described (Zoc.cit.). After continuedcohobation, the sulphuric anhydride will remain liquid down to 15",even in contact with the phosphoric anhydride. Finally the sulphuricanhydride may be distilled over into the opposite end of the distillingtube, and this then sealed off without the air being able to come incontact with the inside of the tube. Phosphoric anhydrille forms acompound P205,3S03, which crystallises out from the excess of sul-phuric anhydride. This compound decomposes at the boiling point ofsulphuric anhydride. L. T. T.Behaviour of Iodine with Realgar and Arsenic Iodosulphide.By R. SCHNEIDER ( J . pr. Chem. [2], 34, 505--514).-Arsenious iodo-subpiuhide, As13,AssS3, is prepared by heating together either a mixtureof realgar ( 1 mol.) and iodine (2 atoms) with the least possible accessof air, or a mixture of 3 parts arsenious iodide with 1.6 parts of arsenictrisulphide.It 'forms an amorphous, vitreous mass with conchoidalfracture, aud is of a dark red or reddish-brown colour. It is not actedon by the air at ordinary temperatures, When heated a t loo", itsoftens, and boils at a higher temperature without evolution ofiodine vapour, but with partial decomposition in to arsenious iodide andsulphide. It is insoluble in hot and cold alcohol, ether, carbon bisul-phide, and chloroform. Hot water slowly decomposes it with forma-tion of hydriodic acid. Boiling hydrochloric acid slowly decomposesit with evolution of iodine. When boiled with concentrated sulphuricacid, it gives off iodine, sulphur and sulphurous anhydride.Potassiumand ammonium hydroxides dissolve arsenious iodosulphide to a colour-less liquid, from which dilute acids precipitate arsenious sulphide,whilst the whole of the iodine and part of the arsenic remain insolution. When treated with an ammoniacal solution of silver nitrate,it is decomposed, forming silver iodide, sulphide, and arsenite. Thisreaction affords a means of determining the composition of thesubstance.When realgar is shaken with a solution of iodine in carbon bi-sulphide, and iodine is added in small quantities until the whole ofthe realgar is dissolved (1 mol. realgar requires 6 atoms iodine), andthe solution then evaporated, arsenious iodide separates, partly inhexagonal plates and partly in rhombohedrons, mixed with longprisms of sulphur. Also, when a mixture of realgar (1 mol.) withiodine (6 atoms) is heated, and the resulting mass is dissolved incarbon bisulphide, arsenious iodide and sulphur are formed.Arsenic Pentasulphide.By L. W. MCCAY (Chem. News, 154,287) .-When a solution of an alkaline arsenate strongly acidifiedwith hydrochloric acid and saturated with hydrogen sulphide isG. H. M214 ABSTRACTS OF CHEMICAL PAPERS.heated in a closed vessel at 100” for one hour, the arsenate is com-pletely converted into pentasulphide. It contains no trisulphide, andif due precautions have been taken to exclude air, no free sulphur.Pure arsenic pentasulphide is lemon-yellow in colour, does riot yieldany sulphur to carbon bisulphide, and dissolves in ammonia withoutseparation of sulphur. When the arnmoniacal soliition is agitatedwith silver nitrate and filtered, a clear filtrate is obtained, fromwhich nitric acid precipitates silver arsenate.The formation ofarsenic pentasulphide in this manner confirms Bunsen’s results, hehaving obtained it by the action of hydrogen sulphide on hot, solutionsof arsenic compounds.Carbonic Anhydride in the Atmosphere. By R. BLOCHMANN(Annnlen, 237, 39--90).-The author gives an account of the variousmethods which have been used for the estimation of the carbonicanhydride in the atmosphere from the time of Saussure to the presentday. It is pointed out that Pettenkofer’s method yields too highresults ; the normal amount of carbonic anhydride in 10,000 volumesof air is 3, not 4 volumes.The author describes a modification ofPettenkofer’s method, which permits of the baryta-water beingfiltered through asbestos and titrnted without coming into contactwith the air of the atmosphere, A double burette of special construc-tion is required. Drawings of the apparatus are given in the original.Bimetallic Phosphates. By A. JOLY (Compt. rend:., 103,1129-1132) .-The action of disodium hydrogen phosphate on solutions ofmetallic salts varies with the conditions, and with the nature of themetal. I n some cases, with silver nitrate for instance, an amorphousprecipitate of the trihasic phosphate is at once produced; in others, a,gelatinous monophosphak is at first precipitated, and t h i s graduallypasses into a crystalhe diphosphate.I n the case of the alkalineearths and manganese, the first stage in the reaction is represented bythe equation 4Na2HPOa + 4M”Cl2 = M,”(PO& + M”H4(POa)z +8NaCI.The monophosphahes decompose in presence of water with a rapiditywhich depends on the nature of the metal and the concentration ofthe solution (Abstr., 1884, 556).In some cases, these is an intermediate reaction, the gelatinousmonophosphate becoming crystalline. This is the final stage of thereaction if the conditions are such as to prevent the formation of a di-phosphate. The diphosphates decompose a t 100” into crystallinetribasic phosphates and the free acid, and a t the ordinary temperaturethe reverse change takes place to a greater or less extent.Thesefacts indicate that the intermediate phosphates described by variousauthors are in reality mixtures. The precipitation of silver phosphatemay be regarded as taking place in two stages, the first productsbeing the trisilver phosphate and the monophosphate, the latter im-mediately decomposing into the tribasic salt and the free acid, whichlimits the extent of the reaction. The formation of disilver phosphateis impossible under these conditions, since this salt is immediately de-composed by water (this vol., p. 215).D. A. L.w. c. wINORGANIC CHEMISTRY. 215In the case of hypophosphoric acid, the precipitate is at first agelatinous bibasic phosphate, which rapidly changes into a crystallinemonobasic phosphate (Abstr., 1886, 200, 408, 593, 662).Silver Phosphates and Arsenates.By A. JOLY (Cmapt. rend.,103, 1071-1074).-Precipitated and amorphous silver phosphate dis-solve in phosphoric acid solution, the solubility increasing with theconcentration of the acid and the temperature. If a liquid containingless than 38 parts of phosphoric anhydride to 100 parts of water issaturated with silver phosphate at 80" and allowed to cool, it depositstrisilver phosphate in pale-yellow, rhombic dodecahedrons modified byfaces of the icositetrabedron. The mother-liquor deposits no morecrystals on standing, but will dissolve a further quantity of amor-phous silver phosphate if heated, and thus the same fiolution of phos-phoric acid can be used for the crystallisation of an unlimited quantityof silver phosphate.If the solution contains 40 parts of phosphoric anhydride to 200parts of water, it deposits disilver hydrogen phosphate, AgzHP04, incolourless crystals derived from a hexagonal prism.They generallyform long prisms with rhombohedra1 terminations. I n contact withwater or alcohol, they became yellow, and decompose into trisilverphosphate and phosphoric acid, but they are not aff'ected by ether. Ifthe concentration of the phosphoric acid solution differs much fromthe strength given, the produet is a mixture of crystals very difficultto purify.When the crystals of disilver hydrogen phosphate are heated to110-150°, they yield silver pyrophosphate, AgtPZO7, which can alsobe obtained by heating the syrupy solution of the silver phosphate tothe same temperature.Hurhig and Geuther obtained the same com-pound by adding ether to the solution which had been heated. Thepyrophosphate is not, however, formed in the wet way as theseauthors supposed, since under the given conditions of concentration,the fused acid salt, and not its solution, is decomposed. The experi-ment simply shows that disilver hydrogen phosphate yields the pjro-phosphate at a lower temperature than that ak which phosphoric acidis converted into pyrophosphoric acid,Silver arsenate is much less soluble than the phosphate in the freeacid. If the solution contains less than 70 parts of arsenic anhydrideto 100 parts of water, the solution saturated with amorphous silverarsenate at 80" deposits rery brilliant, black, opaque crystals of tri-silver arsenate, which are unmodified rhombic dodecahedra.A solution of arsenic acid of the composition H,AsO, + H,O, whensaturated with silver arsenate, yields white monoclinic crystals ofsilver dihydrogen arsenate, a compound which is very readily pre-pared.I t is decomposed into trisilver arsenate and arsenic acid by atrace of water, and if heated t o 100" yields silver metarsenate i n theform of a white powder which absorbs water very slowly. Beforelosing water, the crystals of the acid salt become red, probably owingto the formation of arsenic acid and disilver hydrogen arsenate,AgzHAs04. In fact, if a solution from which silver dihydrogen arse-nate will crystallise is saturated with silver arsenate at a tempera-C. H.B216 ABSTRACTS OF CHEMICAL PAPERS.ture a little below loo", it deposits orange-red hexagonal prisms withrhombohedra1 terminations. Their form agrees with that of disilverhydrogen phosphate, and indicates that they are disilver arsenate, butthey could not be purified.When a syrupy solution of silver arsenate in arsenic acid is heatedabove loo", it yields a white granular powder similar in appearance tothe compound Ag20,2As206, described by Hurtzig and Geuther.Solubility of Silver Chromate in Ammonium Nitrate, ByR. P. CARPENTER (J. Xoc. Chem. Ind., 5, 286).-1t is found that ontreating freshly precipitated silver chromate with B strong solution ofammonium nitrate, the solutioii instantly assumes a bright yellowcolour in the cold.On warming, the rate of solution rapidly increasesup to the boiling point; on cooling, the silver chromate crystallisesout in needle-shaped crystals. In a paper by G. Riscaro (Chern.News, 53, 67) " On a Defect in the Volumetric Estimation of Chlorineby Mohr's Process," it was stated that " if nitrates, especially thoseof the alkalis and alkaline earths, are simultaneously present, the pre-cipitation of the red silver chromate often takes place too late," acircumstance which the author considers to be fully explained by theabove experiments. The subjoined table gives the results of someexperiments made to determine the relative solubility of silver chro-mate in the nitrates of potassium, sodium, ammonium, and magne-sium in cold and hot strong solutions :-One-tenth normal silvernitrate added.C.H. B.Grains of silver chromate7-- 7 dissolved in hot10". 100". solution.Pure water.. . . . . . . 0.05 C.C. 0.25 C.C. 0 064Sodium nitrate . . . . 0.05 ,, 0.25 ,, 0,064Potassium nitrate . . 0.10 ,, 0.75 ,, 0.192Magnesium nitrate. . 0.35 ,, 1.00 ,, 0.25650 grains of each of the above salts were dissolved in 100 C.C. ofwater, and the amount of decinormal silver nitrate solution taken toobtain the reaction with potassium chromate is given in the table. Inthe last three cases, the author has deducted the amount of silverchromate dissolved by the water alone, and has given the amouritdue to the solvent action of the respective nitrates. From all these,the silver chromate crystallised out again on cooling.Tetracalcium Phosphate and Basic Converter Slag.By E.JENSCH (Ber., 19, 3093-3101).-1t has been generally assumed thatthe phosphoric acid in basic converter slag is present as tetracal-cium phosphate. The author has endeavoured t o prepare such aphosphate by heating tricalcium phosphate with calcium carbonate toa high temperature, He has failed to obtain a crystalline substancesuch as is frequently seen in the basic slag, but at the same time theproperties of the tricalcium phosphate are so altered as to indicatesome chemical change having occui*red.The following analyses of basic slag are quoted :-I. Mean resultsAmmonium nitrate. 0.07 ,, 1-23 ,, 0,320D. BINORGANIC CHEMISTRT.217for the slag of all German works (Hasenclever). 11. Mean of12 analyses of slag from the steel works at Friedenshiitte. 111. Meanof four analyses of slag from Witkowitz.P205. CaO. MgO. IFeO. Fe,03. A1,03. MnO. S. SO3. SiO,.I. 17.25 48.29 4.89 9.44 3.78 2.04 3-91 0-49 0.2'2 7.9611. 18.93 54.87 4-90 8-83 5.20 3-51 0.31 0.44 - 6.85111, 16.86 49.45 1.26 9.88 5.96 2.17 2.93 0.61 0.10 10.08The author considers that I1 may be regarded as consisting of-P20,,4Ca0. Mn,03,3Ca0. Fe20,,3Ca0. SiO,,BCaO. CaS.48.78 1.20 30.77 19-59 0.99With regard t o the statement frequently made, that a large propor-tion of the phosphorus is present in the form of iron phosphide, theauthor's results show that at most only 1.5 per cent. can be present inthis form, and that even this is rendered soluble in the soil.A.J. G.The Determination of Water in the Hydrates of StrontiumOxide. By C. SCHEIBLER (Bey., 19, 2865-2868).-A controversialpaper, in which the author rejects the deduction drawn by C. Heyer(this vol., p. l08), as evidence of the existence of a dihydrate ofstrontium oxide. It is also pointed out that Heyer's method for thedetermination of water in the dihydrate has only a limited value, sinceit is inapplicable to the monohydrates of the alkaline earths and to thedihydrate of barium oxide. w. P. w.Action of Carbonic Anhydride on the Dihydrate of Stron-tium Oxide. By R. FINKENER (Bey., 19, 2958-2963).--The authorfinds that well moistened stronbium hydroxide, kept for some time at50" in an atmosphere of aqueous vapour having a tension of 16 mm.,is converted into the dihydrate of strontium oxide.When exposed toa current of dry carbonic anhydride, the dihydrate is decomposedinto the carbonate, but the product dried at 145" is deficient in carbonicanhydride and contains water. In opposition to Heyer's statement thatcarbonate alone is formed under these conditions, the author regardsthis fact as evidence that, in addition, a hydrated basic carbonate isalso formed. The basic carbonate is %L neutral compound which, in anatmosphere of carbonic anhydride, slowly absorbs that gas. It doesnot lose its water completely at 120", but must be raised to incipientredness before complete dehydration occurs ; no evolution of carbonicanhydride occurs at this temperature, but the product on moisteningwith water is strongly alkaline. w.P. w.Estimation of Water in Strontia Dihydrate. By C. HEYER(Bey., 19, 3222--3224).-The author does not believe in the existenceof a basic strontium carbonate, and ascribes the analytical resultsobtained by Finkener (preceding Abstract) to the use of too great anamount of substance (Finkener used over 5 grams), as not more than0.5 gram should be used to ensure complete decomposition (comparethis vol., p. 108). N. E. M218 ABSTRACTS OF CHEMICAL PAPERS.Vapour-density of Zinc. By J. MEXSCHING and V. MEPER (Bey.,19, 3295-3298) .-In their paper, the authors describe the methodused by them in the determination of the vapour-density of zinc, andgive details of the furnace employed, with which a constant tempera-ture of about 1400" was obtainable under the conditions of working.The porcelain experimental tube was filled with nitrogen carefullyfreed from every trace of oxygen by slow passage over red-hot copperturnings, and through chromous chloride and alkaline pyrogallate.Two experiments were made, one at a temperature lower than themaximum, the second a t the maximum temperature of the furnace,and the numbers obtained for the density were 2.41 and 2.36 respec-tively, compared with 2.25, the theoretical density of monatomic (Zn)zinc vapour.Experiments were also made with magnesium, but sofar without success, since it has not been found possible t o volatiliseAmmonio-mercuric Chromates.By C. HFNSGEN (Rec. Trav.Chim., 5, 187-198) .-On dissolving mercuric oxide in ammoniumdichromate, Hirzel obtained a compound to which the formula(NHg2,0H2)2,4HgCr04, was ascribed, although based only on deter-minations of the mercury and chromium. I n this paper, it is shownthat mercuric oxide dissolves readily in a saturated solution of am-monium dichromate ; golden, crystalline leaflets or needles separateout ; these are insoluble in water, alcohol, and ether, very soluble inhydrochloric acid, but only sparingly soluble in dilute nitric or sul-phuric acid. Analytical results showed the atomic ratio Hg : N : Cr =1 : 2 : 2, and that three-fourths of the total nitrogen was in the formof ammonium and the remainder in an amido-group, results whichpoint to the composition ( NHg2,H20),,Cr2073(NE€4)2Cr,07. Thesecrystals when treated with excess of ammonia yield a canary-yellowpowder, which no longer contains nitrogen in the form of ammonium,and to which the formula (NHgz,H20),Cr04 is ascribed.If mercurychromate be digested with a warm, concentrated solution of ammoniumdichromate, a brown solution is obtained, from which, on pouring intoan excess of cold water, a yellow powder is deposited ; the composi-tion of the substance is (NHg2,H,0),Cr04, the analogue of the selenateWater of Crystallisation of Alums. By E. MAUXEN~ (Compt.rend., 103, 1140-1 141 ).-Ordinary potassium-alum, containingaccording to the author 28-73 mols. H,O, was dried for several monthsover sulphuric acid almost completely free from water.It nevershows any condition of equilibrium corresponding with the formationof a hydrate containing 24 mols. H,O. Towards the end of theoperation, dehydration took place very slowly. The product contains3.5 mols. H,O, and seems to have attained a condition of equilibrium.Chemical Composition of some Ancient Ceramics fromBrandenburg. By E. JENSCH (Ber., 19, 28SO-2853) .-Fragmentsof urns from various ancient burying places were analysed. Thefollowing may be quoted as examples :-I. From the urn field betweenthe metal in hydrogen. w. P. w.(NHg2, H,O)LSe04. v. H. v.C. H. BINOlZGANIC OHE1\.IISTRT. 219Reichersdorf and Kuppen, Jessnitz N/L. 11. Funfeichen, Fiirsten-berg a/O.The specimen I1 was taken from the sides, which were covered witha thin glaze, I and I11 were taken from the bottom of the urns.Specimen I1 was coarse-grained and porous. Dried at 105" the lossof weight varied between 0.6-5-3 mean 1.95 per cent., an additionalloss of 1.5-9.4, mean 4*0,2 per cent., occurring when the temperaturewas raised to a red heat.111.Platkow, GUSOW, in the Lebus district.SiO,. A1203. Fez03. FeO. CttO. MgO. Alkalis.I, 62.46 27.27 3.17 0.44 1.21 0.89 2.9311. 61.32 36.57 1.07 0.33 0.18 0.24 0.13111, 64.57 27-70 1.77 - 2.83 0.28 0.69P206. 803. MnO. Total.I. 0.01 0.1 1 0-23 98.7311. - - - 99.84111. 0.75 - 0.27 98.66Owing to the unusual amount of phosphoric acid, analyses of fiveother fragments from the two urns containing the highest amountwere made, with a result that a variation of 0.26-0.85 per cent.,and 0-12-0*97 per cent.respectively were found, This is in allprobability accounted for by imperfect admixture of bone-ash or somematerial rich in phosphorus with the red clay of the district whichwas most probably used in the manufacture of the urns. The clayaccompanying t,he urn from Iiinderode had the composition SiO,,,62-67 ; A1203, 29.34 ; FeO and FezO,, 3'56 ; CaO, 1.17 ; MgO, 0.53 ;Alkalis, 2.02. w. P. w.Heating and Cooling of Fused Steel. By OSMOND COW^^.rend., 103, 1135-1137) .-Iron containing 0.16 per cent. of carbonshows a feeble perturbation at 749" (this vol., p. 14), but the modifica-tion of the iran takes place mainly at a higher temperature. In thecooling of the fused metal, there are in fact three points at which therate of cooling diminishes.Between 863 and 820", the maximum effectbeing observed between 845" and 839"; between 775" and 736", themaximum being between 763" and 749"; and between 693" and 669".The first change indicates the return of the iron from the 6 modifica-tion which is stable at high temperatures, t o the ordinary modificationstable at the ordinary temperature, this return being retarded by thepresence of the small quantityof carbon. The first diminution in therate of cooling corresponds with a development of +3.8 cal. and thesecond with a development of +1*3 cal., the total 5#1 agreeingclosely with Pionchon's determination + 5.3 cal. On reheating, thesecond and third perturbations become coincident.With steel containing 0.57 per cent.of carbon, the two perturbationsat the highest temperatures become merged into one which takes placeat 736-690", but is still quite distinct from recalescence. If the steelcontains 1.25 per cent. of carbon, the temperature at which alterationtakes place is still lower, and in fact coincides with recalescence a220 ABSTRACTS OF CHEMICAL PAPERS.704". It is evident that during cooling the presence of the dissolvedcarbon retards the alteration of the iron the more completely thegreater its quantity.Steel containing 0.16 per cent. of carbon shows the same perturba-tions in an atmosphere of hydrogen as in nitrogen. Steel containing1.25 per cent. of carbon when cooled in hydrogen from 800" showsmuch enfeebled recalescence, a result probabiy due to the fact thathydrogen, as Forquignon has shown, has a strong attraction for thecarbon i n steel, and thus diminishes the proportion of carbon whichcombines with the iron. In another experiment, however, coolingfrom 1100". no anomalies were observed.No noteworthy differences are observed in an atmosphere of coal-gas.C . H. B.Influence of Silicon on the Condition of Carbon in Cast-iron. By F. GAUTIER (Compt. rend., 103, 1137--1140).-The authorhas repeated Stead and Wood's experiments in which white' iron wasconverted into grey iron by melting with a certain proportion of ironrich in silicon. His results were precisely the same, and show thatin presence of not less than 2 per cent. of silicon the combined carbonis almost completely changed into graphite. He points out that thereverse change takes place in the Bessemer process. About half thesilicon is removed before the amount of carbon has appreciablydiminished, and it is then found thah the iron has become white.The presence of manganese intederes with the conversion of com-bined carbon into graphite, owing to the tendency of the manganeseto combine with carbon.Grey iron prepared indirectly in this way is more homogeneous andhas greater tenacity than grey iron obtained in the ordinary way.C. H. B.A New Class of Cobaltic Salts. By I?. KEHRMANN (Bey., 19,3101-3103) .-Potassium cobaltic oxalate, K6C02(C204), + 6Hz0, isobtained by mixing cobaltic hydroxide, potassium oxalate, oxalic acid,and water to a thick paste, and allowing the mixture to remain 14 to21 days. After recrystallisation, &c., the salt is obtained in nearlyblack, well-formed, seemingly monosymmetric crystals, which in thinlamells show distinct dichroism (dark blue and emerald-green).When treated with cold saturated sodium chloride solution, thesodium potassium salt is obtained crystallising in beautiful pyramids.The barium salt crystallises in sparingly soluble, green needles. Thesolutions of these salts are stable in the cold, but quickly decomposeon heating with evolution of carbonic anhydride and formation ofcobaltous salts. Corresponding nickel compounds could not be ob-tained. A. J.

ISSN:0368-1769    

DOI:10.1039/CA8875200211

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

JlISERXLOGICAL CHEMISTRY. Miner a 1 o g i c a 1 C h em i s t r y. 221 Occurrence of Free Iodine in a Mineral Water. By J. A. WANKT~YN (Cliem. News, 54, 300).-The water from Wooclhall S p , near Lincoln, is exceptionally rich in bromides and iodides, and, moreover, contains iodine in sufficient quantity to give it a bro\in tint. On agitating it with carbon bisulphide, the water is decolorised, the bisulphide becoming violet. By R. ROMANIS (Chem. News, 54, 218- 279).-The samplea were found on the banks of the Meza, a tzibutary of the Irrawaddi, about 30 miles from the latter river, and to the westward of Katha. Sample A.-Large irregular fragments with quartzembedded in some of them. Iridosmine and crystals of clirorne iron can be separated under a microscope. The composition is given below.The silver ore is a grey mineral which lose., 49 per cent. on ignition. Sample B.-Fine smooth grains; about 17 per cent. in- soluble in aqua regia, the insoluble matter consists of qnartz, zircon, arid about 7 per cent. of iridosmine in bright, flat grains mixed with a black mineral apparently a platirium ore. D. A. L. Gold from Burmah. A. Gold ............................ Silver.. .......................... I Quartz.. .......................... ?{ Magnetic oxide of iron.. . . . . . . . . . . . . I Silver (? ore).. .................... B. Gold .............................. Silver .............................. Platinum. ........................... Iridosmine .......................... Zirconia ............................ . (Copper pyrites .................... (Loss on ignition.................... Silica (by diff.) ...................... Magnetic oxide of irou . . . . . . . . . . . . . . . . 87.66 5 96 1.95 1.09 0.32 1 *54 1 -48 74-83 2-86 2.53 7-04 7.08 5-66 a litfle D. A. L. Preparation of Crystallised Insoluble Carbonates. By L. BOURGEOIS (Compt. rend., 103, 1088-1091).-0*5 pram of the amor- phous carbonate is heated in a tube a t 150-180", with 20 C.C. of water and 2 grams of ammonium chloride, and then very slowly cooled. After the process of heating followed by slow cooling has been repeated four or five times, the carbonate becomes completely crystallised. The ammonium chloride is partially convet ted into carbonate, which decomposes into ammonia and carbonic anhydride. Part of the insoluble carbonate is thus dissolved, and separates in crystals during the slow cooling.When the heating is repeated, the VOL. LIL P222 ABSTRACTS OF CHEMICAL PAPERS. same changes take place, and the crystals gradually increase at the expense of the amorphous substance. Calcite is obtained in simple rhombohedrons without admixture with axagonits ; strontianite is obtained in short, rhombic prisms ; witherite in long, thin, fibrous needles ; cerusite in long, striated needles, which are always mixed with a variable proportion of a hydrated carbonate in nacreous, he-- gonnl lamella?, with negative uniaxial double refraction, which is probably identical with hydrocerussite. Cadmium carbonate crystal- lises in rhombohedrons similar to those of calcite. Lithium, magcesium, zinc, manganese, iron, nickel, cobalt, and copper carbonates yield only amorphous precipitates or indistinct spheroli ths.Almost identical results are obtained by heating the carbonates at 140" with a solution of urea, which is converted into ammorium carbonate by hydration. In addition, copper yields small prisms, which seem to be identical with malachite. C. H. B. Occurrence of Iodine in Phosphorites and of Lithium in Psilomelane. By F, SANUBERGER (Jahrb. f. Jh., 1887,1, Mem., 9.5). -The author notes the remarkable manner in which elements occurriiig in rocks in very minute quantities become concentrated in certain products of the decomposition of the rocks. This is the case with iodine, which the author has detected in the staffelite from Brilon in Westphalia, separated out from decomposed diabase, and in the osteolite from the weathered basalts of the Kreuzberg on the Rhone.Xot less remarkable is the concentration of small quantities of lithium in psilomelane, a fact first observed in the' Saxon Ore Mountains, but subsequently by the author in various places in the Black Forest. Lithium also becomes concentrated in the hexagonal variety of zinc sulphide, the so-called schdenbleizde. B. H. B, Nephrite from Alaska. By A. B. MEYER (Jahrb. f. Min., 1887,1, Ref., 6-8).-The author describes two axes procured from the Indians of South-east Alaska. The smaller has a sp. gr. of 2-96, and contains some magnetite; the sp. gr. of the larger being 2.92. The hardness of the latter is somewhat less than is usual with nephrite ; the material being no longer quite unaltered, Analysis of the latter gave the following results :- SiOz.A120a. FeO. CsO. MgO. HaO. Total. 61.63 4.31 4.82 10.45 22.36 4.83, 98.41 Under the microscope, it was found that this nephrite resembles moRt closely that from the river Kitoj in East Siberia. I t differs from this, however, in the absence of all accessory constituents, except magnetite, Green nephrite has been found in situ at the extreme north-west of Alaska. The raw material brought from Point, Barrow in Alaska by B&d, proves on analysis to be neither nephrite nor jadeite, buc pectoli te, B. H. B.MINERALOGICAL CHEMISTR Y. 22:; Prehnite from Silesia. By A. BEUTELL (Jahd. f. Mk., 1887, 1, Mem., 89-94) .-1. Prehnite from St&gau.-Prehnite has recently been foiind in tke granite of Striegau. Analysis gave the following refiults :- SiOz.A120,. Fez€&. CnO. Loss on ignitioa Total. 43.29 25-58 trace 26.36 4.77 100~00~ These results correspond with the formula Si3012Ca,A1,H2. The mineral usually occurs in the form of compact masses, isolated crystals being occasionally met with. Thin sections under the micro- scope present the optical anomalies observed by Des Cloizeaux and Mallard in the prehnites of Connecticut and Arendal. 2. Prehnite from Jordansmuh1.-An analysis of prehnite from Jor- dansmuhl has been published by B. Schubert (Abstr., 1883, 35). To this the author now adds the results of an exhaustive crystallo- graphical and optical investigation. The axial ratio he finds to be a : b : c = 0 8420 : 1 : 1.1272.B. H. B. Porphyry from Horka in Prmssia. By V. STEGER (.Jahrb. f. Nin., 1887, 1, Ref., 42). - The porphyry occurring at Horka in Prussian Upper Lausitz exhibits a grey to dirty yeIlow ground-mass, containing numerous reddish-brown, small crystals of orhhoclase and white crystals of oligoclase. Quarta occurs but rarely. As. accessory constituents, the rock contains hornblende and sillimanite. Analysis gave the following results :- SiO,. A1,0,. FezO,. CaO. MgO. P205. KpO. 58.74 14-96 8-75 3.68 1-59 2.62 3.60 Loss on Na@. ignition. Total. 322 287 100.03 In chemical composition, the Horka porphyry resembles most closelv that from Vetakollen and Tvveholmen. near Christiania. It diffe& from these, however, in its pe&entage of 'phosphoric anhydride.B. H. B. Analyses of Persian Eruptive Rocks. By E. DRASCHE (Jahrb. f. Min., 1887, 1, Ref., 65--66).--No. 1. Augite andesite, from the Elburs, near Bumehin, containing plagioclase and augite in a reddish- brown ground-mass. No. 2. Olivine diabase from the same locality; pale brown augite forming small irregular patches between plagio- clase needles. The olivine is for t,he most part altered. No. 3. Plagio- clase basalt from Bumehin, exhibiting a porphyritic structure ; augi tc, plagioclase, magnetite, atnil iron-glance, occurring in a colourless magma. The olivine originally present is entirely decomposed. No. 4. Black rock from Tscliemerin Ruschkek, appearing under the microscope as a compact mass containing numerous granules, in which plagioclase, a chl6ritic mineral, and apatite have separated out.261 ABSTRACTS OF CHEMICAL PAPERS.sio, ................ Fe,O, .............. A&O, .............. CaO.. .............. MgO ................ K,O ............... Na,O ............... P,05 ................ Loss on ignitioii ...... No. 1. 55-10 8-53 19.57 5-90 2.01 4.77 3.67 1.19 - No. 2. 47-51 16.26 16.00 7.63 7.38 1.01 2-29 3.25 - No. 3. 50.53 11.76 18-36 9.33 4.40 3-23 2.0 7 1.35 - No. 4. 55.67 10.89 16-06 5.92 2.93 0.51 3.81 0.83 4.1 5 Totals .............. 100.73 101.S3 101.03 100.77 B. H. B. Investigations on Ore-veins. By F. SANDBERGER (Jahrb. f. Min., 1887, 1, Mem., 111 -113).-To complete his investigations on ore-veins, the author has collected pure material in quantity sufficient to enable a dry siirer assay to be made of the silicates.The sub- stances employed did not coiitain a trace of intermixed sulphides. The mica from the gneiss of Schnpbach was found to contain 0.001 per cent. of silver, and the augite fiDom the granular diabase of St. Andreasberg in the Ham also contained 0.001 per cent. of silver. Nine pears ago the author proved that lead, antimony, zinc, cobalt, copper, nickel, and arsenic w0re present in this augite. Consequently the elements of all the Andreasherg ores are shown to be present in it. B. H. B. Recent Alluvial Deposits in the 15 and the Zuyder Zee. By J. M. VAN BENMELEN (Rec. Trav. Ohhn., 5,199-218) .--In this paper, analyses are given of the recent deposits of eminently fertile clay ill tbe Zuyder Zee and Ij, with especial reference to the proportion of chlorides, sulphates, magnesium and calciam carbonates, and phos- phoric acid, together with the composition of the silicates.I n some localities, there was a considerable accumulation of iron pyrites, especially on the small ancient islands, along the banks of lakes of brackish water, and i n the soil in which plants have taken root and formed deposits of turf. The chemical changes which lead to this accumulation, consists in the simultaneous reduction of ferric oxide and sulphuric acid, accompanied by st slow disappearance of calcium carbonate. The ferrous sulphide thus formed is converted into pyrites as B unsen has previously explained. Analyses of cerhin clays showed from 2 to 5 per cent. of pyrites. When these clays are dried and exposed to the action of the air, EL contrary action takes piace, the pyrites being reconverted into ferric sulphate, which is deposited in the form of a bright, jellow, amorphous mould, this being ultimately coiiverted by rain into a very basic insoluble sulphate.The paper is illustrated by numerous analytical results. V. H. V. Mineral Waters from Java. By S. MEUNIER (Cowpt. r e d . , 103, 1205-1207) .-Three spriiigs from Kapouran, near Boghor, in the kingdom of Koiwipan, were examined. The waters were found to contain the following proportions of solid matter in grams perORGANIC CHEMISTRY. 225 litre :-Great Green Spring, 15.87 ; Hot Spring, 27.00 ; High Plat- form Spring, 28.78. The relative proportions of tlie constituents are practically the ,same in all three springs :- Calcium chloride.............. 54.203 Magnesium chloride . . . . . . . . . . 40.651 Sodium chloride .............. 2.860 Potassium chloride ............ 1.104 Residue insoluble in water.. .... 1.924 100.742 The portion of the residue insoluble in water consists of minute crystals of calcium magnesium carbonate, resembling those of dolo- niite. These springs are characterised by- the absence of carbonates and the presence of a large proportion of calcium chloride. They belong to a hydrological group, representatives of which are found in the CauquenAs, Chili ; Tinguiririca, Peru ; Savu Savu, in tlie Fiji Islands ; Berg Giefshubel, Saxony ; and Pitlseathly, Scotland. C. H. B.JlISERXLOGICAL CHEMISTRY.Miner a 1 o g i c a 1 C h em i s t r y.221Occurrence of Free Iodine in a Mineral Water.By J. A.WANKT~YN (Cliem. News, 54, 300).-The water from Wooclhall S p ,near Lincoln, is exceptionally rich in bromides and iodides, and,moreover, contains iodine in sufficient quantity to give it a bro\intint. On agitating it with carbon bisulphide, the water is decolorised,the bisulphide becoming violet.By R. ROMANIS (Chem. News, 54, 218-279).-The samplea were found on the banks of the Meza, a tzibutaryof the Irrawaddi, about 30 miles from the latter river, and to thewestward of Katha. Sample A.-Large irregular fragments withquartzembedded in some of them. Iridosmine and crystals of clirorneiron can be separated under a microscope. The composition is givenbelow. The silver ore is a grey mineral which lose., 49 per cent. onignition.Sample B.-Fine smooth grains; about 17 per cent. in-soluble in aqua regia, the insoluble matter consists of qnartz, zircon,arid about 7 per cent. of iridosmine in bright, flat grains mixed witha black mineral apparently a platirium ore.D. A. L.Gold from Burmah.A.Gold ............................Silver.. ..........................I Quartz.. ..........................?{ Magnetic oxide of iron.. . . . . . . . . . . . .I Silver (? ore).. ....................B.Gold ..............................Silver ..............................Platinum. ...........................Iridosmine ..........................Zirconia ............................. (Copper pyrites ....................(Loss on ignition....................Silica (by diff.) ......................Magnetic oxide of irou . . . . . . . . . . . . . . . .87.665 961.951.090.321 *541 -4874-832-862.537-047.085-66a litfleD. A. L.Preparation of Crystallised Insoluble Carbonates. By L.BOURGEOIS (Compt. rend., 103, 1088-1091).-0*5 pram of the amor-phous carbonate is heated in a tube a t 150-180", with 20 C.C. ofwater and 2 grams of ammonium chloride, and then very slowlycooled. After the process of heating followed by slow cooling hasbeen repeated four or five times, the carbonate becomes completelycrystallised. The ammonium chloride is partially convet ted intocarbonate, which decomposes into ammonia and carbonic anhydride.Part of the insoluble carbonate is thus dissolved, and separates incrystals during the slow cooling.When the heating is repeated, theVOL. LIL 222 ABSTRACTS OF CHEMICAL PAPERS.same changes take place, and the crystals gradually increase at theexpense of the amorphous substance. Calcite is obtained in simplerhombohedrons without admixture with axagonits ; strontianite isobtained in short, rhombic prisms ; witherite in long, thin, fibrousneedles ; cerusite in long, striated needles, which are always mixedwith a variable proportion of a hydrated carbonate in nacreous, he--gonnl lamella?, with negative uniaxial double refraction, which isprobably identical with hydrocerussite. Cadmium carbonate crystal-lises in rhombohedrons similar to those of calcite.Lithium, magcesium, zinc, manganese, iron, nickel, cobalt, andcopper carbonates yield only amorphous precipitates or indistinctspheroli ths.Almost identical results are obtained by heating the carbonates at140" with a solution of urea, which is converted into ammoriumcarbonate by hydration. In addition, copper yields small prisms,which seem to be identical with malachite.C. H. B.Occurrence of Iodine in Phosphorites and of Lithium inPsilomelane. By F, SANUBERGER (Jahrb. f. Jh., 1887,1, Mem., 9.5).-The author notes the remarkable manner in which elementsoccurriiig in rocks in very minute quantities become concentrated incertain products of the decomposition of the rocks. This is the casewith iodine, which the author has detected in the staffelite fromBrilon in Westphalia, separated out from decomposed diabase, and inthe osteolite from the weathered basalts of the Kreuzberg on theRhone.Xot less remarkable is the concentration of small quantities oflithium in psilomelane, a fact first observed in the' Saxon OreMountains, but subsequently by the author in various places in theBlack Forest.Lithium also becomes concentrated in the hexagonalvariety of zinc sulphide, the so-called schdenbleizde. B. H. B,Nephrite from Alaska. By A. B. MEYER (Jahrb. f. Min., 1887,1,Ref., 6-8).-The author describes two axes procured from theIndians of South-east Alaska. The smaller has a sp. gr. of 2-96, andcontains some magnetite; the sp. gr. of the larger being 2.92. Thehardness of the latter is somewhat less than is usual with nephrite ;the material being no longer quite unaltered, Analysis of the lattergave the following results :-SiOz.A120a. FeO. CsO. MgO. HaO. Total.61.63 4.31 4.82 10.45 22.36 4.83, 98.41Under the microscope, it was found that this nephrite resemblesmoRt closely that from the river Kitoj in East Siberia. I t differsfrom this, however, in the absence of all accessory constituents, exceptmagnetite,Green nephrite has been found in situ at the extreme north-west ofAlaska. The raw material brought from Point, Barrow in Alaska byB&d, proves on analysis to be neither nephrite nor jadeite, bucpectoli te, B. H. BMINERALOGICAL CHEMISTR Y. 22:;Prehnite from Silesia. By A. BEUTELL (Jahd. f. Mk., 1887, 1,Mem., 89-94) .-1. Prehnite from St&gau.-Prehnite has recentlybeen foiind in tke granite of Striegau.Analysis gave the followingrefiults :-SiOz. A120,. Fez€&. CnO. Loss on ignitioa Total.43.29 25-58 trace 26.36 4.77 100~00~These results correspond with the formula Si3012Ca,A1,H2. Themineral usually occurs in the form of compact masses, isolatedcrystals being occasionally met with. Thin sections under the micro-scope present the optical anomalies observed by Des Cloizeaux andMallard in the prehnites of Connecticut and Arendal.2. Prehnite from Jordansmuh1.-An analysis of prehnite from Jor-dansmuhl has been published by B. Schubert (Abstr., 1883, 35). Tothis the author now adds the results of an exhaustive crystallo-graphical and optical investigation. The axial ratio he finds to bea : b : c = 0 8420 : 1 : 1.1272.B. H. B.Porphyry from Horka in Prmssia. By V. STEGER (.Jahrb. f.Nin., 1887, 1, Ref., 42). - The porphyry occurring at Horka inPrussian Upper Lausitz exhibits a grey to dirty yeIlow ground-mass,containing numerous reddish-brown, small crystals of orhhoclase andwhite crystals of oligoclase. Quarta occurs but rarely. As. accessoryconstituents, the rock contains hornblende and sillimanite. Analysisgave the following results :-SiO,. A1,0,. FezO,. CaO. MgO. P205. KpO.58.74 14-96 8-75 3.68 1-59 2.62 3.60Loss onNa@. ignition. Total.322 287 100.03In chemical composition, the Horka porphyry resembles mostcloselv that from Vetakollen and Tvveholmen. near Christiania. Itdiffe& from these, however, in its pe&entage of 'phosphoric anhydride.B.H. B.Analyses of Persian Eruptive Rocks. By E. DRASCHE (Jahrb.f. Min., 1887, 1, Ref., 65--66).--No. 1. Augite andesite, from theElburs, near Bumehin, containing plagioclase and augite in a reddish-brown ground-mass. No. 2. Olivine diabase from the same locality;pale brown augite forming small irregular patches between plagio-clase needles. The olivine is for t,he most part altered. No. 3. Plagio-clase basalt from Bumehin, exhibiting a porphyritic structure ; augi tc,plagioclase, magnetite, atnil iron-glance, occurring in a colourlessmagma. The olivine originally present is entirely decomposed.No. 4. Black rock from Tscliemerin Ruschkek, appearing under themicroscope as a compact mass containing numerous granules, inwhich plagioclase, a chl6ritic mineral, and apatite have separated out261 ABSTRACTS OF CHEMICAL PAPERS.sio, ................Fe,O, ..............A&O, ..............CaO................MgO ................K,O ...............Na,O ...............P,05 ................Loss on ignitioii ......No. 1.55-108-5319.575-902.014.773.671.19-No. 2.47-5116.2616.007.637.381.012-293.25-No. 3.50.5311.7618-369.334.403-232.0 71.35-No. 4.55.6710.8916-065.922.930.513.810.834.1 5Totals .............. 100.73 101.S3 101.03 100.77B. H. B.Investigations on Ore-veins. By F. SANDBERGER (Jahrb. f.Min., 1887, 1, Mem., 111 -113).-To complete his investigations onore-veins, the author has collected pure material in quantity sufficientto enable a dry siirer assay to be made of the silicates.The sub-stances employed did not coiitain a trace of intermixed sulphides.The mica from the gneiss of Schnpbach was found to contain 0.001per cent. of silver, and the augite fiDom the granular diabase ofSt. Andreasberg in the Ham also contained 0.001 per cent. of silver.Nine pears ago the author proved that lead, antimony, zinc, cobalt,copper, nickel, and arsenic w0re present in this augite. Consequentlythe elements of all the Andreasherg ores are shown to be present init. B. H. B.Recent Alluvial Deposits in the 15 and the Zuyder Zee. ByJ. M. VAN BENMELEN (Rec. Trav. Ohhn., 5,199-218) .--In this paper,analyses are given of the recent deposits of eminently fertile clay illtbe Zuyder Zee and Ij, with especial reference to the proportion ofchlorides, sulphates, magnesium and calciam carbonates, and phos-phoric acid, together with the composition of the silicates.I n somelocalities, there was a considerable accumulation of iron pyrites,especially on the small ancient islands, along the banks of lakes ofbrackish water, and i n the soil in which plants have taken root andformed deposits of turf. The chemical changes which lead to thisaccumulation, consists in the simultaneous reduction of ferric oxideand sulphuric acid, accompanied by st slow disappearance of calciumcarbonate. The ferrous sulphide thus formed is converted intopyrites as B unsen has previously explained. Analyses of cerhinclays showed from 2 to 5 per cent. of pyrites. When these clays aredried and exposed to the action of the air, EL contrary action takespiace, the pyrites being reconverted into ferric sulphate, which isdeposited in the form of a bright, jellow, amorphous mould, this beingultimately coiiverted by rain into a very basic insoluble sulphate.The paper is illustrated by numerous analytical results.V. H. V.Mineral Waters from Java. By S. MEUNIER (Cowpt. r e d . ,103, 1205-1207) .-Three spriiigs from Kapouran, near Boghor, inthe kingdom of Koiwipan, were examined. The waters were foundto contain the following proportions of solid matter in grams peORGANIC CHEMISTRY. 225litre :-Great Green Spring, 15.87 ; Hot Spring, 27.00 ; High Plat-form Spring, 28.78.The relative proportions of tlie constituents are practically the,same in all three springs :-Calcium chloride. ............. 54.203Magnesium chloride . . . . . . . . . . 40.651Sodium chloride .............. 2.860Potassium chloride ............ 1.104Residue insoluble in water.. .... 1.924100.742The portion of the residue insoluble in water consists of minutecrystals of calcium magnesium carbonate, resembling those of dolo-niite.These springs are characterised by- the absence of carbonates andthe presence of a large proportion of calcium chloride. They belongto a hydrological group, representatives of which are found in theCauquenAs, Chili ; Tinguiririca, Peru ; Savu Savu, in tlie FijiIslands ; Berg Giefshubel, Saxony ; and Pitlseathly, Scotland.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8875200221

出版商:RSC    

年代:1887

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ORGANIC CHEMISTRY. 225 Organic Chemistry. Russian Petroleum. By J. A. LE BEL (COW,@. remd. 103 1017 -1019).-It is well known that American petroleum) consists mainly of paraffins whilst BakQ petroleum consists mainly of naphthenes ClrHfle and uaphthylenes C,H2,-2. Boussingault has shown that Alsatian petroleum contains other hydrocarbons. At Tiflis a petroleum is obtained with a composition similar to thatt of the American oil and in the Crimea heavy and light petro- leums are obtained from neighbouring strata The followinq table gives the sp. gr. of corresponding fractions of oil from different sources :- Sp. gr. Pennsylvania ............ 236-240" 0.81 BakQ .................. 240-241 0.83 Alsace . . . . . . . . . . . . . . . . . . 235-24.5 0.86 Tschungnelek (Crimes) . .235-245 0.89 The Crimean oil contains 87.4 per cent. of carbon and 12.5 per cent. of hydrogen. The differences in sp. gr. are greater than the differences in the amount of carbon and these differences do not remain constant when the more volatile fractions are examined :-226 ABSTRACTS OF CHEMICAL PAPERS. SP. gr. Pennsylvania ............ 92-94' 0.690 BakQ .................... 90-95 0.738 BakQ .................... 90-91 0.747 Tschungnelek. ............ 80-93 0,750 Toluene hydride .......... 96-97 0.758 The more volatile fractions of the Crimean oil are rely similar to the correspondirig fractions of the oil from BakQ and differences only become evident with t h e fractions boiling above 150". The sp. gr. of the Russian oils agrees with that of toluene hydride with which Beilstein and Kurbatow regard them as identical.I t may also be supposed that the Russian oil contains naphthenes belonging to the trimethylene series ; in this case it should contain a term C6H,0 boil- ing at 30-35" with a sp. gr. about 0.04 higher than thah of the cor- responding fraction of American oil. If on the other hand these naphthenes are hydrides of the benxene series the first term would be CsHI2 boiling at 70". I t is found that fyactions of Baka oil boiling at 30-35" have a sp. gr. whieh agrees closely with that of the same fraction of -4merican oil and also with that of pentane boiling at 30". The differences only become evident with the fractions above 60° and it may be taken that the Russian oils boiling above 60" contain no naphthenes a result which confirms Beilstein and Rurbatow 's con- clusion as to their identity with the benzene hydrides.C. H. B. Action of Heat on Ethylene. By L. M. NORTON and A. A. NOYES (Amer. Chem. J. 8 362-364 ; compare Abstr. 1886 604 and 781).-Ethglene was slowly passed through a hard glass tube heated to dull redness the escaping gascs passed through condensing tubes arnmoniacal cnprous chloride and bromine samples of the gases being ultimately collected. After a month 15 C.C. of liquid had been con- densed and was found to contain benzene naphthalene and anthra- cene ; only a very slight precipitate was formed in the cuprous solu- tion. There were about 300 grams of bromides of unsatiirated hydrocarbons consisting largely of ethylene bromide ; but methylene propylene and butylene bromides were also present as well as a solid bromide.The solid bromide is identical in composition and properties with the crotonylene tetrabromide obtained from coal-gas from cro- tonylene from erythrol and from oil-gas it is therefore divinyl CH2 CH-CH CH2. The escaping gases consisted of methane and ethane. The author believes that the aromatic hydrocarbons are formed directly from the ethylene withoiit the intermediate forma- tion of acetylene. H. B. Reaction of Organic Bisulphides and Bisulphoxides with Potassium Sulphide. Bey R. OTTO and A. ROSSING (Ber. 19 3129 -3132) .-When the bisulphides of ethyl smyl pbenyl pnratolyl or benzyl are treated with potassium sulphide in alcoholic solution they are converted into the corresponding mercaptides according to theORGANlC CHElllISTRY.227 equation X,S + 2K2S = 2XSK + KzSz the reaction thus seeming to be general for organic sulphides. Potassium bisulphide seems to be without action on these bisul- phides. I n like manner the thiosulphonates of the general formula RS02*SR are decomposed by potassium sulphide into the potassium salts of the thiosulphonic acids and potassium mercaptides. I n a foot-note the following boiling points are given:-Pam- toluene hydrosulphide 190*2-191.7". Paratoluene bisulphide begins to boil at 307" (thermometer in liquid) but is in great part de- composed during the distillation. Phenpl bisulphide beginsl to boil at 320° but is also in great part decomposed on distillation. By L. LINDET (Compt. rend. 103 1014-1017).-TriethyZ chlorazwophos- yhite EhPAuCZO3 is obtained by allowing absolute alcohol to drop on a mixture of dry aurous chloride and phosphorus both of which are immediately dissolved.The product is mixed with water and the insoluble oily ethereal salt is separated. Ethyl phosphite dis- solves aurous chloride and yields an oil identical in appearance with triethyl chloraurophosphite but the product could not be purified. The ethereal salt is also obtained by dissolving aurous chloride in a solntion of ethyl phospliite in alcohol prepared by Railton's method of allowing phosphorus trichloride to drop into a large excess of absolute alcohol. Triethyl chloraurophosphite is a liquid which solidifies to a white crystalline mass at about -10". It is not volatile and is stable when exposed to air at the ordinary temperature but begins to de- compose at 100"; spa gr.= 2.025. It is insoluble in water but dis- solves in alcohol ether and benzene. Ammonia dissolves it readily with formation of the compound Et3PAuC103 + 2NH3 which is ob- tained in Romewhat deliqnescent leaflets by evaporating the ammo- niacal solntion a t 40". This compound dissolves in water and when the solution is acidified the ethereal salt is precipitated. Tri- ethyl chloraixrophosphite also dissolves in potassium hydroxide soh- tion and is reprecipitated on adding an acid. If the solution is concentrated on the water-bath or in a vacuum at the ordinary tem- perature the ethereal salt separates as an oil mixed with crystals of potassium hydroxide hut both dissolve on addition of water.At lOU" potassium chloride and potassium aurite are formed but the etbereal salt is not completely decomposed unless evaporated to com- plete dryness in presence of excess of potassium hydroxide. Under these conditions gold separates in the metallic state Propyl butyl and amyl alcohols yield similar products. Trimethyl chloraurophosphite Me3PAuC103 is obtained by the action of pure methyl alcohol on aurous chloride and phosphorus. It forms slender colourless needleB which melt at 1 00-lOl" alter slightly when exposed to air and do not volafilise without decomposition. It is insoluble in water and is somewhat less soluble than the ethyl- compound in alcohol ether and benzene. It also dissolves in methyl alcohol. C. H. B. A. J. G. Action of Alcohols on Aurophosphorous Chloride,228 ABSTRACTS OF CHEMICAL PAPERS.Dextroratatory Hexyl Alcohol from Essence of Chamomile. Hg P. r. ROMIRURGH (Rec. Trav. Chim. 5 219-227).-By frequent f ractioual distillation of essence of Roman chamomile a dextrorotatory alcohol (methethoprop y l cr Zcohol) CH31 eEt*CH,.CH,*OH is obtained boiling a t 154"; sp. gr. 0.829 a t 15" ; [a]D = 8.2 a t 17". On oxidation with chromic mixture the alcohol yields a dextrorotatory caproic acid (met hethopropion ic acid) C HMeEt*CH,*C 0 OH boiling a t 19 6- 1%"; sp. gr 0.930 at 15"; = 8.92. I t s calcium and silver salts crystallise in needles and its amide in long needles melting a t 124" soluble in water. A hexyl caproate is formed as a subsidiary product of oxidation. This boils a t 233-234" with slight decomposition ; sp.gr. 0.867 a t 15" ; [aID = 12.86 at 19". As both the alcohol and also the acid obtained therefrom are optically active substances according t; the hypothesis of Van't Hoff and Le Be1 they must contain an asymmetrical carbon-atom. Of the three possible hexy 1 alcohols satisfying this condition two have been identified by Lieben and by Zeisel and Silva. The alcohol now described must therefore hare the remaining formula $hat ascribed to it above. V. H. V. Thiodiglycol-compounds. By V. MEYER ( B e y . 19 3259-3266).. -Thiodiglycol is obtained by treating a concentra:ed aqueoiis solu- tion of potassium sulphide with glycol chlorhydrin. The product is evaporated on a water-bath and extracted with alcohol. It is a syrup almost without odour.TltiodiglycoZ chloride S(CH2*CH,C1) is formed by gradnally mixing phosphorus chloride with thiodiglycol (kept cool) and ponring the product into water. It is an oil having a slighti sweet ethereal odour. When cooled in ice-water it solidifies to long prisms. It boils a t 217" and is almost insoluble in water. It has very poisonous properties a rabbit exposed to air previously passed over filter-paper saturated with the substance died in three dajfi. When ethylene bromide is heated to boiling for a long time with aqueous potassium sulphide an amorphouq insoluble product is ob- tained differing from the polymerised diethyleno disulphide (formed by adding ethylene bromide gradually to a solution of potassium sul- phide in alcohol). It remains unchanged when boiled for days with phenol.The polymeride which is decomposed by boiling with phenol can also be prepared by adding ethylene bromide to the sodium salt C,H4( SNa) covered with a little alcohol ; if 50 times the weight of alcohol is used tbe whole well cooled and the bromide gradually added diethylene disulphide is obtained. The author is making experimenhs with a view to synthesise the ethyl vinyl ether of thioglycol SEt*C2H4*S*CE€ CHz in order to com- pare it with the product obtained by the reduction of diethylene disulphide ethyl iodide (Mansfeld this vol. p. 122). N. 11;. M. Preparation of Derivatives of Carbohydrates. By E. BAUMANN ( B e y 19 3218-322'2).-Tetr~iberzzoyZ dextrose C6HQ06Bz1 is prepared by mixing a solution of 5 grams of grape-hugar in 15 C.C.of water with 210 C.C. of a 10 per cent. soda solution adding 30 C.C. of benzoic cliloride and shaking until the odour of the chloride disappears. ItORGAAIC CHEMISTRY. 229 is insoluble in water readily soluble in ether alcohol and benzene ; it melts at 60-64". It is only slowly decomposed by boiling. acids o r alkalis. 0.001 or 0.002 gr,tm of grape-sugar dissolved in 100 C.C. of water can be detected by shaking with 2 C.C. of benzoic chloride and the corresponding amount of soda solution ; the benzoyl- derivative separates as a flaky precipitate. Hexnbenzoyl sacchnrose ~ ~ 2 ~ 1 6 ~ l l ~ z 6 is obtained in a manner similar to the above compound. l'efrabenzoyl glucosa mine C6H9NO5BzP is prepared by shaking a solution of 5 grams of glucosamine in 20 C.C. of water with 140 C.C.of 10 per cent. soda solution and 20 C.C. of benzoic chloride. I t is readily soluble in chloroform insoluble in water sparingly soluble in alcohol from which it separates in long needles melting a t 197-198". It is completely decomposed bx boilinq with alkali. Glycerol dibenzoate C3H502Bz,*OH crystallises from light petroleum in long colourless needles melting a t 70" ; it is very readily soluble in alcohol ether and chloroform insoluble in water. N. H. M. Formation and Composition of Humous Substances. By M. CONRAD and M. GUTHZEIT (Ber. 19 2844-2850).-1n their pre- vious papers (Abstr. 1885 745; 1886 138; this vol. p. 25) the authors have shown that when cane-sugar is inverted by dilute acids the lawulose is more quickly and completely decomposed and yields more humous substances than the dextrose.Ulmin is the chief product from laevulose whilst from dextrose ulmic acid entirely soluble in aqueous potash is obtained. If a more concentrated acid is employed the hurnous substances from dextrose are less soluble and concentrated hydrochloric acid yields a product practically in- soluble in cold aqueous potash. The authors draw the following con- clusions from their experiments :- (1.) That when saccharoses and glucoses are decomposed by dilute acids the yield of humous substances stands in no direct relation to that of formic and acetopropionic acids. (2.) Saccharoses by the action of dilute acids first suffer hjdrolysis and the resulting glucoses by the elimination of the elements of water yield on the one hand formic and acetopropionic acids and on the other humous substances.(3.) Saccharoses and gliicoses with the exception of laevulose yield more humous substances by boiling with dilute (7-10 per cent.) hydrochloric acid than with sulphuric acid. (4.) The more concentrated the acid the greater is the yield of humous substances. (5.) With dilute acids laevulose yields more humous substances than dextrose. (6.) The percentage composition of the humous Substances varies between 62-3-66.5 C and 3.7-4.6 H ; those obtained by the action of concentrated acids containing the highest percentage of carbon. The authors have confirmed Sestini's observation that air-dried humous substances when heated above 110" give off a vapour of acid reaction and capable of reducing silver from solutions of its salts.w. P. w. Arabinoae. By H. KILIANI (Ber. 19 3029-3036) .-Arabiaose is prepared by heating cherry gum (1 part) with 8 litres of 2 per cent. sulphuric acid fgr 18 hours in a water-bath neutralising with hot,230 ABSTRACTS OF CHEMICAL PAPERS. saturated aqueous baryta and evaporating the solution (without filtering) to a small bulk; it is then shaken with much 96 per cent. alcohol. The clear solution is decanted moat of the alcohol distilled off and the residue evaporated down ; it is again shaken with alcohol and the solution concentrated by distillation. On cooling crystals separate ; these are washed with alcohol and recrystallised from six or seven times their weight of alcohol (sp. gr. 0.825); the product is then pnre.Arabonic acid (Bauer Abstr. 1885 501) is prepared by shaking a solution of 20 grams of the sugar i n 100 C.C. of water with 40 grams of bromine for an hour; the bromine is then removed by warming and the hydrobromic acid by means of silver oxide. Analytical results show that it is a tetrahydroxyvaleric acid CliH1006 and not an acid of the formula C6H1207 (Bauer loc. cif.). The calcium salt (CaH,06)&a + 5H20 and the barium salt which forms microscopic plates were analysed. Arabinosecarboxy lamide C1HI5o7N separates as a fine white crystal- line powder when a clear solution of arabinose (1 part) in water (1 part) is mixed with 60 to 70 per cent. hydrocyanic acid and kept for eight days in a closed vessel. It dissolves readily in water but is insoluble in strong alcohol and ether ; when heated it becomes yellow at 130° and decomposes completely a t 160° with evolution of gas Boiling water and hot alkali solutions decompose it with evolution of ammonia.The lactoite of arabinosecarboxylic acid C7H,207 is prepared by dissolving the amide in the corresponding amount of hot baryta- water evaporating until the odour of ammonia has disappeared and precipitating the barium exactly with sulphuric acid. The filtrate is made clear by the addition of a few drops of hydrochloric acid and evaporated. It crystallises from water in very lustrous prisms (pro- bably rhombic) melting a t 145-150" ; it is very sparingly soluble in alcohol. It har nearly the same rotatory power a8 the lactone of dextrosecarboxylic acid; [a]= = - 54.8.The calcium and barium salts are amorphous. The mother-liquor from the preparation of arabinosecarboxylamide contained chiefly ammonium arabinosecar boxylate. Decomposition by Heat of the Nitrates of the Paraffinoi'd Amines. By P. v. ROMBURGH ( R e c . Trau. Chern. 5 246-251).- The decomposition of ammonium nitrate may be explained on the supposition that the nitrite is at first formed on which the oxygen liberated acts to form an unstable combination NH,OH,NO*OH which in its turn is decomposed into water and nitrous oxide. I f this were the interpretation of the reaction the nitrates of the paraffino'id amines should yield a nitrossmine as a product of their decomposition thus NNe2H,0HN02 = NMe.?H,OHNO + 0 = NMe2*N0 + H20 + 0 ; the liberated oxygen would partly oxidise either the salt or the nitros- amime formed.Dimethylamine nitrate decomposes at 150" with evolution of nitrogen and carbonic anydride ; and from the residue dimethylnitros- nmine is obtained the yield of which is 50-54 per cent. of that The acid could only be obtained as a syrup. N. H. M.ORGANIC CHEMISTRY. 231 required by the above theory. Similarly also diethylamine nitrate is decomposed when heated a t 1 70° and the reaction becomes violent with rise of temperature ; carbonic anhydride and nitrogen together with an inflammable gas are evolved and from the residue diet hylnitrosamine may be obtained. Experiments on the decomposition of methylamine ethylamine and tetrethylammonium nitrate were not so successful. V. H V. Action of Hydrogen Chloride on Mixtures of Aldehyde with Alcohols and Phenols respectively. By A.CLAUS and E. TRAINER (Ber. 19 3004-3011).-When a mixture of aldehyde and methyl alcohol (1 vol. 2 vols.) i8 treated with hydrogen chloride at a tem- perature below O" dried and treated with sodium isobutoxide the chief product is dimethylwetal ; methylisobutylacetal (from chlor- ether contained in the original product) is also formed; it boils at 124-128". When equal mols. of aldehyde and methyl alcohol are used dimethylacetal methyl-isohutylacetal and di-isobutylacetal are obtained ; the last compound would be formed from a-dichloro-ether in the original product. Ethyl alcohol and aldehyde give a good yield of a-chlor-ether together with diethylacetal and a-dichlor-ether (compare Wurtz and Frapolli Anwalen.108 226). Isoamyl alcohol and aldehyde (equal mols.) yielded a-chZorethy I isoamyl ether ; when 2 mols. of the alcohol are used di-isoamylacetal C,H402( C,H,,) alone is formed. It boils a t 209-211" jnncorr.). Isobutyl aloohol (1 mol.) gave a better yield of monochlorether than amyl alcohol and in the reaction with 2 mols. of alcohol a small amount of a-chlorethylisobutylacetal (boiling at 155-160") could be isolated. Bthy Zidene diphenyl CHMe( C6H4.0H) is obtained by passing hydrogen chloride through a mixture of aldehyde (1 mol.) with phenol (2 mols.). It is readily soluble in alcohol ether chloro- form &c. insoluble in water benzene and light petroleum ; it could not be obtained in the crystalline state. It softens a t loo" and becomes viscous at 125".Aqueous alkali dissolves it readily Ethylidene-di-a-na~hthQZ is formed in a similar manner and is completely analogous in its properties to the diphenyl-derivative. When P-naphthol and aldehyde are treated with hydrogen chloride a crystalline compound melting at 162-163" is formed having the formula C2H,0,(CloH,)2. It has none of the properties of a phenol but corresponds with the acetals. The authors consider that this different lnehaviour of a- and /%naphthol (the one behaving like a phenol and the other like a fatty alcohol) is fresh evidence in favour of his unsymmetrical naphthalene formula. N. H. M. Acid Propionates and Butyrates. By W. G. MIXTER (Amer. Chem. J. 8 34%-346).-The following salts are described Acid barium propionute ( C,H502)Ba,C3H602 + 3H20 forms tabular crystals that very slowly lose water and acid in dry air.Acid strontium propionate ( C3H502)2Sr,C3J3602 + 34$&0 forms long thin232 ABSTRACTS OF CHEMICAL PAPERS. crystals that lose acid on exposure to the air. Acid calciunt pro- pionate 2( C3H502)LCa,C3H602 + 5H20 forms long needles that have an acid reaction and decompose on heating. Acid bar?;lLm isobzhpate (C,H,02)2Ba,C4H was obtained by heating a solution of the normal salt with the excess of the acid a t 100" until constant. H. B. Preparation of pIodopropionic Acid. By V. MEYER (Ber. 19 3294-3295).-The author finds that /?-iodopropionic acid can be readily prepared from the glyceric acid obtained by tbe oxidation of glycerol with nitric acid since the accompanying products neither form crystalline compounds with phosphorus iodide nor interfere with the crystallisation of the iodo-acid.The syrup obtained by the oxidation of glycerol and subsequent removal of nitric acid is diluted with water to a sp. gr. of 1.26 and 30 C.C. of the solution is theii poured into a flask containing phosphorlis iodide prepared from 50 grams of iodiue and 6.5 grams of yellow phosphorus. A vigorous action takes place either in the cold or on gently warming and the contents of the flask on cooling solidify owing to the separation of 6-iodopropionic acid in large colourless lamina which after one crystallisation fro= water are quite pure. w. P. w. Methylisopropylacetic Acid. By P. v. ROMRURGH ( B e e . T ~ a v . Chew. 5,228-239).-Kobig concluded that the caproic acid obtained b y the oxidation of the hexyl alcohol from the essence of Roman chamomile was identical with that obtained by Narkownikoff from the nitrile derived fi-om methyl isopropyl carbinol.This view is not con- firmed in the present paper in which it is shown that mekhylisopropyl- acetic acid is not identical with the caproic acid obtained from the essence of chamomile. Two methods mere used for the synthetical formation of methylisopropylacetic acid CHMePr*WOOH namely the conversion of ethyl sodiomaloiiate into the isopropyl-derivative and this into the ethereal salt of methylisopropylmalonic acid from which the acid itself was obtained by hydrolysis ; this when heated readily decomposed into carbonic anhydride and the corresponding acetic acid; (ii) the conversion of ethyl acetoacetate into ethylic me thylisopropylacetoacetate and the decomposition of this by alkalis into methylisopropyl acetone and methylisopropylacetic acid.Of these methods the former is preferable. The acid boils a t 189-191"; sp. gr. = 0.928 at 15"; its silver salt crystallises in delicate needles and its amide in micaceous scales. MethyZisopropy Zacetone CHMePrWOMe boila at 135-l$O" has a strong odour resembling menthol; sp. gr. = 0,815 af 20"; it does not seem to react with sodium hydrogen sulphite or with pheiiyl hydrazine. Methy Zisopro~yZmrtZon~c acid CHMePr(COOH) is crystalline melts though not very definitely at 124"; its silver and calcium salts are sparingly soluble ; its ethyl salt is a colourless liquid boiling at 221"; sp.gr. = 0.990 a t 15" ; it has an agreeable odour. As a subsidiary product isopropylmalonic acid was obtained a substance previously described by Conrad and Bischoff. V. H. V.ORGANIC CHEMISTRY. 233 Derivatives of Erncic and Brassic Acids. By C. L. REIMER and W. WILL (Ber. 19 3320-33:!7).-Erucic acid is best obtained by saponifying rape oil with alcoholic potash distilling off the alcohol and dissolving the acid liberated on addition of sulphuric acid in three times its volume of 95 per cent. alcohol; on cooling to 0" crystals of erucic acid separate in an alniost pure condition. The melting point of the acid was found to be 34". Ethyt erucute Cz2H4,0sEt is a colourless odourless oil boiling above 360" without decomposition ; its vapour-density however could not be determined.The anhydride CJls203 is prepared by heating erucic acid and phosphorus trichloride in molecular proportions. It is an oil cry stallis- ing in a freezing mixture to a mass of scales and is very readily soluble in ether benzene and chloroform sparingly soluble in alcohol. The amide Cz2H4,0(NH,) crystallises in colourless needles melts at 84" and is readily soluble in ether and benzene sparingly soluble in alcohol insoluble in water. The anilide is c~ystalline melts at 55". and is readily soluble in ether and benzene sparingly soluble in alcohol. Dierucin C3HaOH( C22€&102)2.-When rape oil is allowed to stand for a long time a yellowish tallow-like deposit is frequently found in the casks ; this by repeated solution in ether and subsequent addition of alcohol can be obtaitied in silky needles.Dierncin melts at 47" and is readily soluble in ether and light petroleum insoluble in cold but soluble in hot alcohol. A trierucin could not be separated from rape oil. Brassic acid is best prepared by warming erucic acid with dilute nitric acid to the melting point and then adding sodium nitrite ; the product is quite pure after two crystallisations from alcohol. The ethyl salt is obtained directly from the acid or by the action of nitrous acid on ethyl erucate; it crystallises in lamina showing a vitreous lustre melts at 29-30" and boils above 360" without decomposition ; the vapour-density could not however be determined. The u?thydir'de ClaH,03 formed by heating the acid with phosphorus trichloride orystallises in lustrous tables melts at 28-29" and is insoluble in water and alcohol readily soluble in ether and benzene.The amide melts at go" and resembles in its properties the amide of erucic acid; both atnides can be obtained by heating the corresponding ethyl salts t o 230' with ammonia. Tribrassidiit is formed when rape oil (100 parts) is treated with nitric acid ofsp. gr. = 1.2 (5 parts) and sodium nitrite (1 part) ; after some time the resulting crystalline mass is washed dissolved in ether and from the solution cooled to 0" a lustreless crystalline powder is obtained. Tribrassidin melts at 47" but when heated above its melting point and allowed to cool the melting point is subsequently found to be 36"; it is insoluble in alcohol readily soluble in ether and chloroform.Dibrassidin C3H50H( CnH4102)2 is formed when dierucin is treated with nitrous acid ; it forms feebly lustrous crystals melts at 65" and is less soluble in ether than tribrassidin. By distilling the calcium salts of erucic and brassic acids two ketones are obtained which seem to be different; they are both very sparingly soluble in alcohol. w. P. w.234 ABSTRACTS OF CHEMICAL PAPERS. Dry Distillation of Calcium Tetramethylenecarboxylate with Lime. By H. G. COLNAN and W. H. PERKIN Jun. (Uer. 19 3110-3115).-The products of this reaction are much ethylene (together with hydrogen and small quantities of carbonic anhy- dride and methane) ditetramethylene ketone and an oil boiling at 136-137" and uniting with hydrogen sodium sulphite phenyl- hydrazine and hydroxylamine ; this is either tetramethylenealde- hyde or acetyltetramethylene but there is not suficient evidence to say which.Ditstramethylene ketone CO(CoH,)2 is a colonrless oil of pepper- mint-like odour ; i t boils a t 204-205" gives a colourless crystalline compound with hydrogen sodium sulphite and is acted on by bromine with evolution of hydrogen bromide. The phenylhydrazine compound is obtained as a yellow oily precipitate. The oxime C19H15N0 forms a colourless syrup. A. J. G. Oxalimide. By H. OST and A. MENTE (Ber. 19 3228-3230).- Oxamic acid is best prepared by heating hydrogen ammonium oxalate at 140° stirring all the time extracting with aqueous ammonia and converting into the sparingly soluble barium salt. This is eonverted into the ammonium salt and precipitated with hydrochloric acid.The yield is 16 per cent. co OaaZirnide <co>XH is obtained by treating 20 grams of oxamic acid with 50 grams of phosphorus pentachloride and 20 grams of phosphorus oxychloride and heating a t 80-90". The product is put into ice-water warmed at 40° filtered and extracted with water a t 60". It is purified by dissolving in very dilute warm aqueous ammonia precipitating with hydrochloric acid and recrystallising from water. It forms very lustrous prisms which seem to be monoclinic. It is sparingly soluble in water more soluble in warm aqueous ammonia. Boiling water decomposes it into oxamide and oxalic acid. Concen- trated aqueous ammonia converts it into oxamide. When a cold satu- rated solution of oxalimide is treated with mercurous chloride a crystalline m ercnry salt C20,N.HgCI separates. Oxalimide is also formed by the action of nitrous acid on comenamic acid (dihydroxypyridinecarboxylic acid).This reaction together with the results of experiments made by v. Pechman and others is in favour of the Tiew that meconic and cnmalinic acids are derivatives of pyridone C5H,0-NH. Ethyl Oxalacetate. By W. WISLICENUS (Ber. 19 3225-3228). -Ethyl oxnlacetnte COOEt.CO*CH,*COOEt is prepared by dissolving 20 grams of ethyl oxalate in 100 grams of absolute ether adding 3 grams of sodium wire and then gradually adding 12 grams o€ pure ethyl acetate. After 12 hours the product is solid and is then washed with absolute ether and dried over sulphuric acid. The sodium-derivative CaHl105Na ci~ystallises from absolute alcohol in microscopic matted needles ; it is decomposed by dilute sulphuric acid.The ethyl salt is a rather viscous oil almost without colour and odour ; it decomposes when heated. The dilute alcoholic solution N. H. DiI.ORGAKIC CHEMISTRY. 233 gives with ferric rhloride an intense dark red coloration. When boiled with dilute alkali or baryta-water it yields oxslic and acetic acids. Warm 10 per cent. sulphuric acid decomposes it with evolu- tion of carbonic anhydride and formation of pyruvic acid. When saponified by Ceresole's method for the preparation of acetoacetic acid monethyl oxalacetute C6H,0 is obtained. The latter crystallises from benzene in stellate groups of needles melting a t about 90". It is readily soluble in alcohol ether and water and has a strongly acid reaction.Phenylhydrazine ethyl oxalacetatp crystallises in plateu ; when boiled with water it yields an acid C,,H,N,O (analogous to that obtained by Knorr from phenylhydrazine ethyl acetoacetate (Abstr. 1884 1377). This dissolves readily in alcohol sparingly in water. and decomposes at about 250" without melting. N. H. M. Glycuronic Acid. By H. THIERFELDER (Ber. 19 3148).- Bromine converts glycuronic acid into saccharic acid thus showing the presence in the former acid of an aldehydic group and also its close relation to dextrose. L. T. T. Fermentation of Citric Acid. By P. WATTS (J. XOC. Chen?. Ind. 5 215-218).-Warington (this Journal 1875 936) has made an attempt to ascertain the amount and nature of the volatile acids in concentrated Sicilian lemon-juice with a view to determine the acids other than citric which OCCUI' in concentrated juice.When perfectly fresh juice is distilled the distillate is neutral and consists only of water with a small amount of essential oil derived from the peel. It is thus clear that volatile acids are not normal constituents of the juice. When lemon-juice is allowed to remain for some days in aii open vessel a film of mould gradually forms on the surface consisting of a large number of minute cells of saccharomyws mycoderma. If this juice is now distilled the distillate is found to be acid. From an examination of the distillate purified by redistillation the author infms the presence of acetic acid traces of formic acid and possibly some propionic acid and indirectly the existence of el hyl alcohol with possibly some propyl alcohol and minute quantities of methyl alcohol in the original juice after fermentation.It is also shown by experiment that under the influence of snccliaromyces mycoderma citrio acid is split up directly into carbonic anhydride and water oxygen being absorbed. It was found that the growth of this fungus ceased shortly after air was excluded. Decomposition of Amides by Water and Dilute Acids. By BERTHELOT and ANDRE (Compt. reid. 103 1051-1057).-Urea is decomposed by hydrochloric acid at the ordinary temperature. 100 C.C. of solution containing 1.0293 gram of urea was mixed with 10 C.C. of hydrochloric acid containing 3.78 grams of HC1 allowed to remain 24 hours diluted with water neutralised with magnesia and the ammonia estimated by Schloesing's method.After boiling for one and a half hours about one-ninth of the tota! nitrogen in the urea was obtained in the form of ammonia (0.0523 gram). A similar D. B.236 ABSTRACTS OF CHEMICAL PAPERS. quantiky of urea solution was boiled for an hour and a half with 2 grams of magnesia and 0.0353 gram of ammonia was obtained the amount evolved being practically the same in each half hour. The difference between the two quantities represents the ammonia formed by the action of hydrochloric acid in the cold and is equivalent to the conversion of about 4 per cent. of the total nitrogen into ammonia in 24 hours. The action of the acid increases with the concentration arid also with the temperature.It is well known that urea is partially decomposed when boiled with iva ter. At the ordiiiary temperature however there is no appreciable clecomposi tion even after five days. Dilute &odium hydroxide solution decomposes urea slowly in the cold but the action is much less marked than that of hydrochloric acid. Asparagine is also decomposed by hydrochloric acid in the cold to R somewhat less extent than urea and the decomposition increases with the concentration of the acid. It is decomposed by magnesia as Boussinpnult observed and also by boiling water although only to a very slight extent. The adion of soda is much more marked than with urea. 0.5 gram of asparagine mixed with 50 C.C. of water and G gmms of sodium hydroxide loses one-third of the total nitrogen in 24 hours and about half of the total nitrogen in five days or almost the whole of the nitrogen which is evolved as ammonia in the ordinary reaction.Oxamide when triturated with hydrochloric acid of 10 per cent. loses 0.7 per cent. of the total nitrogen in the foi*m of ammonia in two hours. When boiled with magnesia 6.3 per cent. of the total nitrogen is evolved as ammonia in the first half hour and 3.4 per cent. in the second half hour. The first loss is due t,o the decomposition of the oxamide arid the second to decomposition of magnesium oxamatre. I n all these cases the action of acids varies with the nature of t h s amicle is proportional to the time of action and increases with the concentration of the acid and with the temperature. The action of acids or alkalis on the amides derived from the alcoholic amineR and from the hydroxg-acids will be different since these amines are reconverted into ammonia with great difficulty.Hydrochloric acid tends to regenerate the amines from theiia deriva- tives in consequence of the alkalinity of the amines. I n the case of substances of complex function like glycollamine and the leucines both acids and alkalis will tend to produce the same azotised and oxygenised derivative because each can combine with it. Aspartic acid is not sensibly affected either by boiling water or by magnesia. Uric acid yields no ammonia when boiled with magnesia for an hour but if triturated for two hours with hydrocliloric acid of 10 per cent. it loses about 1 per cent. of the nitrogen in the form of ammonia.C. H. B. Derivatives of Acetothienone. By H. B RUNSWIG (Ber. 19 2890-2896).-B1.omacetothie?irone C4SHJ-CO*CH2Br prepared by the bromination of acetotbi6none dissolved in carbon bisulyhide is a pale yellow oil the vaFour of which affects the mucous membrane. It cannot be distilled uiider ordinaery pressures without decomposition ;ORQ ANIC CHEMISTRY. 237 n t a low temperature it forms small yellow crystals. The nnilide C18H,*CO*CH,*NHPh crystallises in leaflets melting at 80" ; its acetyl derivative C,SH,*CO*CH,*KPhAc forms hard brown crystals melting at 141*5" and its nitroso-derivative rhombic crystals meltinq at 81" soluble in ether and alcohol sparingly soluble in water. The thio- cyanate CaH3S*CO*CH2*SCN ci~ystallises in colourless leaflets melting a t 88" ; sparingly soluble in water and light petroleum readily soluble in chloroform.Dibroniacetothierione C4SHJCO*CHBrz is a heavy colourless oil solidifying in a freezing mixture and completely decomposed when heated under ordinary pressure. Ciiznamyl thienyl ketone C,SH,*CO*CH CHPh pypared by satu- rating with hydrogen cliloride a mixture of acetothienone and benz- aldehyde in equimolecular proportions crystallises in grouped needles or prisms very soluble in ether and chloroform sparingly soluble in water. The di bromo-compound crystdlises in colourless leaflets melting a t l57" and is soluble in alcohol. Isomerism of the Thiophenic Acids. Derivatives of p- Thio- phenic Acid. By A. DAMSKY (Ber. 19 3282-3286 ; compare this vol. p. 129).-The ordinary method of preparing P-thiophenic acid by the oxidation of P-thiotolen affording only a poor yield the a ithcr prepared p-ethylthiophen and oxidised it with potassium p arman- ganate ; no advantage however was derived thereby since the amount of P-acid obtained was not greater than that formed by the oxidation of 3-thiotolen.The besh yield 8 per cent. of the theoretical quantity was obtained by oxidising @-thiotolen in quantities of 1 gram with a mixture of 6.7 grams of sodium hydroxide and 3-3 grams of potassium permanganate in 333 grams of water. When dissolved in water a t 15" or 18" 100 C.C. of the soiution contain 0.44 gram of /-l-th iophenic acid ; the solubility of the barium salt is 11.54 a t 17" and that of the calcium salt is 7.92 a t 14.5".The amide crystallises in slender colourless needles melts a t 177*5-178" and is very sparingly soluhle in ether ; the phenylcarhamide crystallises in concentrically-grouped needles melts at 206" and is sparingly soluble in alcohol. p-E'th ylthiophen C4SH3Et. -When ethyl ethenyltricarboxylate (Abstr. 1883 45) is treated with the calculated quantities of sodium ethoxide and ethyl bromide a vigorous action takes place accom- panied by considerable development of heat and ethyl butenyltricar- boxylate is obtained as an oil. This is saponified and from the acid by heating it a t 120-170" untd evolution of carbonic anhydride ceases p-ethylsuccinic acid is obtained which by distillation with phosphorus trisulphide yields P-ethylthiophen. This is an oil re- V. H. V.sembling a-ethylthiophen in properties. w. p. w. Reduction of aZ-Thiophendicarboxylic Acid. By Y. ERNST (Bey. 19 3;!74-33;!78).-'etra~~ydrothio~hendicarbo~~Zic acid is prepared by adding 15 parts of sodium amalgam (4 per cent. Na) to 1 part of a-a-thiopbendicarboxylic acid and 0.5 part of sodium hydroxide dissolved in water and heating at 100" for two hours; the CISH,(COOH)z [ = 2 51 VOL. LlI. r2 38 ABSTRACTS OF OBEBIICAL PAPERS. product is converted into the silver salt and from this by treatment with hydrogen sulphide the hydro-acid is obtained. It crystallises in yellowish-white probably monoclinic tables melts a t 162" (corr.) is readily soluble in water less so in ether and shows all the properties of a hydro-acid. Thus it reduces an ammoniacal silver solution and when heated with sulphuric acid decomposes into thiophenic acid and carbonic oxide.The barium salt C4SH6(C00)2Ba crystallises in small lustrous scales ; and the silver salt CaSH6(COOAg) is a white powder. When an alcoholic solution of the hydro-acid is saturated with hydrogen chloride meth2/ltetrahydrothio~hendicarboxylate C,SH6( CO OMe)2 is obtlained as an oil which cannot be distilled and does not solidify. a-Thiophencarboxylic acid on reduction yieldR an acid which crys- tallises in colourless needles melts at about 48O is readily soluble in water and reduces ammoniacal silver solution. w. P. w. Synthetical Investigations in the Thiophen Series. By F. ERKST (Bey. 19 32'78-3282).-The author has endeavoured to effect the synthesis of an anthracene of the thiophen series but with- out success.The following compounds prepared in the course of the work are described :- OrthotolugZ thienyl ketone C6H4Me*CO*C4SH3 obtained by the action of orthotoluic chloride on thiophen in the presence of aluminium chloride is a colourless oil ; when boiled for some time it loses water and is completely resinified. Phenyl thiotoZyZ ketone C6H,*CO*C4SH,Me is formed by treating coal-tar thiotolen with lnenzoic chloride in the presence of aluminium chloride. The ketone is a syrup and on long boiling loses water and is resinified. The acetoxime was prepared but is not described. When thii3nylglyoxylic acid is reduced with sodium amalgam in the cold thieny7gZycoZZic acid C4SH3*CH( OH)*CO@H is obtained. 1 t crystallises in white needles melts at 115" is readily soluble in water alcohol ether and benzene and decomposes on distillation.Oxida- tion with manganese dioxide converts it into thiophenaldehyd e ; the yield however is small. The barium and caZcium salts are readily soluble in water ; the silver salt is obtained as a white precipitate. Thienylncetic acid CaSH,*CH,*COOH is obtained by boiling tbi6nyl- glycollic acid with hydriodic acid and amorphous phosphorus. It forms colourless crystals melts a t 7 6 O and is soiuble in hot water alcohol and ether. The barium salt forms white crystals readily soluble in water ; the sizzler salt is obtained as a white precipitate. The acetoxime is a non-volatile oil. w. P. w. Synthesis of &-Phenylthiophen. By W. KUES and C. PAAL ( n e r . 19 3141-3144) .-Following out their previous work (Abstr.1886 5:<6) the authors find that if p-benzopropionic or p- benzoiso- succinic acid is substituted for levulinic acid similar reactions occur. I n these cases however the intermediate hydroxy-product appears to be less stable than thiotolen and traces only were obtained. The main product was a-phenylthiophen C,SH,Ph [Ph = 11. With theORGANIC CHEUIbTRY. 239 isosuccinic acid evolution of carbonic anhydride and formation of the ketonic acid takes place before the reaction occurs. a-Phenylthiophen crystallises in plates melting a t 40-41" and is soluble in carbon bisul- phide and the usual organic solvents insoluble in water. It is volatile i n steam and has the characteristic odour of diphenyl. It dissolves in cold concentrated sulphuric acid and is reprecipitated unchanged on the addition of water.It shows the indophenin reaction but does not give cny characteristic coloration with Laubenheimer's reaction. When added to cold bromine it forms parabromophenyltribrorno- thiophen which crystallises in white needles melting a t 145 -146" sparingly soluble in alcohol and acetic acid easily in carbon bisulphide and benzene. It is a very stable compound may be heated with dilute nitric acid at 180" without change and is only oxidised by continued boiling with chromic acid in acetic solution and then forms parabromobenzoic acid. Attempts made to form a phenyltri- bromothiophen were unsuccessful. A mixture of a compound crys- tnllising in white needles melting ak 55-56' (probably a phenyl- dibromothiophen) with a very soluble bromo-derivative melting at 33-36" was produced.Pentathiophen-group. By K. KREKELER (Ber. 19 3266-3274). -The lactone of a-methylhydroxyglutaric acid (Block and Tollens Abstr. 1886 533) is prepared by slowly adding 100 grams of levulic acid to 100 grams of potassium cyanide finely rubbed with 10 grams of water the whole being well cooled. It is then kept for 24 hours in a loosely-closed vessel treated with the necessary amount of fuming hydrochloric acid and left for three or four days. It is extracted with ether saponified by heating for one hour on a water- bath with fuming hydrochloric acid and again extracted with ether. It is purified by means of the barium salt. The hydroxy-acid is con- verted into niethylglutaric acid by boiling with twice its volume of hydriodic acid and amorphous phosphorus.p-~~ethylpentathiophen CHI<Ck-CH>S is obtained by distilling 5 grams of sodium methylglutarate (dried a t 160') with 10 grams of phosphorus trisulphide at 180-250". From 550 gram? of sodium salt 20 grams of crude oil were obtained; this is boiled for some hours with strong potash solution distilled the oily distillate treated with a little dilute permanganate solution and then re-distilled over sodium. It is a colourless very refractive oil boiling a t 134" and has the odour of pure xylene. Sp. gr. = 0.9938 a t 19" (water at 19" = 1). When the solution of the substance in glacial acetic acid is treated with a solution of isatin in the same solvent and then with sulphuric acid (keeping it cold) an intense dark-green coloration is produced. When poured into water a green flaky precipitate is formed soluble in ether.Laubenheimer's reaction jields a dark violet coloration in sulphuric acid. l-l-iMethylaceto~entatliietrone C,SH,MeAc is prepared by treating a solution of 1 part of P-methylpentathihone in 10 parts of light petroleum with the calculated amount of acetic chloride and adding aluminium chloride until the evolution of hydrogen chloride ceases. L. T. T. CMe'CH r 2240 ABSTRACTS OF CHEMICAL PAPERS. It is purified by steam distillation. It is a clear heavy oil having an odour resembling that of acetophenone; it boils a t 233-235" (uncorr.). The ketoaime C6SH4Me*CMe N*OH was prepared by Peter's method (Abstr. 1885 141).It crystallises from ether in long branched needles melting at 68" ; it dissolves readily in alcohol and ether. When /I-methylpentathiophen is treated with 0.3 per cent. alkaline potassium permanganate solution the oxidation takes place very quickly with formation of acetic and oxalic acids. When air saturated with methy lpentathiophen is passed through fuming nitric acid a nitro-compound is formed. The alcoholic solu- tion of the latter treated with a drop of potash solution acquires an intense violet-red colour which disappears in a few minutes. N. H. M. Action of Light on Nitrobenzene in Alcoholic Solution. By G. CIAM~CIAN and P. SILBER (Ber. 19 2899-2900).-1n contiaua- tion of experiments on the transformation of quinone to qiiinol on exposing its alcoholic solution to sunlight (Abstr.1886 695j the authors have studied the chemical change induced in nitrobenzene under similar conditions. Among the products obtained were alde- hyde aniline and a quinoline base probably quinaldine. V. H. V. Orthoethyltoluene Oxidation of Orthodialkyl-derivatives of Benzene with Potassium Permanganate. By A. CLAUS and E. PIESZCEK (Ber. 19 3083-3O92) .-The common statement that ortho-xylene on oxidation with potassium permanganate yields first orthotoluic acid and then phthalic acid is incorrect nothing but phthalic acid being formed; not even a trace of orthot)oluic acid is detectable. By the oxidation of orthoethyltoluene with potassium permanganate ortho toluic phthalic and terephthalic acids were ob- tained according to the temperature and concentration of the solutions.At loo" in alkaline solution total combustion took place. The results obtained with cymene completely corresponded with those obtained with orthoethyltoluene. BromorthoRthllZtoZuene is a colourless oil boiling a t 220-221" (uncorr.) ; when heated with nitric acid sp. gr. 1.2 in sealed tubes at 190-200" it is oxidised to a bvornorthotoluic a,cid [Me COOH Br = 1 2 41. This forms snow-like flocks composed of slender needles melts a t 118" (uncorr.) is sparingly soluble in cold water readily soluble in alcohol ether and hot water and yields readily soluble crystalline salks with the alkali metals and with barium and calcium. It is not identical with the acid described by Jacobsen (Abstr. 1885 143) to which he assigned the same constitution ; the authors consider it more probable that his acid has the constitution [l 3 41.By the action of nitric acid on orthoethyltoluene in the cold a wtono- and dinitro-derivatiye are formed ; the latter is a pale-yellow oil and does not solidify at 0". Orthoethyltoluene-~-,~ul~~onic acid C6H3MeEt*S03H [l 2 41 is obtained together with the a-acid which has not yet heen investigated by the action of pyrosulphuric acid on orthoethyltoluene; it forms a deliquescent colourless crystalhe mass. The potassium sodium,ORGANIC CHEMISTRY. 241 barium calcium. lead comer and silrer salts are described. The chloride is a yellow oil; the' lam& forms a yellow buttery mass. A. J. G. Oxidation of the Homologues of Phenol. By B. HEYMANN and W.KONIGS (Ber. 19 3304-3315) .-Continuing their experiments (Abstr. 1886 542) the authors find that the oxidation of the homo- logues of phenol can readily be effected if the phenols are converted into the corresponding dipotassium phosphates ; these double salts axe pre- pared by heating the phenols (1 mol.) with phosphoric oxychloride (1 mol.) carefully adding water to the cooled product extracting the re- sulting chlorinated phosphorus compounds with ether and decompos- ing them with potassium carbonate. The double phosphates are then oxidised with alkaline potassium permanganate acidified with hydro - chloric acid and boiled for a short time. The double phosphates of the pheriols are found to be more stable than the corresponding double sulphates and a better yield is obtained when the former are oxidised.By this method orthocresol is readily oxidised t o salicylic acid. Thymol treated with potassium pyrosulphate yieldsadouble sulphate C6H3MePra*SOaK [Me SOaK Pr = 1 3 41 crystallising in fine silky fibres which decomposes readily on keeping or when heated on a water-bath although it is stable in alkaline solution ; it is sparingly soluble in 50 per cent. alcohol readily soluble in absolute alcohol and in water. When the double sulphate or double phosphate is oxidised tthymohydroxycnmic acid COOH*C,H,Pr@*OH [COOH OH Pr = 1 3 43 (Abstr. 1879 LSS) is obtained. Carvacry 1 potassium subhate C,H&lePr.SO& crystallises in silvery scales decomposes very readily on keeping or on gently heating is stable in alkaline solution and is soluble in water and absolute alcohol.Carvacryl dipotnssium phosphate CBH3MePr*P0,K2 + 5H20 crystallises in large silvery lamin= decomposing a t loo" readily soluble in water and in absolute alcohol. Some tricarvacryl phosphate was formed in the preparation of the double salt. When oxidised with permanganate both the double sulphate and double phosphate yield paruhydrozyisoproivy lsalicylic acid COOH*C6H3(0H)*CMe,.0H [COOH OH CMe,*OH = 1 2 43 which crystallises from water in large flat needles and in slender concentrically grouped needles from chloroform. The acid melts at 130-1 35' ; a more exact determination was not possible owing to the tendency to dehydrate aEd form parapropenylsalicylic acid. Hydroxy- isoprop~lsadicylic acid is sparingly soluble in cold water readily soluble in chloroform alcohol and ether insoluble in carbon bisul- phide and gives with ferric chloride an intense reddish-violet coloration.'l'he silver salt Cl,,Hl,OaAg crys tallises in colourless needles ; the copper salt (C,oHl,Oa),Cu + H,O crystallises in green prisms which do not lose their colour on drying; it is sparingly soluble in water. When heated with concentratcd hydriodic acid and amorphous phosphorus the acid is reduced to isohydroxycumic acid OH.C6H3Prfl*COOH (Abstr. 1878 731). COOH*C6H3(OH)*CMe CH [COOH OH (CMe CH,) = 1 2 41 Yurapropeny lsalicy lic acid,242 ABSTRACTS OF CEEMICAL PAPERS,. is readily obtained from hydroxyisopropylsalicylic acid by gently warming it on a water-bath with dilute hydrochloric acid.It crystallises in slender needles melts a t 145-146" is sparingly soluble in cold water readily soluble in alcohol ether and boiling carbon bisulphide and gives an intense reddish-violet coloration with ferric chloride. It is volatile with steam and when heated at 1.50" sublimes with slight decomposition. The silver salt CI0H9O3Ag forms a crystalline powder very sparingly soluble in water ; the copper salt (C,0H903)2Cu + 2H20 forms small green crystals insoluble in water the anhydrous salt is not hygroscopic. By reduction with sodium amalgam in the cold an acid agreeing in its properties with Jacobsen's isohydroxycumic acid (Zoc. cit.) was obtained ; the melting point however was 96-97' instead of 93-94'. When a boiling aqueous solution of hydroxyisopropylsalicylic acid is treated with an equal volume of concentrated hydrochloric acid R polymeride propemylsnlicylic acid (C,OH,,O,) is obtained in small white crystals which melt at 230" with evolution of carbonic anhydride.It is insoluble in water and carbon bisulphide soluble in hot acetic acid alcohol and ether and the alcoholic solution is coloured an intense reddish-violet with ferric chloride. The acid is not volatile with steam nor is it reduced by sodium amalgam. Attempts to oxidise the ethyl isopropyl isobutyl and amyl Action of Sodium Methoxide on Bromobenxene. By F. BLAU (Monatsh. Chem. 7 621-636).-When bromobenzene is heated with sodium methoxide in sealed tubes aniso'il is formed together with phenol ; the sodium methoxide thus acting like a niixture of the alcohol and alkali a considerable proportion of the bromobenzene is unaltered.The reactions with di- and symmetrical tri-bromobenzenes are precisely analogous; thus from the former are obtained brom- aniso'il dimethylquinol and bromophenol ; from the latter a dibromo- phenol and dibromaniso'il. The dibromophenol forms white crjstnls melting at S6*5" readily soluble in alcohol and ether sparingly in water and petroleum ; on fusion with alkali it yields phloroglucol ; it is therefore a symmetrical compound. Bisulphides with Mixed Organic Radicles. By R. OTTO and A. ROSSING (Ber. 19 3132-3138).-Hitherto no organic bisulphides with mixed rsdicles have been obtained. The authors 6nd that such compounds are formed when a mixture of two mercaptans are treated w-ith bromine and that the reactions take place the more readily the more closely allied are the radicles of the reacting mercaptans.The reaction is R-SH + R'*SH + Br = 2HBr + R*S,*R'. YhenyZ pai-atoZyl bisadphide C7H7*S2*Ph is obtained by dissolving molecular proportions of pheriyl and paratolyl hydrosulphides in ten times their volume of ether arid slowly adding a molecular proportion of bromine. It is insoluble in water miscible in all proportions with alcohol and ether has an odour somewhat resembling that of tolyl hy drosulphide is heavier than water and scarcely volatile in steam. When heated with alcohol and zinc-dust it is decomposed into the corresponding zinc mercaptides. potassium sulphates led to no result. w. P. w. V. H. V. This substance is a thick pale-yellow oil.ORGANIC CHEMISTRY.243 Ethy'l amyZ biszcZp7~ide prepared in a similar way is a thin colourless liquid of very strong and unpleasant garlic-like odour. It is insoluble in water soluble in ether and alcohol lighter than water and volatile in steam. Ethyl plhenyl bisulphide.-The authors attempted to obtain this compound by the above method but it was only formed in very small quantity the principal products being diethyl and diphenyl bisulphides. But by modifying Schiller and Otto's method for the preparation of organic bisulphides (this Journal 1877 i 306) the authors were successful. 10 grams of phenylsulphinic acid (1 mol.) and 15 grams of ethyl mercaptan ( 3 mols.) in alcoholic solution were heated in sealed tubes at 100". The action took place according to the equation PhS02H + 3EtSH = PhSz*Et + EtzSz + 2Hz0.Ethyl phenyl bisulphide is a thick oily strongly refractive liquid heavier than water and only very slightly volatile in steam. It is insoluble in water soluble in ether and alcohol. Phenyl paratolyl bisulphide was also prepared by the action of phenyl hydrosulphide on paratolyl- eulphinic acid. When the ethyl salts of the thiosulphonic acids are heated with mercaptans reactions similar to the above occur ; these are not how- ever of so simple a kind but take place simultaneously according to the two equations :- I R*SOZ*SR + 4R*SH = RzSz + 2R'zSt + 2HZO. 11. R*S02*SR + 4R''SH = 2R.Sz.R' + R z S z . Phenyl disulphoxide /Ph.S,O,*Ph) and ethyl mercaptan thus yield Action of Silicon Fluoride on Organic Bases. By C.L. JACKSON and A. M. COMEY (Ber. 19 3194-3195).-The authors intend studying these reactions. When silicon fluoride is passed over aniline a compound of the formula 3NH2Ph,SSiF4 is formed. This compound was obtained by Laurent and Delbos (Ann. Chirn. Phys. 22 l O l ) but its composition was not established. It forms white microscopic needles and sublimes without fusion. It is insoluble in ether benzene and light petroleum. With water or alcohol it forms aniline hydrosilicofluoride. Ortho- and para-toluidine diphenylamine and dibenzylamine form similar compounds. L. T. T. Aniline and Diphenylamine from Phenol. By V. MERZ and P. MGLLER (Ber. 19,2901-2917).-1n this paper the various methods used and the conditions required for the conversion of phenol into aniline and diphenylamine are fully described.Thus when phenol and ammonium zinc chloride or simply ammonium chloride are heated at 330" 70 to 80 per cent. of the phenol is converted into the amine the yield of which is dependent on an excess of the ammonium salt the temperature and the time of heating. The same change may also be effected with zinc oxide or magnesia and ammonium chloride the presence of an excess of the latter preventing the formation of diphenylamine. Experiments in an autoclave were not so satisfactory ; ethyl bisnlphide phenyl bisulphide and ethyl phenyl bisulphide. L. T. T.244 ABSTRACTS OF OHEMICAL PAPERS. the pressure when the mixture was heated at 320° was 20 to 25 atmospheres. V. H. V. Action of Alcoholic Hydrogen Chloride on Nitrosamines.By 0. FISCHER and E. HEPP (Ber. 19 2991-2395).-The authors find that certain nitrosamines undergo intramolecular change by the action o€ alcoholic hydrogen chloride thus ; for example methylphenyl- nitrosaniine is converted into 1 4 nitrosomethylaniline. 1 4 N~trosniethyZatziline is prepared by adding alcoholic hydro- gen chloride to an ethereal solution of methylphenylnitrosamine ; a vigorous action takes place after some time and small yellow needles of the 1 4 nitrosomethylaniline hydrochloride separate in an almost pure state. The base is obtained by precipitation with sodium carbonate or ammonia either in yellowish-green laminae or from very dilute solutions in large steel-blue prisms; it is readily soliible ia alcohol ether and chloroform sparingly soluble i n benzene and only slightly soluble i n light petroleum and in water.It melts a t 118" and suffers decomposition when more strongly heated. When heated with solution of sodium hydroxide it is decomposed into 1 4 nitrosophenol and methylamine ; whilst by reduction methylparaphenylenediamine is obtained. Paranitrosomethylaniline is a secondary base and by the action of nitrous acid yields 1 4 nitrosomethylpheny lnitrosamine NO*C6H4*NMe*N0 ; this compound crystallises from alcohol in nodules and melts at 101". Careful oxidation with nitric acid of sp. gr. = 1.13 converts it into 1 4 nitromethy Zphenylnitrosamine; this forms yellow needles melting a t 104". When methylaniline dissolved in alcoholic hydrogen chloride is treated in the cold with one molecular proportion of sodiuni nitrite there separate after long standing two compounds 1 4 nitrosomethyl- aniline hydrochloride and 1 4 nitrosomethylphenylnitrosamine the latter being formed in the greater quantity and a corresponding pro- portion of the methylaniline remaining nnacted on.1 4 NitrosoethyZaniZine obtained i n a manner similar to the methyl- deriva,tive crystallises in green lamina melts at 78" and is readily soluble in alcohol ether and benzene sparingly soluble in water. Its hydrochloride crystallises i n stellate groups of needles. By reduction ethy~al.aphen?/lendiamine is obtained; this base is a thick oil and distils a t 270". Its hydrochloride forms colonrless narrow scales readily soluble in water less soluble in alcohol.From 1 4 nitroso- ethylaniline 70 per cent. of the nitrosophenol and 80 per cent. of the ethylamine hydrochloride required by theory were obtained by heating it with sodium hydroxide solution. 1 4 Nitrosoethylorthotoluidine melts a t 140" and crystallises in green scales fi-equen tly exhibiting a bluish shimmer. 1 4 Nitrosodi~,henylamine obtained from Witt's diphenylnitrosamine crystallises in green tables showing a bluish shimmer melts at 143" and dissolves readily in alcohol ether and chloroform giving brown solutions and in sulphuiic acid with a red colour which at once changes to violet on warming. The 71 ydrochloride crystallises in brown tables having a bronze lustre or in dark reddish-brown needles and is decomposed by water with liberation of the base.w. P. w.ORGANIC CHEMISTRY. 245 Preparation of Benzylamine and Phenethylamine. By S. HOOGEWERFF and W. A. VAN DORP ( R m Trau. Chiw. 5 252-254). -Hofmann has suggested the action of bromine on phenylacetamide in presence of dilute alkali as a convenient method for the preparation of benzylamine (Abstr. 1886 45). It is here shown that the yield is considerably increased by preparing the alkaline hypobromite first and then adding it subsequently to the amide. The preparation of benzylamine and phenethylamine by this method is described. V. H. V. Isodinitrodimethylaniline. By P. V. ROMBURGH (Bec. Trav. Chim . 5 240-245) .-According to Mertens when dinitrophenyl- nitramine is heated with phenol tetranitrodimethylazobenzene a red compound is produced reconvertible into the nitramine by treatment with nit'ric acid (Abstr.1885 1022). As however trinitrophenyl- methylnitramine yields a similar red substance reconverti ble into the nitramine which has been shown to be trinitrophenylmethylaniline i t is probable that the red substance obtained by Blertens is a dinitro- methylaniline. The analytical results support this view quite as well as that of Mertens. As a confirmation the author by acting on tetrarnethyl benzidine with nitric acid obtained a product resembling the isodinitrodimethylaniline of Mertens which when boiled with nitric acid yielded the corresponding nitramine ; from this the red substance was obtained the analysis of which showed that it was a tetranitrodimethylbenzidine. Wlien treated with nitric acid this yielded the theoretical quantity of the nitramine.V. H. V. New Synthesis of Thiodiphenylamine. By A. BERNTHSEN (Ber. 19 3255-3256).-Tliiodiphen~lamine is obtained by heating orth- amidophenyl mercaptan and cntechol a t 220-240" for about 30 hours. The product is extracted with alkali and acid and crystallised from ether and light petroleum. This synthesis forms an important sup- port in favour of thiodiphenylaniine being a di-ortho-compound (corn- pare Bernthsen Abstr. 1886 53 and Mohlau Ber. 19 2013). N. H. M. Ethereal Carbonates. By G. BENDER (Ber. 19 2950-2952). -0xycarbimidopheno1 described by Halckhoff (Abstr. 1883 1 1 6 ~ ) andpreviously by Groenvik (Bull. SOC. Chim. 25 177) and hydroxy- methenylamidophenol prepared by Sandmeyer (this vol. p. 135) are identical with the author's anhydro-orthamidophenyl carbonate (Abstr.1887 37) which melts a t 137-138'. Kalckhoff's compound on further purification becomes white and its ncetyl-derivative is soluble in water like the corresponding substance obt.ained by the author. The ethyl salt prepared by Sandmeyer has the formula -nT C6H4<z>C*OEt that of the salt obtained by the author is NEt C,H,<-O->CO. In the existence of these two isomerides the parent substance exhibits a remarkable analogj to carbostyril and isatin; it also has st pseudo-form in addition to its ordinary216 ABSTRACTS OF CHEMICAL PAPERS. one although whether the latter is a lactim or lactam cannot yet be decided. The author's ethyl salt melts at 29" and has a bitlter taste. Con- centrated hydrochloric acid is without action on it at loo" but dissolves it in the cold forming a highly unstable hydrochloride.w. P. w. Benzyl-derivatives of Hydroxylamine. By F. WALDER (Ber. 19 3287-3294).-Further investigation has shown that the con- clu sions respecting the composition of these compounds arrived at in the author's previous paper (Abstr. 1886 796) are erroneous A complete analysis of the compound obtained by the action of methyl iodide and sodium on dibenzylhydroxylamine and described as tri- benzylbenzoxyammonium iodide shows that it has the formula N2(C7H,)40,HI. The hydriodide can be decomposed by alkalis but since the base is soluble in water and only sparingly soluble in ether a separation is better effected by employing moist silver oxide. The base crystallises over sulphuric acid distils with decomposition a t high temperatures and is very deliquescent ; when heated with water it yields dibenzylhydroxylamine whilst by the action of acetic anhy- dride acetyldibenzylh~droxylamine is obtained. The pZatinochZoride Nz( C7H7)40,HzYtC16 crystallises in slender yellow needles melts at 133" and is insoluble in cold water and ether.The sdphate N2( C,H7)40,H,S04 forms transparent prisms melts a t 152" and is insoluble in alcohol and ether readily soluble in water containing acid. The nitrate N,( C7H7)40,2HN03 crystallises in white feathery flat needles melts at 159" and is sparingly. soluble in water. The hydrochloride N2( C7H7),0,2HC1 forms thick prisms showing a iiacreous lustre is insoluble in ether and only sparingly soluble iu. water after it has once separated from solution.9 second hydriodide Nz(CiH7)40,2HI crystallises in bright yellow aggregates melts at 27" and is soluble in alcohol. From a black resinous mass formed in the preparation of the hydriodide N,(CiH,)aO,HI a black crystalline compound may be ob- tained ; it appears to be a periodide of the formula N,(C7H7)40,MeI,12. The base previously described as benzy lbenzenylamine proves to be dibenzylamine NH(C7H,)z. It is found that when dibenzylhydroxyl- amine is lieated with phosphorus trichloride and the product extracted with dry ether an unstable bright-yellow viscid oil con- taining phosphorus and chlorine is obtained which on addition of water yields dibenzylamine. The nitrosamine ( CiH7>,N*NO forms brittle curved white crystals melts a t 61" and is readily soluble in alcohol ether and light petroleum insoluble in water.'the piatino- chloyide N( C7H7)zH,H2PtC1 crystallises in golden-yellow needles ; the nitrate N ( C,H7)zH,HN03 crystallises in slender glistening needles melts at 186" and is sparingly soluble in water. When heated with benzyl chloride a t loo" the base is converted into tri- benzy lamine. When dibenzylhy droxylamine hydrochloride is treated with potas- sium nitrite in the cold ~iit~osodibenxylh~jdroxylallzine N(C7H7)zO*N0 is obtained; this crystallises in flat white needles melts at 82-84",ORGANIC OHEMISTRT. 247 and is soluble in alcohol and ether sparingly soluble in light petro- leum insoluble in water. If however cooling be omitted and the nitrate be added rapidly to the hydrochloride nitrosodibensy 1- amine is obtained N(C7H,),0H + 2HN02 = HKO + H20 + The author finds that mono- di- and tri-benzylamine are also formed when dibenzylhydroxylamine is prepared by Schramm's method N ( C H7) 2*NO. (Abstr.1884 51). w. I?. w. Correction. By L. KNORR (Bey. 19 3303).-In a previous paper (Abstr. 1884 1198) a compound C14Hl,N204 was stated to have been obtained by the action of ethyl acetoacetate on orthophenylene- diamine instead of on paraphenylenediamine. Sulphnric acid is without action on the compound iu the cold but a t 100" paraphenyl- enediamine is eliminated. w. P. w. Action of Ethyl Acetoacetate on Aromatic Diamines. By 0. N. WITT (Ber. 19 2977-2978 and 3299).-By the action of ethyl acetoacetate on orthotoluylenediamine ethenyltoluylenediamidine is formed.This confirms the resdts obtained b Ladenburg and Riigheimer (Abstr. 1879 915) the priority oP whor;le work is acknowledged by t4e author in the second communication. Condensation Products from Carbo-imides and Orthodi- amines. By C. DAHM and K. GASIOROWSKI (Ber. 19 3057-3060). -Carborthotoluylenedipkenyltetramine CTH,<NH> C (NHPh) is pre- pared by heating carbodiphenylimide and orthotoluylenediamine (mole- cular weights) for four hours at 130-lev. It crystallises from benzene in needles melting at 161" and is readily soluble in alcohol and ether. It does not react with an excess of imide. The hydro- chloride 2CmH20N4,3HC1 crystallises in white needles melting at 173-174"; it is very soluble in alcohol and ether rather sparingly in water. The sulphate was also prepared.Carborthotolzcylenediparatoly ltetramine C,2H2JYa is prepared in a manner similarly to the above-mentioned compound. Tte product is extracted with boiling benzene and the white powder dissolved in alcohol from which it separates in needles melting at 196". The 7ydrochEoride 2CzpHz4N4,3HC1 crystallises from tho strong acid solu- tion in needles melting at 143O. NH N. H. M. Derivatives of Parachlorazobenzene. By E. MENTELA and K. HEUYANN (Ber. 19 2970-2974 ; comp. Abstr. 1886 €3741.- ChZorodiainidodip~enyZ NH2*CsH,*CsHSC1*NHz.-When pnrachlorazo- benzene in dcoholic solution is treated with zinc chloride and sul- phuric acid and the solution after precipitating the zinc with hydrogen sulphide is made alkaline with caustic soda chlorodiamido- diphenyl is obtained and can be extracted with ether.It is a bright yellow powder which very readily becomes oxidised. The hydrochloride C12Hl,N,Cl,2HCl crystallises in tufts of white needles,248 ABSTRACTS OF CHEMICAL PAPERS. Parn,nifrochlorazobpntene N02*C6H4*N2*C6H4C1 [4 1 41 is prepared by treating parachlorazobenzene with fuming ni trio acid. It forms slender pale-jellow needles melts at 132*S" and is insoluble in water sparingly ,soluble in cold alcohol and ether readily soluble in acetic acid. Parac~~lorazobeizxenesi~lphonic acid SO3H*C6H4*N,*C6H4Cl [4 1 41 is obtained by heating parnchlorazobenzene with 10 per cent. fuming sulphuric acid a t 60-70" for some time. I t crystallises in brown needles melts at 149" and is very soluble in water and alcohol. The sodium and barium salts are described.The chloride C1,H,N2C1-SO,Cl melts a t 1W0 and crystallises in glistening red prisms soluble in alcohol and ether; boiling with water converts i t into the acid. The ainide forms brownish-yellow prisms melts a t 211" and is insoluble in water sparingiy soluble in ether and cold alcohol. w. P. w. Cyanazobenzene and Parazobenzenecarboxylic Acid. By E. MENTHA and I(. H EUMANN (Be).. 19 3022-3W5) .-Paracyanazo- benxme CI3H9N3 is prepared by slowly adding a solution of diazoben- zene chloride (from 40 grams of nmido-azobenzene hydrochloride) to a solution of copper sulphate (100 grams) and potassium cyanide (90 per cent. 112 grams) in ti00 C.C. of water a t 90".When cold it is filtered well washed and dried ; it is then sublimed and recrystallised from benzene from which i t separates in short brown nkedles. It melts a t 100-101" is insoluble in water readily soluble in warm alcohol ether and benzene. PiLrazobenxenscarbozylic acid NPh N*CsH4-COOH is obtained by boiling the above nitrile in the pure state for three hours with con- centrated aqueous potash. It crystallises from alcohol in long lustrous brown prisms soluble in ether and warm benzene. When heated above 210" i t becomes dark and decomposes at a higher tem- perature. When heated with lime a sublimate is obtained which melts a t 170-171" and is probably azophenylene. The potassium saZt crystallises in brownish-yellow needles soluble in water and in alcohol; the barium salt forms needles sparingly soluble in water rather readily soluble in alcohol.Several other salts were pre- pared. N. H. M. Chloroparazotoluene. Ry E. MEETHA (Bey. 19 3026) .-Chloro- pnrazotoluene C1,HI3N3C1 is prepared by treating 4.5 grams of amido- pnrazotoluene (obtained by Nolting and Witt's method Abstr. lF84 742) with 200 C.C. of water and 150 C.C. of strong hydrochloric acid and adding a solution of 5 grams of cuprous chloride in 45 C.C. of hydrochloric acid. It is then heated to go" and a solution of 2.5 grams of sodium nitrite in 25 C.C. of water gradually added. The product is filtered treated with hydrochloric acid and with soda solution and ultimately crystallised from alcohol. It forms brown plates which melt at 97' dissolves readily in et>her alcohol arid benzene and closely resembles parachlorazobeuzene (compare Abstr.1886 874). N. H. M.ORGANIC CHEMISTRY. 249 Reduction of Aldoxirnes and Acetoxirnes. By H. GOLDSCHMIDT (Bey. 19,3232-3234).-Cart.yZumine CIOH17N is obtained by reducing carvoxime in alcoholic solution with sodium amalgam in presence of acetic acid. Benzylamine can be conveniently prepared by gradually adding 160 grams of 24 per cent. sodium amalgam to a solution of 5 grams of benzaldoxime in 20 C.C. of alcohol a t 50-60"; the solution must be kept acid by addition of acetic acid. It is poured into water satu- rated with ether made alkaline and again extracted with ether. The ethereal extract is dried and treated with hydrogen chloride ; benzyl- amine hydrochloride then separates as a white precipitate.Benz- hydrylamine and isobntylamine were prepared in a similar manner from benzophenoxime and isobutylaldoxime respectively. N. H. M. Pyrogenic Formation of Phenazine. By A. BERNTHISEN (Rw. 19 3256-3258) .-The author succeeded in isolating phenazine from the product obtained by passing aniline through a red-hot tube (Abstr. 1886 471). The product was repeatedly exhausted with moderately dilute hot hydrochloric acid the brown solution precipi- tated with ammonia extracted with ether and the ethereal solution shaken several times with dilute hydrochloric acid. I n this waty the stronger bases were dissolved but not the phenazine. The ether was distilled off the residue extracted with hot dilute hydrochloric acid filtered when cold and precipitated with ammonia.I t was then sub- limed and the lustrous yellow needles identified as phenazine. This pyrogenic formation of phenazine corresponds with that of anthracene from toluene. N. H. M. Safranine Dyes. By R. NIETzKI (Ber. 19 301'7-3022).-Pre- vious experiments (Abstr. 1883 731) made it probable that safranine contains two amido-groups and that the third nitrogen-atom is tertiary or quaternary. When phenosafranine ClaH14N4 is boiled with alcohol sulphuric acid and sodium nitrite the compound C,Jl,3N3 is formed. This is a dye of a bluer shade than safranine from which i t is also distin- guished by the absence of fluorescence of its alcoholic solut,ion and in its behaviour towards strong sulphuric acid :-safranine dissolves with a green colour which changes to blue and red on addition of water ; the new compound dissolves yielding a yellowish-brown solution which when diluted becomes first green and then red.The monacetyl- deriuative is violet and yields crystalline yellow salts. The second amido-group in safranine can be removed only with difficulty and in strongly acid solution. A reddish-violet base "as obtained which yields brownish-yellow salts. It shows the same re- actions as the acetyl-derivatives of safranine. The two constitutional formula for safranine lately proposed by Bernthsen (this vol. p. 139) are shown by the author to be incorrect. With the one the existence of the two isomeric diethylsafrani~les obtained by the author (Zoc. cit.) cannot be accounted for ; the otIier formula permits the existonce of the two isomerides but only one of250 ABSTRACTS OF CHEMICAL PAPERY.the latter could be diazotised. It has been shown tlint both the diethylsafranines very readily yield diazo-compounds. N. H. M. Constitution of the Safranines. By 0. N. WITT (Ber. 19 3121-3124) .-The author criticises the constitution assigned to the phenosafranines by Andresen (Abrtr. 1855 1026) and by Bernthsen (this vol. p. 139) and suggests the following :- N Lencosafranine. Phenosafranine hydrochloride. A. J. G. Constitution of Safranine. By R. NIETZKI (Bey. 19 3163- 3166).-The author supports the correctness of the formula suggested by Witt (see preceding Abstract). 0. Lehmnnti has examined crys- tallogrsphically the nitrates of the two dimethylsafranines previously described by the author and the non-identity of which has been lately called in question by Bernthsen (this vol.p. 139). Lehmann de- elares the two compounds to be undoubtedly different. The author has carried out the idea mentioned in his last paper on this subject and tested the safranine-forming power of the six isomeric xylidines C6H,Me,*NHz and of the three isomeric com- pounds ( C6H2Me3*NHz) cumidine mesidine and isocumidine when heated with paradiamidodiphenylamine. The results-takiny NH as always occupying the position l-may be expressed a8 follows :- The xylidines 1 3 4 and 1 2 4 gave safranine; 1 2 5 1 2 6 and 1 3 5 gave no safranine; and 1 2 3 gave only traces which were probably due to traces of the 1 3 4 compound present as impurity in the xylidine used.Ordinary cumidine [l 2 4. 51 gave a safranine whilst mcsidine [l 2 4 61 and isocumidine [l 3 4 51 gave none. It is therefore clear that the position of the meth yl-groups in the monamine plays a determining part in the formation o r non-formation of safranines. The author considers that Witt’s formula is much more in har- mony with the above and other facts known about safranine than is either Andresen’s or Bernthsen’s formula. L. T. T. Paranitroformanilide. By T. B. OSBORN and W. G. MTXTER (Aimer. Chew. J. 8 346-347) .-This substance NO,*C,H,*NH*COH was prepared b-j adding formanilide to fuming nitric a d sp. gr. 1-53 in a freezing mixture and pouring the product into cold water; it was washed with water and ether then cryatalliscd from alcohol.ItORGANIC CHEMlST RY. 251 melts at 187" or 194" according as it has been crystallised from alcohol or from hot water. When boile3 with caustic potash it yields para- nitraniline. Attempts to obtain azo-compounds by its reduction were unsuccessful. H. B. Orthazoparabromacetanilide. By C. H. MATTHIESS EN and W. G. MIXTER (Arner. Chem. J. 8 347-349).-Parabromacetanilide was converted into orthonitroparabromacetanilide and then treated in warm alcoholic solution with zinc and strong aqueous ammonia for half an hour. The red precipitate mas wasbed with water dilute acid and alcohol. During the reduction a portion of the bromine is displaced with formation of azoacetanilide which is only removed by heating with concentrated hydrochloric acid at 100".The product thus purified is orthazoparabl.omacetcrnilide N,( C6H3Br-NHAc),. It is a pale red substance melting a t 280-282" and is acted on by potash with great difficulty. Halogen-derivatives of Oxanilide. By J. 0. DYER and W. G. MIXTEE (Amer. Chem. J. 8 349-357).-Tetrachloro3anilide C20,(NH*C6H3C1)2 [l 2 41 is obtained by passing chlorine into an acetic acid solution of oxan- ilide. It separates in slender white fibres melting at about 255" and is difficult to obtain quite pure. On decomposition it yields meta- dichloraniline melting a t 63". Paradibromoxanilide C202(NH.C,H,Br)2 is obtained by adding bro- mine in excess to a boiling acetic acid solution of oxanilide. I t melts above 300". Treated with alcoholic potash it yields parabromaniline. Paradiiodozanilide is prepared by the action of iodine and strong nitric acid ; crystallised from aniline it is quite white.It decomposes before melting. Boiling alcoholic potash converts oxanilide into oxanilic acid and thcn into oxalic acid and aniline. The substituted oxanilides behave similarly Metadichlorozanilic acid (=6H3C12*NHmCO*C001 is formed along with metadichloraniline by the hydrolysis of the tetrachlor- oxanilide. It dissolves in 808 parts of water a t 25" and melts a t 122" ; the potassium salt crystallises from hot water in fine fibres. Parabromoxanilic acid C6H4Br*NH*CO*COOH is readily soluble in hot water and in 515 parts of water at 25"; i t melts a t 198". The potassium salt is anhydrous and forms tabular monoclinic crystals ; the calcium barium and silver salts are also anhydrous and sparingly soluble in water.Paraiodoxclnilic acid C6HJ.NH*C0.COOH melts with decomposition at 197-200° and dissolves in 1385 parts of water a t 25" ; the potassium salt is anhydrous. Action of Concentrated Sulphuric Acid on Aromatic Ke- tones. By A. CLAUS (Bey. 19 2879-2881).-1n this paper pre- liminary experiments are described on the decomposition of aromatic ketones by fuming sulphuric acid. The reaction consists in the de- composition of the ketone and formation of a carboxylic acid and A sulphonic acid thus mesitpl phenyl ketone yields mesitylsnlphonic and benzoic acids. It is proposed to carry on a series of investiga- H. B. Treated with potash it yields paraiodaniline. H. B.252 ABSTRACTS OF CHEMICAL PAPERS. tions to determine in the case of mixed ketones containing a simple and a replaced pbenyl-group whether in all cases the former remains combined with the carbonyl grouping and the latter yields the sul- phonic acid as also to investigate the changes produced in the case of a ketone containing the subptituted phenyl groupings of differing degrees of complexity.At a low temperature a sulphonic acid of the ketone is formed ; thus barium salts of mesitqlphenylketonemono- sulphonic and para-xylylphenylketonedisulphoni~ acids are described. V. H. V. Aromatic Ketones. Ry 0. PAMPEL and G. SCHMIDT ( B e y . 19 2896-2899) .-PhenyZ e t h y l ketone (propiophenone) COEtPh is ' con- veniently prepared by Friedel and Crafts' aluminium chloride reaction. I t s acetoxime- and phenylhydrazine-compounds are colourless oils ; with bromine i t yields a monobromo-derivative as a dark oil which gives an anilide COPh*C?H,*NHPh separating in yellow glistening crystals me1 ting a t 38" ; its acetyl-derivative crystallises in colourless needles melting a t 103".Naphthyl methyl ketoue C,,,H,*COMe prepared by amid of t'be aluminium chloride reaction is a pale-yellow oil boiling at 296-299". Its acetoxime- and phenyl hydrasine-derivatives are crystalline com- pounds melting a t 101" and 146" respectively. C,H,*CO*CH,*NHPh separates in golden-red crystals melting at 130" ; its thiocvnnate crys- tallises in micaceous crystals. Its anilide V. H. V. Benzene-derivatives of High Molecular Weight By F. KRAFFT (Bey. 19,2982-2988).-PentadecyZphenyZ ketone C15H3,*COPh is obtained by gradually adding aluminium chloride (16 parts) to a cooled solution of palmitic chloride (1 part) in benzene (2 parts) and afterwards gently warming; the product is poured into water excess of benzene removed by distillation and by fractional distillation under 15 mm.pressure the ketone is approximately separated from the regenerated palmitic acid the last traces of which are removed from an alcoholic solution of the distillate by precipitation as barium palmi- tate. The ketone crystallises in large glistening laminae melts a t 59" boils a t 250.5-251" under 15 mm. pressure and is very sparingly soluble in cold alcohol soluble in ether and hot alcohol. On oxidation with chromic acid it yields benzoic and pentadecylic acids. Eeradeay Zbenzene CIGHBBPh is prepared by the action of sodium on a mixture of cetyl iodide and iodobenzene.It crystallises i n glistening tables which subsequently become opaque melts a t 27" and boils at 230" under 15 mm. pressure. When dissolved in fuming eulphuric acid hexadecylbeiizene yields a nzonosuZphonic acid and by fusing its sparingly soluble sodium salt with potas- sium hydroxide a t 250" hezadecyZphenoZ ClsH33*C6H4*OH is obtained. This is a colourless odourless and tasteless compound melting a t '77.5" and boiling a t 260-261" under 16 mni. pressure. E e x a - derylnitrobenzene is a crystalline powder melts a t 3.5-36" and when reduced yields hexadecylan,idobenzene which melts a t 53" and distils without decomposition a t 254-255" under 14 mm. pressure ;ORQANIC CBEMIYTRT.253 its phtinoch Zoride ( C16H3,*C,H,*NH,)2,H,PtC16 is soluble in ether and alcohol. Octndecylbenzene CIsH,,Ph is obtained by the action of sodium on a solution of octadecyl iodide and iodobenzene in benzene. It forms either an oil which soon solidifies 01- crystallises in colourless odonr- less and tasteless silvery scales melts a t 36" and boils at 249" under 15 mm. pressure. Octa,decylbenzenesulpho~ic acid is prepared by treating octadecylbenzene with fuming sulphuric acid and gently warming ; the sodium salt when heated with eight times its weight of potassium hydroxide a t 250-270" for 10 to 12 hours yields octadecyl- phenol C,,H,,*C,H,*OH almost quantitatively. This cr~stallises in glistening lamins melts a t 84" and boils without decomposition a t 277" under 15 mm.pressure. Octadecylbenzene is converted by fuming nitric acid into an almost colourless mononitro-compound melting at about 48" ; by reduction this yields octcrdecylamidobenzene which melts a t about 61" and boils a t 274" under 15 mm. pressure. HexyldiplienyZmethane c6Hl3*CHPh2 is formed when 0.2 part of aluminium chloride is slowly added to 1 part of oenanthylidene chlo- ride dissolved in 4 parts of benzene ; after standing for two days the whole is heated at 30" for a short time. It melts a t 14" and boils a t 186" under 10 mm. or 193" under 15 mm. pressure. By the action of nitric acid hexyldinitrodipheiiylmetharLe CsH1,'CH(C6H,*NO,) is obtained and this on reduction yields T~exyld iamidodiphenylnlethane. Hex~lltetranzefhljldi~~idoaipheny Zmetl~ane can be prepared either from the latter or by the condensation of oenanthaldehyde and dimdhgl- aniline with zinc chloride.It melts a t 59.5" boils a t 272-278" and yields a platinochloride C23'113N2,H2PtCl~ sparingly soluble in water aud ether-alcohol. When a larger proportion of aluminium chloride is added to enanthylidene chloride in benzene heptylbenzene C7H,,Ph is obtained. It boils a t 108-110" under 10 mm. pressure. The corresponding lwxyl phenql ketone C6H13*COPh is prepared by the action of 0 5 part of aluminium chloride on 1 part of heptoic chloride in 2-3 parts of benzene. It melts a t 17" boils at 155" under 15 mm. pressure and yields ail acetozime which melts a t 55" and crystallises from alcohol in stellate groups of needles. By the action of zinc chloride on hcptoic chloride and dimethylaniline a base melting a t 72.5" and boiling at 278" under 15 mm.pressure is obtained together with hexyl dirnetlranzidophenyl ketone C6H,,*CO*CsH4*NMe,. The ketone melts at 48*5" boils a t 190" under 20 mm. pressure and yields an acetoxime which crystallises in silvery glistening scales. Paraxylyl Ethyl Ketone and its Oxidation to Orthometa- dimethylbenzoylacetic Acid. By A. C ~ a u s and E. FICKERT (Rer. 19 3182-3184) -paraxy7yZ ethy! ketone C)GH~M~~'COE~ obtained from parxxylene and propionyl chloride is am colourless mobile highly refractive liquid having an aromatic odour and strong bitter taste. It is lighter than water and boils a t 237-2:38" (uucorr.). When oxidised with dilute solution of potassium permanganate it yields a mixture of xsly 1 car box y li c aci d and par ax y ly 1-p- ketonic (or t h ome t ad inz et h y Ib mi xoy 1 acetic) acid CsH3Me2*CO*CHz*COOH.The acids are best separated w. P. w. VOL. L11. S254 ARSTRACTS OF CHEMICAL PAPERS. by means of their barium salts the ketonate being very sparingly soluble. The ketonic acid is sparingly fioluble in water and light petroleum easily in alcohol ether benzene &c. It crystallises in needles melting at 132" (uncorr.). The sotlizm salt (with 1H,O) is easily the calcium ( + 2$H20) barium (+ 4H20) and silver salts very sparingly soluble. Similar reactions have been obtained with aromatic ketones contain- ing the ethyl and propyl &c. groups and are now being investigated. Nitrophenyl Benzoates and Nitrobenzoates and their Pro- ducts of Decomposition.By G. NEUMANN (Ber. 19 2979-2982). -Continuing his previous work (Abstr. 1886 350 939) the author prepared metunitrophenyZ benzoate by heating metanitroplienol with benzoic chloride. It is readily soluble in acetic acid alcohol and hot light petroleum and forms pale yellow crystals which melt at 95". When treated with nitric acid of RP. gr. 1.48 it yields metanitrophenyl wrtanitrobenzoate. This compound forms white crptals melts at 129" and is readily soluble in cold chloroform and hot alcohol ether and light petroleum. Metaparadinitrophenyl metanitrobenzoate is obtained by the action of nitric acid of sp. gr. 1-53 on metanitrophenyl benzoate. It crystallises in bright yellow needles melts at 149" and is sparingly soluble in most ordinary solvents especially in ether and light petroleum. Metanitrophenyl benzoate when dissolved in a mixture of equal parts of nitric acid of sp.gr. 1.51 and sulphuric acid of sp. gr. 1.82 yields trinitroresoroinol and metanitrobenzoic acid. L. 1'. T. W. P. W. Method for the Introduction of Carboxyl into Aromatic Hydrocarbons. By E. LELLMANN and 0. BONHOFFER (Ber. 19 3.231) .-Benzoic acid can readily be prepared by acting with diphenyl- carbnmide chloride on benzene in presence of aluminium chloride and heating the benzoyldipheuylarnine so obtained with hydrochloric acid. Paratoluic and xylic acids [COOH Mez = 1 2 41 were obtained in a similar manner from toluene and metaxylene respec- tively. Paraxylene does not react with the chloride ; hence it would seem that the group CO*NPhi can only take up the para-position with respect to methyl.By J. PLOCHL (Ber. 19 3167-3172) .-In answer to the colninunications of Lipp (this vol. p. 142) and E. Erlen- meyer jun. (ibid.) the author upholds the correctness of his view (Abstr. 1884 604) that his acid C9H80 is the true phenylglycidic N. H. M. Phenylglycidic Acid. /"\ acid CHPh.CH*COOH and that Glaser's acid is p-hjdroxycinnamic acid. The author finds that paranitrobenzaldehyde forms with hippuric acid 8 condensation-derivative corresponding with benzoylimidocinnamic anhydride. This substance when heated with fuming nitric acid firBt forms paranitrobenzoylimidocinnamic acid but at 120-130" it isORQANIC CHEMISTRY. 255 decomposed yielding a brownish-red compound (a polymeric nitro- phenylethylene oxide) whilst carbonic anhydride is a t the same time evolved.Lipp's paranitrophenylglycidic acid gives the same decom- position-products. The author points out that in many other cases also the introduction of a nitro-group into the benzene nucleus causes a variation in the behaviour of the side-chain in reactions. E. Erlenmeyer jun. objects to the author's formula bxause the latter's phen~lglycidic acid yields a phenylhydrazine and a hydroxyl- amine compound and shows the thiophen reaction. The author states that with ammonia his acid gives a compound C,H,NO. He believes this compound to have the constitution CHPh< I >CO and thinks that Erlenmeyer's compounds have probably analogous structures. As further strongly supporting the correctness of his formula the author cites-( 1) the gradual decomposition of the acid when exposed to moist air into benzaldehyde and a new acid ; (2) the formation of a polymeric phenylethylene oxide (and not Erlenmeyer and Lipp's polymeric phenylethylaldehyde) by the action of hydrochloric acid ; and (3) the easy convertibility of the acid into pheizylpyruvic acid; the latter is easily soluble in boiling water crystallises in tables and melts a t 160-161". CH N - It is still under investigation.L. T. T. Benzoquinonecarboxylic Acids. By J. U. NEF (Annalen 237 1-39).-This paper contains a description of the derivatives of durene durylic acid and quinonetetracarboxylic acid which has already been published by the author (Abstr. 1886 64 241 5.50).The following substances have not been previously mentioned :-The acetic derivative of diamidodurylic acid prepared by the action of acetic anhydride on the amido-acid a t 140" crystallises in quadratic plates and melts a t 275'. Dihydroxydurylic acid C,Me,(OH)2*COOH (Abstr. 1886 24l) is soluble in alcohol ether and in hot water. The acid forms an amor- phous lead salt and reduces ammoniacal silver nitrate solution. The ethyl salt C6Me3(OH)2*COOEt forms colourless needles. It melts at 1@9" and is soluble in hot water alcohol and the usual solvents with the exception of light petroleum. The alcoholic solution is oxidised by ferric chloride ethyl duroqui?l.onecarboxyZate C6*@zMe,GOOE t being formed. This substance is best prepared by the action of an ethereal solution of ethyl iodide on silver duroquinonecarboxylate.It crystal- lises in golden needles melts at 51" and Hublimes easily. It is in- soluble in cold water but dissolves freely in alcohol ether and in (warm) light petroleum. On reduction with sulphurous acid i t yields ethyl dihy droxydurylate. Duroquinonecarboxylic acid is co .npletely con- verted into nitropsewdocumenequinone C,O2Me3.NO2 by the action of warm strong nitric acid. The nitroquinone crystallises in golden scales soluble in ether chloroform benzene light petroleum alcohol and nitric acid. It melts a t 113" and sublimes readily. The corresponding quinol c6Me,( OH),*N02 is obtained by the action of sulphurous acid on the alcoholic solution of the nitroqninone a t 100". s 2Ethyl succinosuccinate .. . . . . . . . . Ethyl paradiketohexamethylenetetra. carboxylate. Ethyl paradihydroxyphthalate . . . . Ethyl quinoltetracarboxylate . . . . . Paradihjdroxyterephthalic acid . . . . Quinoltetracarboxylic acid . . . . . . . Ethyl paradiamidoterephthalate.. . . Ethyl diamidopyromellitate.. . . . . . . Properties. -- :olourless needles m. p. 126-127" :olourless needles m. p. 142-144" pale yellow nee- dles or prisms m. p. 133" yellow needles m. p. 126-128" yellow scales pale yellow broad needles golden needles m.p. 168' strong baee red prisms m. p. 134' feeble bas( Solutions. -- pale blue fluores- cence pale blue fluores- cence strong blue fluo- rescence strong blue fluo- resence yellowish-green with green fluo- rescence yellow with green fluorescence brown with gold- en yellow fluo- rescence red yellowish-red fluorescence Colour mith Fe2CI,.- cherry cherry blue-green blue-green intense blue intense blue NaOEt. :olourless bftemards pale pink :olourless ifterwards pale pink red red - - - - Zn + HC1 in alco- holic solution. ethyl succinosuc- cinate ethyl paradiketo- hexamethylene- te tmcar boxylatc ethyl succinosuc- cinate ethyl paradiketo hextimethylene- tetracarboxylatc Oxidation with Br in CS,. ethjlic paradihy- droxy terephtha- late ethyl quinoltetra- carboxylate with HN03 no quinone ethyl quinonete- tracarboxy late C 0 2 evolved ni- tranilic acid (30% evolved total decomposition no quinone ethyl quinonepy- romellitateORGANIC CHEMISTRY. 257 It crystallises in golden needles melts at 106" and is soluble in ether alcohol chloroform acetic acid and in hot water.The compound obtained by the reduction of ethyl dinitropyromelli- tate and described by the author as ethyl azopyromellitate (Abstr. 1886 64) ib now foiind to be ethyl dianzido~yronzellitate By reducing the alcoholic solution with zinc-dust and mlphnric acid ethyl paradiketohexamethylenetetracarboxylate is produced. Ethyl diamidopyromellitate yields a diacetic derivative C ( NH Ac) 2 ( C 0 0 E t) 4 which crystallises in colourless plates and melts at 149". It is freely soluble in acetone chloroform acetic acid and hot alcohol. It is not decomposed by boiling with alkalis or with hydrochloric acid. Ethyl quinoltetracarbo;lute C,(OH)-(COOEt)4 (Abstr. 1886 550) bears a striking resemblance in its properties to Herrmann's ethyl quinonedihydrodicarboxylate which Baeyer has shown (Abstr.1826 445) to be ethyl paradihydroxyterephthalate. &uinoZtetracarboxyZic acid crystallises with 14 mols. H,O which it retains a t 100". It dissolves freely in hot water forming a fluorescent solution from which it is precipitated by mineral acids. Ferric chloride gives a blue coloration. The soluble salts of this acid form yellow solutions which exhibit a green fluorescence. Attempts to oxidise quinoltetracarbo- xy lic acid to quinonetetracarboxylic acid were unsuccessful. E thy1 quinoltetracarboxylate is converted in to ethyZ paradiketo- hezamethyZAnetetracarboxyZlLte by shaking the alcoholic solution with zinc-dust and hydrochloric acid (Abstr. 1886 551). This substance yields ethyl quinoltetracarboxylate on treatment with bromine and carbon bisulphide and it readily enters into reaction with ammonium acetate and with phenylhydrazine. The resemblance between the derivatives of ethyl diamidopyrornelli- tate and etbyl succinosuccinate is shown in the table (p.256). w. c. w. Constitution of Azo-opianic Acid. By C. LIEBERMANN (Bar. 19 2920-2922) .-Although the so-called azo-opianic acid has been recognised as the anhydride of orthnmidohemipinic acid yet hitherto it has not been found possible to convert the latter into the former by the abstraction of the elements of water. In this paper however it is shown that both orthnmidohemipinic and azo-opianic acids yield an identical acetylazo opianic acid. The last acid when warmed with alkali and subsequently acidified yields acetylorthamido- hemipinic acid CsH( OMe)P( COOH),*NHAc + HzO which crystallises in colourless needles melting at 160-1 i O O with complete decomposi- tion.The acetyl-group is still retained when the acid is heated with concentrated sulphuric acid ; a result to be explained by the former researches of the author and Kleemann which have proved t h a t the acetyl-group in acetylazo-opianic acid is attached to the nitrogen and not to the oxygen-atom. V. H. V.2.58 ABSTRACTS OF CHEMICAL PAPERS. An Isomeride of Hemipinimide. By C. LIEBERMANN (Ber. 19 29234927) .-The author has recently shown that hemipinimide is produced by boiling a mixture of opianic acid with hydroxylamine hydrochloride in equiinolecular proportions. If however the change be effected a t ordinary temperatures a substance isomeric with hemi- pinimide is produced which it is proposed to call opianoxzrnic anhy- dride.It crystallises in long colourless needles melting a t 114- 115"; its alcoholic solution unlike that of hemipinimide is not fluorescent. When melted the substance is converted with con- siderable development of heat into hemipinimide. This anhydride only displays feeble acidic properties but on protracted heating with water it is converted into hemipinic acid. Similarly when ethyl opianate and hydroxylamine hjdrochloride are heated the above anhydride is also formed; all attempts to pre- pare opianoximic acid have hitherto failed. V. H. V. Isomeric Aldehydophenoxyacetic Acids. By T. ELKAN ( B e y 19 3041-3054) .-Paraldehydophenoxy acetic acid CHO*C,H4*OCH,*COOH [CHO OCH = 1 41 is obtained by heating equivalent amounts of parahydroxgbenzalde- hyde and monochloracetic acid in a silver dish on a water-bath and adding sufficient caustic soda to give an alkaline 1-eaction.When it begins to solidify a slight excess of chloracetic acid is added the solution being always kept alkaline ; it is then treated several times with water and evaporated to dryness. The product is dissolved in hot water precipitated when cold with hydrochloric acid and the yellowish acid so obtained purified by boiling with calcium carbonate. I t crystallises from water in small plates melting at 198" is very sparingly soluble in cold water more soluble in alcohol ether benzene and chloroform and shows aldehydic properties. It yields a sparingly soluble double compound with hydrogen sodium sulphtte and reduces ammoniacal silver solution but not E'ehling's solution.The silver salt C9H701Ag crystallises in needles. Bromine-water acts on the acid with formation of a brorniize-dei*ivative C3H,01Br; this crystallises from hot water in slender branched needles melting at 185". Ethyl paraldehydophenoxyacetate is a crystalline substance which begins to decompose at IOO" and melts at 155". The hydroxyl- arnine-derivative C9H901N forms large spear heads melting a t 145". Metaldehydophenoxyacetic acid CgH,04 is prepared in a manner similar to the para-compound. It crystallises from warm water in slender needles which melt a t 148" and shows the same aldehydic reaction as the isomeride; it is rather more solub!e than the latter.The silver and ethyl salts were prepared. The monobromo-derivative forms lustrous plates melting at 154". The hydl.oxylanaiiie-comp~,und crystallises in sleuder needles melting a t 168'. When oxidised with potassium permanganate both isomerides yield the corresponding dicarboxylic acids. C 0 0 H*C6H4*0 CH2* CO 0 H [ = 1 41 crystallises in white needles melting at 278" ; it dissolves Phenozyacetic-paracarbozy lic acid,ORGANIC CHEMISTRY. 259 readily in alcohol ether and glacial acetic acid less in benzene and chloroform and only very sparingly in water. The siher salt was analysed. The pheii y Zhydraaine-deTivatiue C15H14N203 forms slender yellowish-white needles which melt a t 159" and dissolve sparingly in water readily in alcohol and ether.Phe.rzoxyacetic-n~etacarboxyZic acid melts at 206O and is analogous in its solubility &c. to the para-acid. The pheny lhydrazine-compound forms slender needles which melt a t about 140'. Pheizoxz~acetic-paracrz~lic acid COOH CH CH*C6H4*OCHz*COOH is prepared by gently boiling equal parts of paraldehydophenoxyacetic acid and dry sodium acetate with acetic anhydride (3 parts). It melts a t 625" dissolves readily in alcohol ether and glacial acetic acid ; i t is also soluble in benzene and light petroleum. Phenoxyacetic-metnc?yZic acid CllHI0O5 is obtained in like manner to the para-compound and crystallises in needles melting a t 219". OTthacrylaldehydophenoxyacetic acid CHO'CH CH*C6H4*OCHz*COOH is prepared by exactly neutralising a dilute solution of orthaldehydo- plienoxyacetic acid heating it at 50" to 60° and gradually adding simultaneously an aqueous solution of acetaldehyde and 5 per cent.soda solution so as to keep the solution always slightly alkaline. It is then warmed on a water-bahh cooled down and acidified with dilute sulphuric acid. The acid crystallises from hot water in trans- parent plates which melt at 153". The rneta-acid crystallises (with 1 mol. H,O) in long yellowish needles which melt a t 100". The para-acid forms a crystalline yellowish precipitate melting at 182". All three isomerides show aldehydic properties ; they combine with hydrogen sodium sulphite reduce ammoniacal silver solutions and condense with phenylhydrazine. P hsnox y acetic- ort hacry lic acid met hy 1 ketone COMe*CH CH*CsH4*O*CH2GOOH is obtained by adding pure acetone (from the hydrogen sodium sulphite compound) to the warm slightly alkaline solution of sodium orthaldehydophenoxyacetate. It melts a t 108".The meta-compound Cl2HI2O4 crptallises in well-formed anhgdrous prisms which become opaque when kept. The para-compoud melts at 177-li8". The hlldroxl/lami.re-deriz~ative of orthaldehydophenoxyacetic acid (Rbssing Abstr. 1885 388) crystallises in plates very readily soluble in hot water alcohol and ether more sparingly in benzene chloro- form &c. It melts at 138". N. H. M. It melts at 122". Vanillinoxyacetic Acid. By T. ELKAN (Ber. 19 3054-3056). -VaniZZinozyncetic acid CHO*C6H3(OMe)*0*CHl~COOH [ = 4 2 11 is prepared by fusing monochlo~*acetic acid with vanillin in a silver dish and adding an excess of caustic potash until the solution is distinctly alkaline. After four hours (during which the water lost by2 60 ABSTRACTS OF CHEMICAL PAPERS.evaporation must be from time to time replaced) the reaction is completed. It crystallises from hot water in slender yellowish-white needles melts at l88" and dissolves readily in ether alcohol chloro- form &c. It combines with phenylhydrazine and with hydrogen sodium sulphite and reduces ammoniacal silver solution. The copper and silver salts were prepared. Vanillic-ozyacefic acid COOH*CsH3(OMe)*O*CH:,.COOH [ =4 2 11 is formed in the preparation of vanillinoxyacetic acid when the trent- ment with potash and chloracetic acid is too prolonged. It crystal- lises from water in slender branched needles which melt a t 256" ; it dissolves in ether benzene chloroform; &c. The copper salt has a fine green colour; it is insoluble.N. H M. Derivatives of Pyruvic Acid. By G. GERSON (Ber. 19 2963- 2969). - When ethyl a-cyano-a-hydroxypropionate is treated with phenylhydrazine a compound melting at 116" and identical a-ith Fischer's ethyl phenylhydrazinepyruvate (Abstr. 1884 52) is ob- tained. E t h y l a-anilido-a-cyanopro~ioiaate NHPh*CMe(CN).COOEt is pre- pared by treating ethyl a-cyano-a-hydroxypropionate with aniline in alcoholic solution. It crystallises in large transparent cubes be- longing to the rhombic system with the axial ratio a b c = 0.79063 1 1.56366 ; the followi!g faces were observed mP pre- dominating mPm mP00 narrow Po= fairly large Pm smaller than f'm.It melts at 101*5" and is insoluble in water but readily soluble in alcohol and ether. Ethyl anilidoisosuccinamate NHPh. CMe(CONH,) COOEt is formed when ethyl a-anilido-a-cyanopropionate is dissolved in con- centrated sulphuric acid poured into water and neutralised with ammonia. It crystallises from benzene in slender white needles melts a t 86" is sparingly soluble in cold water readily soluble in hydrochloric acid alcohol and benzene but insoluble in light petro- leum. The crystalline hydrochloride is very soluble in water. On boiling ethyl anilidoisosuccinamate with a solution of soda as long as ammonia is evolved acidifying with acetic acid converting into lead salt and decomposing it with hydrogen sulphide a-aniliilopropionic acid NHPhGMeH-COOH (Tiemann and Stephan Abstr.1883 1991 is obtained in white crystals meltling at 160". E t h y l a-orthotoluido-a-cyn.noprop~~~~~te C,H,-NH*CMe( CN)*COOE t prepared in a similar manner to the anilido-compound crystallises in rosettes of small whito needles melts a t 93" and is insolnbIe in water sparingly soluble in cold alcohol readily soluble in hot alcohol and benzene. On treating i t with concentrated sulphuric acid and neutral- ising with ammonia it yields ethyl orthofoluidoisosucci.namate C7H7*NH*CMe( CONH,) *COOEt which crystallises in long transparent needles and resern bles the anilido-compound in all its properties. By boiling the isosuccinamate with potash solution &c. orthotoluiLZopropionic acid C7H7*NH* CMeH- C OOH,ORGANIC C;HE&IISTRT.261 is obtained in slender white needles which melt a t 116" and dissolve readily in water alcohol and benzene. E t h y l a-paratohido-a-cyanopropiowate crystallises in light brown glistening spangles melts a t 80*5" and is insoluble in alcohol amd benzene sparingly soluble in water. E t h g l aa - naphtli y lavnido-a-cyanopropionate forms slender white scales which melt at 134" and are readily soluble in alcohol and benzene sparingly soluble in cold water. By treatment with sul- phuric acid &c. ethyl a-na~htl~ylnmidoisosucctnumate is obtained in long white needles melting at 159". It dissolves readily in alcohol and benzene sparingly in cold water. Etlzy 1 ap-n apht h y 1 am ido-a- cy asiopropion a te cry stallises in small rosettes is almost insoluble in water and cold alcohol soluble in hot alcohol and benzene and decomposes a t 200" without melting.w. P. v7. Two New Diketonic Acids. By W. KUES and C. PAAL (Bey. 19 3144--3148).-The authors have examined the insoluble crystal- line substance obtained by them during the hydrolysis of ethyl benzoylisosuccinate (Abstr. 1886 354) and find it to be ethyl cli- phenncylmalonate C( CHBZ)~ COOEt),. Its formation must be due t o the formation of some ethyl disodiomalonate and the action of the bromacetophenone thereon. This substance forms large colourless prisms melts at 118-119" and distils almost without decomposition. It is easily soluble in water benzene acetic acid and carbon bisul- phide more sparingly in alcohol and is irisoluble in light petroleum.i t reacts strongly with phenylhydrazine b u t no homogeneous sub- stance could be isolated from the product. Hydroxylamine is with- out action on it as are also aqueous solutions of the alkalis. When digested with strong alcoholic potash it is saponified and yields dipheiracy Zmnlonic acid cryatallising in colourless prisms melting with evolution of carbonic anhydride at 134". I t is spa~ingly soluble in water easily so in ether alcohol and acetic acid insolable in benzene. It forms a compound with phenylhydrazine. When care- f u l l y melted carbonic anhydride is evolved and diphenacglncstic arid CH (CH,Bz),*COOH is formed. This crjstallises in silky needles easily soluble in ether alcohol and benzene and mells a t 132-133".When heated with an acetic solution of phenylhydrazine it yields a compound of the formula C30H26N40 crystallising iii white needles which melt a t 164-166" and are soluble in alcohol and acetic acid insoluble in alkalis. The hydrazine-compound is not decomposed by dilute acids. Adopting the views of the composition of such com- pounds advocated by E. Fischer and W. Roser the authors consider the following as the most probable formula for this substance :- NzHPh CPh*CH,*CH<CH CO*NPh- Cph>N. L. T. T. Action of Zinc Alkyl Compounds on Ethyl Malonate. By E. LANG (Bey. 19 2937-293Y).-Zinc methyl or zinc ethyl acts at ordinary temperatures on ethyl malonnte with evolution of methane and ethane and formation of a crystalline magma of ethyl phloro-262 ABSTRACTS OF CHEMICAL PAPERS. glucinoltricarboxylate C,(OH),(COOEt),.The reaction thus con- sists of the abstraction of the elements of alcohol and subsequent condensation. V. H. V. Furfurane-derivatives from Resorcinol. By A. HANTZSCH(Ber. 19 2927-2934).-1t has been shown that the sodium compounds of the monohydric phenols when treated with ethyl chloracetate yield at first ethyl phenoxyncetoacetate and finally ethyl furfurocarboxylate. The dihydric phenols undergo a similar but more complicated reac- tion according as the mono- or di-sodium compound reacts with one or two molecules of the ethereal salt. In the former case hydroxy- cumarones are obtained in the latter benzodifurf uro-derivatives the nature of the isomerism of which is dependent on the relative position of the carbon-atom to which the furfuryl-ring is attached.Thus in the case of resorcinol two such isomeric hydroxy- and difurfuro- derivatives are possible precisely as two quinolines the meta- and the ana-series are synthetically formed from amines of the metn-series. E t h y l metahydroaycuwiarilate OH*C,OH,*COOEt [OH COOEt Me = 2 2' 3'1 formed from mono-sodium resorcinol and ethyl chlor- acetate crystallises in white needles melting a t 178" readily solable in ether. The corresponding acid crystallises with + mol. H,O in needles which melt a t 226" with evolution of carbonic anhydride and forma- tion of hydroxymethy Zcumarone CsOH4Me*OH. This compound crystallises in needles melting at 96-97' soluble in water alcohol and ether. From disodium resorcinol and ethyl chloracetate two isomeric ethyl benzodimethylfurfurodicarboxylates are formed the nature of the isomerism of which is analogous to that of anthracene and phenan- threne.These are provisionally designated the a- and @-series as the experimental results are insutiicient to fix the formula of each corn po imd. E t h y 1 metabenzodimethyl-a-difurfurocarboxylate C,0,H2Me2(C00Et) crystallises in needles melting a t 186" and its isomeride in more soluble aggregates melting a t 140-141". Both isomeric ethereal salts are readily saponified ; the corresponding acids melt above 310" with decomposition and are sparingly soluble in water but more soluble in alcohol. Both the acids and their salts are difficult to distinguish one from the other. Only one of the isomeric difurfuranes C H e 0 CMe ->C,H2<- CM :>CH is described corresponding with the ethereal salt which melts a t 186" ; it is a clear brown oil boiling at 270" solidifying in a freezing mixture aiid melting at 17"; witli concentrated sulphuric acid i t gives a light blue coloration resembling that obtained with coeruglignone.Furfurane-derivatives from Phloroglucinol. By E. LANG (Bey. 19 2934-2937).-The reactions between the butyric alcohol phloroglncinol and ethyl chloracetate in presence of sodium ethylate are analogous to those of resorcinol described in the preceding Abstract. The three series of compounds are formed in a similar way yet the presence of alcohol is necessary for the production of V. H. V.ORGANlG CHEVISTRY. 263 the dihydroxy-product and its absence for that of the trif urfuralde- hy de-derivatives.Ethyl metu-dihydroxymefhylcumarilate C,OH,Me(OH),*COOEt forms small white needles melting at 242" readily saponitied and converted into the corresponding acid which crystallises with 8 mol. HpO and melts a t 281" with evolution of carbonic anhydride. obtained by treating trisodium phloroglucinol with 3 mols. of ethyl chloracetate crystallises in satiny needles melting at 296 -298" sparingly soluble in all menstrua. The corresponding acid separates with 1 mol. H,O in a gelatinoua form. On distillation with alkali the benzotrimetbyltrifurfurane c6( <-o ->CH) is obtained ; it crystallises in needles melting a t 115-120" and is very soluble in most menstrua. CMe V. H. V. Sulphobenzidedisulphonic Acid.By R. OTTO and A. ROSSING (Bet-. 19 31 24-3129).-Su~I~obenzidedi~uiphonic acid is prepared as already described (Abstr. 1879 649) by the action of sulphuric hydroxychloride (2 mols.) on sulphobenzide. It is very probably the dimetasulphonic acid. It forms a yellowish fibro- crystalline deliquescent mass readily soluble in alcohol and water but insoluble i n ether and benzene. It forms only normal salts. The potassium salt crjstallises with 1 mol. H,O ; the sodium with 3 mols. H20 calcium with 6fr mols. H20 barium 5 mols. H20 copper with 3; mols. H,O and the lead salt with 3 mols. H20. The chZoricle crystallises in smali fatty plates and melts a t 175-176'. The umide forms white needles melts a t 240" is nearly insoluble in ettier acd benzene sparingly soluble in boiling water more soluble in alcohol.The a n i l i d e forms lustrous white plates and melts at 212'. The ethyl salt melts a t 81-82". The diphcmyZsuZphone S02(C6H4*S02Ph) is obtained in small quantity by heating the disulphonic acid with benzene and phosphoric anhydride ; it melts a t 192-193". Experiments to obtain a trisulphonic acid from sulphobenzide were unsuccessful . A. J. G. Non-existence of Claesson's Phenylsulphineacetic Acid. By R. OTTO and E. ENGELHARDT (Ber. 19 3138-314l).-Claefison states (this Journal 1876 i S67) that he obtained the above acid (aceto. phenylsulphinic acid) Ph*SO*CH2*C00H by the partial oxidation of phenylthioglycollic (pbenylthiacet'ic) acid. The authors have carefully repeated these experiments and find that the substance described by Claesson was not a homogeneous compound but a mixture of phenyl- sulphonacetic acid Ph*S02.CH2*COOH with nnoxidised phenyl- thioglycollic acid.L. T. T. Metatoluenesulphonic Acid and its Salts. By K. VALLIN (Her. 19 2958-2953) .-The metatoluenesulphonic acid employed in the previous research (Abstr. 1880 256) contained para-acid as an so2 C12H*(SOsH)2,264 ABSTRACTS OF CHEMICAL PAPERS. impurity; the author has therefore repeated the work with pure meta-acid obtained from toluidinesulphonic acid [CH3 S0,H NH = 1 3 41 by diazotising and boiling with alcohol. The acid crystallises in slender needles or thin scales. The potassium sodium silver calcium barium lead magnesium zinc cadmium and copper salts are described. The chloride C7HI,*SOzC1 has not been solidified ; the amide crystallises from water in lamina melting a t 107" from alcohol in moiioclinic crystals melting a t 108".At 14" 1 part of the ariiide dissolves in 376.7 parts of water and 5.74 parts of alcohol. The hydrosubhide C,H7*SH boils at i95-205" and does not solidify at -20". S o d i u m paratoluenesubphonate does not crystallise with 3 mols. of H20 but either with 2 mols. in laminated masses or a t low tempera- tures in rectangular tables with probably 4 mols. H,O. The hydro- sulphidc of the para-acid melts at 43-44' and boils at 194" that of the ortho-acid melts a t 15" and boils a t 193". w. P. w. Tolwnedisulphonic Acids. By P. KLASON (Ber. 19,2887-2890). -Toluenemetasulphonic acid is convertible into a rriixture of two disnlphonic acids separable by the difference in solubility of their barium salts the less soluble separating with 1 mol.H,O as a crystalline powder. Its potassium salt crystallises with 1 mol. H,O in pointed prisms the acid chloride in rhombic tables melting at 96" and the arnide in minute prisms melting at 224". This acid is iden- tical with one obtained by Hgkausson from the mother-liquors of potassiiim a-toluenedisulphonate. The more soluble barium salt crystallises in prisms containing 3& mols. HpO the chloride in trun- cated prisms melting at 95" ; the amide melts at 214". This acid is identical with one obtained by Limpricht from toluidinedisulphonic acid. V. H. IT. Cumene-orthosulphonic Acid and Orthocumic Acid. By A. CLAUS and J. A. SCHULTE IM HOF (Ber.19 3012-3017) -When cumene-P-sulphonic acid (Abstr. 1885 903) is oxitiised with chromic mixture. it is destroyed without formation of intermedidte products ; it is therefore concluded that the acid has the constitution [C3H7 S03H = 1 21. Orthocumic m i d CHMez*C6H4*COOH is obtained by fusing the potassium or barium salt of the above sulphonic acid with sodium formate ; it is insoluble in cold water readily soluble in alcohol ether glacial acetic acid &c. When heated at 200° it becomes brown and partly sublimes and does not melt a t 300". It distils with steam. The barium and caZcium salts (each with 2 mols. HzO) and the nzagnesium salt (with 6 mols. H,O) crptallise in needles readily soluble in water. The alkali salts are crystalline but Fery hygroscopic. The chloride forms a yellow oil readily soluble in ether chloroform &c.; when treated with dry ammonia it is converted into the nmide. The latter crystallises from alcohol in small needles melting a t 124" (uncorr.) . Orthocumic acid is not acted on by chromic mixture of ordinary strength. When oxidised with potassium permanganate it is con-ORGASIC CHEMISTRY. 2 fi5 verted into phthalic acid; no hydroxycumic acid is formed. The reaction is of interest as showing that the reaction by which isopropyl in paracumic acid is oxidised to hydroxyisopropyl does not hold good when the isopropyl-group is in the ortho-position to carboxyl (R. Meyer Abstr. 1878 878). Action of Aldehydes Anhydrides and Diazo-compounds on the three Methylindoles. By E. FISCHER (Ber. 19 2988-2991).-When benzaldehyde (1 part) is heated with methylketole (2 parts) at loo" an almost quantitative yield of be~azyli~enemethy172etole Ph-CH (C9H,N) is obtained. This substance crgstallises well from acetone and most probably has the constitution N. H. M. With paraldehyde and zinc chloride methylketole yields a crystalline compound soluble in hot alcohol and in acetone. 1' Methylindole combines slowly with benzaldehyde a t loo" the reaction however is hastened by the addition of a small quantity of zinc chloride; the product crystallised from acetone melts at 197" and is isomeric with that obtained from methylketole. Skatole and benzaldehyde on the contrary combine only slowly in the presence of zinc chloride a t 100" and the resulting compound which forms colourless crystals differs from the preceding derivatives in its much greater solubility and lower melting point.Equal parts of phthalic anhydride and rnethylketole heated a t 100" with zinc chloride yield a compound C9HgN.C8H4O3 which when heated to about 200" is converted into an acid C9H8N*CO*C6H4*COOH with loss of carbonic anhydride. From I' methylindole at 100" a com- pound having different properties is obtained. The action of acetic anhydride on methylketole in the presence of sodium acetate has already been studied (Abstr. 1881 734) ; since however the acetyl derivative reacts with phenylhydrazine to form a compound CI7Hl7N3 and is therefore a ketone Jackson's formula C6&<NAc>CMe must be regarded as incorrect ; the substitution of acetyl GCcurring probably in the position 3'. When 1' methylindole is heated a t lo()" with acetic anhydride and zinc chloride a ketone is obtained which is probably identical with Baeyer's acetylindole (Abstr.1879 938). Methylketole readily reacts with diazobenzene chloride in the presence of acetates dissolved in weak alcohol and forms an azo-compound of the composition C6H5*N N.C9HsN. It crystallises in yellow needles melts at 115-116" and by reduction with zinc and hydrochloric acid CH yields aniline and amidomethylketole. w. P. w. Hydrocarrotene and Carrotene. By F. REINITZER (iUonat&. Qhem. 7,59'7-608).-Two crystalline substances have been extracted from carrots the one colourless hydrocarrotene the other dark red carrotene ; these have been more recently examined by Huseman and Arnsud the latter of whom has found carrotene associated with chlorophyll in the leaves of various plants and assigns to it the formula2 66 ABSTRACTS OF OHEMTCAL PAPERS.of an unsaturated hydrocarbon c26H38 whilst hydrocarrotene is con- sidered to be allied to cholesterin. The method used for the extraction of these substances is fully described as also their separation from one another by frequent recrystallisation from boiling acetone and methyl alcohol. Hydro- carrotene is insoluble in water sparingly soluble in cold more readily in boiling alcohol very soluble in acetone from which it crystallises out in long needles but from methyl alcohol in micaceous leaflets. I t contains 5 per cent. of water melts at 137.4" ; [a]= = -37*4" t = 21" C = 4.131 in chloroform.I n these physical properties as also in various chemical reactions it resembles cholesterin a view further coilfirmed by the formation of its acetate and benzoate the melting points and specific rotatory powers of which at*e compared with those of other cholesterins. Hydrocarrotene appears t o be more nearly identical with phytosterin although i t is thought advisable for the present to retain its particular name. From cholesterin itself hydro- carrotene differs in its behaviour with bromine which is a t first absorbed and subsequently the change is accompanied with evolution of hydrobromic acid. The bromide formed crystallises in long colourless transparent needles moderately soluble in alcohol readily soluble in ether and carbon bisulphide.Husemann's observation that hydrocarrotene is converted into carrotene by bromine is apparently erroneous. The improbability that carrotene a coloured substance is a hydrocarbon is pointed out although no experiments are described but allusion is made to the similarity of carrotene to a colouring matter present in the paradise apple Lycopersicum esculentum. Diphenylmetaxylylmethane and Diphenylorthoxylylme- thane. By W. HEMILIAN (Ber. 19,3061-3075).-Diphenylmetax~ZyZ- methane CHPh2*C6H3Me2 [Me Me CHPh = 1 3 61 is prepared in a manner similar to diphenylparaxylylmethane (Hemilian Abstr. 1884 321) by heating benzhydrol dissolved in pure metnxylene with phosphoric anhydride for four hours a t its boiling point. The product is treated with water and with aqueous soda and the oil dis- tilled.It solidifies when kept for a few days and is pnrified by treating a warm saturated solution in glacial acetic acid with twice the amount of ethei. and allowing it to evaporate slowly. It forms large six-sided prisms which melt a t 61.5" and distil above 360". It dissolves readily in alcohol ether benzene &c. When boiled for a long time with chromic mixture and the product extracted with boiling soda solution an insoluble residue i8 obtained consisting of dipl~enylmethy~l~thal~de CPh2<- ha&- _> ; this crystallises from alcohol in lustrous prisms which melt at 147Oand distil a t above 360" without change ; it is soluble in ether benzene &c. insoluble in aqueous alkalis. MethyZtr~p~~enyl~~~ethaneearbory7~~ acid CHPh2*C6H3Me*COOH is obtained by boiling diphenylmet,hylphthalide with alcoholic soda solution and reducing the sodium salt of the hydroxy-acid so formed by boiling with zinc in alkaline solution.It forms large lustrous tabular crystals which melt at 203" and distil without change. It is v. H. v. C €3 MeORGANIC CHESIISTRY. 267 rather readily soluble in hot alcohol ether and acetic acid. The bariihm salt (with 3 mols. H,O) crystallises in slender needles almost insoluble in water rather readily soluble in boiling 70 per cent. alcohol. Other salts were prepared. When carefully oxidised it is reconverted into diphenylmethylphthalide. When the solution of the acid in strong sulphuric acid is poured into water a precipitate is obtained consisting of meth ylpheizy Zanthranol C2,H160.It crystallises from alcohol in small yellow plates which soften a t 150" and melt at 170" ; when oxidised it is converted into methy~henylhydroxanthranol C6H&te< -CO.CoH,->. The latter forms large colourless prisms melting at 213" ; it is insoluble in aqueous alkali; the solution in sulphuric acid has an intense purple-red colour. When distilled with an excess of alkali paramethyltriphenylmethane is obtained identical with that prepared by E. and 0. Pischer from phenylparatolglcarbiiiol and benzene (Abstr. 1879 384). Dip hen y lp h t ha lidecarb oxy 1 ic acid 0 < !:;:> C6H3- C 0 OH is con- tained as sodium salt in the alkaline extract from the oxidation experiment with diphenylmetaxylylmethane. It crystallises from warm alcohol in large tabular crystals (with 1 mol.EtOH) ; it is insoluble in water readily soluble in alcohol ether benzene &c. ; it melts a t 228" and distils unchanged. The calcium salt (with 3 mols. H20) crystallises from 70 per cent. alcohol in slender lustrous needles ; the silver salt crystallises from the same solvent in hair-like needles insoluble in water. When the acid is distilled with excess of baryta benzophenone and barium isophthalate are formed. Tripheny Zmefl~a~edicarboxyl~c acid CHPh2*C6H3(COOH) [ =1 2 41 is prepared by the action of zinc-dust on the alcoholic solution of the anhydro-acid. It forms slender lustrous needles readily soluble in alcohol and acetic acid. It melts a t 2 B 0 and partly sublimes a t a higher temperature. The calcium salt (with 2 mols. H20) forms matted micro- scopic needles ; the barium and silcer salts are also described.When distilled with excess of haryta it is converted into triphenylmethane. Diphenylortho-xylylmethane C6H3Me2*CHPh2 [ 1 2 51 was prepared fi-om ortho-xylene (from orthobromotoluene). It crystallises in long lustrous needles melts at 68.5" and distils at above 360". It is readily soluble in alcohol ether benzene &c. When oxidised with chromic mixflure a mixture of acids is obtained but no indiiferent phthalide-derivative. When the mixed acids are treated with potas- sium permanganate triphen ylcarbinol-dicarboluy lic acid OH*CPh,*C6H3(COOH) is formed. The latter forms silky matted slender needles very readily soluble in alcohol ether and glacial acetic acid rather soluble in boiling water and sparingly soluble in benzene.The salts with the exception of the alkali salts are very sparingly soluble. The acid melts a t 180" with effervescence and is converted into the anhydride Cz,Hl40,. This is a transparent amorphous substance readily soluble in alcohol ether and benzene. Boiling water has no action on it. When the acid is distilled with an excess of baryta it is converted into triphenylcarbinol. N. H. M. C Ph (0 H)268 ABSTRACTS O F CHEMICAL PAPERS. Diamidostilbene and Diamidostilbenesulphonic Acid. By p. BESDER and G. SCHULTZ (Ber. 19. 3234-3239).-By reducing ortho- nitrotolueneparasulphonic acid Neale obttined an azosulphonic acid which when treated with stannous chloride yielded R compound which he described as hydrazotoluenesulphonic acid (Abstr.1880 806). The authors show that this compound is toluiclinedisul phonic acid as it yields toluidine when distilled with lime DinmidostilbenePul~honic acid is obtained by dissolving 50 grams of sodium paranitrotolueneortho- sulphonate in boiling water gradually adding 100 C.C. of 33 per cent. soda solution. The soliition is diluted 50 grams of zinc-dust are then gradually added and the whole boiled until the colourless solution no longer becomes coloured on exposure to air. It is filtered preci- pitated with hydrochloric acid again filtered and dried. It is almost insoluble in water. The salts are readily soluble. When distilled with soda-lime i t yields stilbene. The base obtained by Klinger by the action of zinc chloride on the condensation product from paranitro- toluene and sodium methoxide (Bey.16 943) and described by him as diamidnbenzyltoluene is shown by the authors to be diparamido- stilbene ; the same base was also prepared by the reduction of dinitro- stilbene from paranitrobenzyl chloride. The properties of the base are as described by Klinger (loc. cit.) except that the acetyl-deriya- tive melts a t 312" (not 212'). By combining tetrazostilbene chloride with 2 mols. of a-naphthol- sulphonic acid a blue-violet dye is formed. With /3-naphthol- disulphonic acid (R) a-naphthylaminesulp honic acid and salicylic acid (each 2 mols.) blue red and yellow azo-dyes are formed respec- tivel y. N. H. M. By A. CLAUS and M. ERLER (Ber. 19 3149-3156).-Bromine even in the nascent state acts exceedingly slowly at ordinary atmospheric temperature on diphenic acid but a t 60" and upwards reaction takes place readily.If less than 2 mols. of bromine are employed to 1 mol. acid a part of the acid remains unacted on. At temperatures from 60-120° the product consists of a mixture of bromodipheiiic acid aiid bromodi- phenic acid dibromide ; at temperatures ranging from 120-3OO" part of the latter derivative is converted into dibromodiphenic acid and above 200" only mono- and di-bromodiphenic acids are found in the product of bromination. Bromodip henic acid CO OH*CsH4*CGH3Br*C 0 OH crys tallises in acicular prisms melting a t 235-236" (uncorr.). I t is not volatile in steam and sublimes only with considerable decomposition the small sublimate (melting slightly lower than the acid) appearing to be the anh7ldride.The acid is very sparingly soluble in boiling water easily in alcohol ether and benzene. The neutral and acid sodizcm salts are very soluble the brcrium (with 3H,O) silver and copper neutral salts are very sparingly soluble in water. The ethyl salt forms crystals melting at 65" (uncorr.). Bromodiphenic acid dibromide is Brominated Derivatives of Diphenic Acid.ORGANIC CIIE \lISTRT. 269 always formed (sometimes to the extent of 15 per cent.) in the bromi- nation below 200" of diphenic acid but its production from the bromo- acid already formed appears only to take place to a very slight extent. It is sparingly soluble in alcohol and cold chloroform and crystal- lises in colourless glistening needles having a very bitter taste.It turns brown a t 200° and melts at about 256" (uncorr.) with decom- position. Heated in closed tubes a t 200" it undergoes decomposition di bromodiphenic acid being formed. The dibromide is very sparingly soluble in the usual solvents but dissolves readily in alkalis and alkaline carbonates to form solutions of unstable salts which especially when warmed rapidly decompose into salts of dibromo- diphenic acid. It is soluble in concentrated sulphuric acid and in fuming nitric acid and is reprecipitated unchanged on the addition of water. The neutral sodium salt forms glistening scales but its solution is rapidly decomposed if boiled. Dtbromodiphenic acid ClzH6Br2(COOH) is easily soluble in alcohol ether and glacial acetic acid.It crystallises in needles melts a t 245" (uncorr.) and is not volatile in steam. It sublimes with diffi- culty yielding the anhydride. Its alkali salts are easily soluble the calcium (with 3H20) silver and lead salts sparingly soluble. The ethyE salt is crystalline and melts at 105-106". This dibromodiphenic acid is evidently isomeric but not identical with that (melting a t 295" obtained by Ostermayer Ber. 7 1091) from dibromophen- ant hraquinone. When the bromo-acids are subjected t o dry distillation with lime brominated diphenylene ketones are formed. Bromodiphenylene EetoNe CI2H,Br CO forms yellow scales melting a t 122" (uncorr.) and is easily soluble in alcohol ether benzene &c. very sparingly in wster. When heated with zinc-dust it yields flnorene.No hydroyen sodium sulphi te compound could be obtained. Uibromodiphenyleae ketone forms yellow scales melting a t 133" (uncorr.). p-Naphthol-p-Disulphonic Acid. By A. CLAUS and 0. SCHMIDT (Ber. 19 3172-3179).-The authors have endeavoured to determine the constitution of this acid by the action of phosphoric chloride on it. The material used was the commercial sodium salt (the so-called G-salt). Reaction takes place readily but if only the temperature of the water-bath is used p-naphtholdisulphonic chloride is produced. This is a thick reddish-brown liquid and neither it nor the corresponding amide could be obtained in a crystalline form. If the sodium salt is heated at 100-200° with more than two inolecu ar proportions of the pentachloride the principal products are ethereal phosphates corresponding with those obtained by Clans and Zimmermann from @-naphtholsulphonic acid (Abstr.1881 914). If the reaction is carried out above 200" (nnder pressure) and with R large excess (5 mols.) of the pentachloride dichloronaph tho1 and tri- chloronaphthalene are formed. The yield is however small 100 grams of salt only yielding about 6 to 8 grams of chloro-derivatives. Dichloronaph t halene (probably from impurity of rnonosulplionate in the salt) and tetrschloronaphthalene are also alaays present in small L. T. T. VOL. LIT. t270 ABSTRACTS OF CHEMICAL PAPERS. quantity. The dichloronaphthol is easily isolated as it alone of the products is soluble in alkalis. It cryatallises in colourless needles which melt at 125' (uncorr.) and sublime with partial decomposition.It is moderately soluble in boiling water easily in alcohol ether &c. The trichZol.o?zaphthnZene is readily soluble in ether benzene chloroform glacial acetic acid and boiling alcohol. It cryatallises in white needles melts at YO" (uncorr.) and may be sublimed. It is not identical with the trichloronaphthalene of the same melting point obtained by Claus and Knyrim (Abstr. 1886 156). When heated with dilute nitric acid at 210° it yields a dichlorophthalic acid a yellow syrup which could not be obtained in a crystalline form. The potassiunt sodium and barium salts are easily soluble the silver salt sparingly soluble the lead salt insoluble. This acid is being further investigated. When heated with chromic acid in acetic solution the trichloronaphthalene yields a trichloronaphthapuilzone which how- ever is very readily further oxidised to a chlorinated phthalic acid.Attempts to separate the quinone from the unchanged trichloro- naphthalene were unsuccessful but alkalis removed it in form of a salt of a chlorinated hydroxyquinone. The best result was however obtained by treating the mixture with aniline when dichloronayhthn- quinone anilide CloH,C1,O,*NHPh was obtained. This is almost insoluble in water sparingly soluble in ether. It crystallises in dark reddish-violet scales melts at 228" and may be sublimed. The formation of this anilide by the displacement of a chlorine-atom (the corresponding quantity of hydrochloric acid being formed) leaves no doubt that the original quinone is a trichlorinated compound.But as experience teaches that if in a chlorinated naphthalene a chlorine-atom is present in the a-position that chlorine-atom is expelled in the formation of an a-naphthaquinone the above tri- chloronaphthalene must have the constitution [Cl = 2 3 2'3. Which of the chlorine-atoms represents the hydroxyl and which the sulphonic groups in the original acid cannot yet be decided. By L. CLAISEN (Ber. 19 3316-3320).-When a-naphthol is treated with benzaldehyde a white pulverulent compound benxaZdi-a-naphthol CHPh(C,oH6*OH)z is ob- tained which turns brown on exposure to the air and dissolves readily in alkalis t h e alkaline solution assuming a dark reddish-violet but unstable colour when oxidised. The reaction however proceeds differently when P-naphthol is treated with benzaldehyde.When an acetic acid solution of the two t o which a few drops of hydrochloric acid has been added is main- tained at a low temperature benzalglycoldina~hth ylacetal CHPh(OCioH,)z separates as a crystalline compound melting at 203-205" and sparingly soluble i n ordinary solvents almost insoluble in aqueous alkalis. Heated with acetic acid and a few drops of hydrochloric acid a t looo it is converted into benzaldi-clAaphthyl oxide L. T. T. Action of Aldehydes on Phenols.ORGANIC CHEMISTRY. 271 this melts at 189-190° crystallises well and is insolubIe in alkalis. Benzaldi-naphthyl oxide is also obtained when the acetic acid solution of benzaldehyde and P-naphthol with a little hydrochloric acid or sulphuric acid is heated at looo or in Che absence of the acids a t 200".The author has also obtained results which are not in complete accordance with those published by Claus and Trainer (this vol. p. 231) and points out that the ethylidenediphenol described by them has already been prepared by Fabinyi (Ber. 11 283). With acet- aldehyde p-naphthol yields compounds similar to those formed when it is treated with benzaldehyde; thus either ethylidenedinaiul~thnJlacetal C2Ha( OC10H7)2 melting at 20O-2Ol0 or ethyZidene-P-dinaphtl~?/Z oxide C2H (C10H6)2 0 melting at 173" is obtained ; both crystallise well and are insoluble in alkalis. The compound described as dinaphthyl- acetal by Claus and Trainer but melting at 162-163" was not obtained in the author's experiments. The remainder of the paper is devoted to a theoretical discussion in which the author states his views as to the cause of the difference in behaviour of a- and p-naphthol under these conditions and arrives at conclusions at variance with those put forward by Claw and Trainer (loc. cit.).w. P. w. a-Naphthyl Methyl Ketone. By A. CLAUS and P. FE~ST (Ber. 19 3180-3182) .-The authors have also independently obtained this ketone lately described by Pampel and Schmidt (this vol. p. 252) but some of their results differ from those of the latter authors. They find that the ketone solidifies if cooled below O" and the crystals then melt at 34". They find the melting point of the acetosime to be 145" (uncorr.) that of the hydrazine 173" (nncorr.). When this ketone is treated in the cold with a dilute aqueous solution of the theoretical quantity of potassium permanganate a-naphthylglyoxylic (a-naphthoylformic) acid CloH7"*CO*COOH is formed.This acid is a thick oil which only solidifies slowly and with difficulty. It is very unstable and is easily oxidised by dilute nitric acid or warm permanganate to a-naphthoic acid and carbonic anhydride. The calcium and barium salts (each with 4&H,O) are easily the silver salt very sparingly soluble. The formation of a-naphthoic acid proves this acid to be an a-naphthyl-derivative. It is probably identical with Bossneck's acid melting at 113.5" (Abstr. 1883 808) ; the diEculty experienced in crystallising it being in all probability due to traces of oily impurity. Pyrene. By E. BAMBERGEK. and M. PHILIP (Ber.19 3036-3040). - Nuphthalenetetracarboxytic diunh ydride C14H406 is obtained by slowly heating naph thalenetetracarboxylic acid (Abstr. 1886 948) t o 150-170" or by recrystallising the acid from glacial acetic acid. I t does not change when heated at 300° at a higher temperature it sublimes in lustrous needles an inch long. When naphthalenetetra- carboxylic acid is suddenly heated to 200-250" it is converted partly into the anhydride and partly into naphthalenetricarboxylic acid. L. T. T. t 22 72 ABSTRACTS OF OHEXICAL PAPERS. ~~2)l~thalenetetracarbozylic diirnide Cl4H6OPN2 is formed when the anhydride is treated with aqueous ammonia and separates in groups of branched needles. It is very sparingly soluble does not alter in appearance at 270" and sublimes at a higher temperature in yellow lustrous needles. The formation of the above dianhydride and diiinide shows that the two pairs of carboxyl-groups in naphthalene- tetracarboxylic acid have the ortho-position. Pyrene ketone CuH80 crystallises from alcohol in gold- coloured lustrous plates melting at 142" ; when oxidised with potassium per- nianganate it ia converted into Behr and Van Dorp's naphthalic acid (Annalen 172 266).N. H. &I. Terebenthene - derivatives. By PESCI and BETTEILLI (Arch. Pharm. [3] 24,1037) .-The preparation of the hydrocarbodn phelland- rene of nitrophellandrene phellandrendiamine and amidophellandrene from OZeum phellandrii was recently described (dbstr. 1886 1038). Subsequently by similar treatment with nitrous acid lmvorotatory terehenthene has yielded a dextorotntory nitroterebenthena CloH15*N02 from which nascent hydrogen produces the primany baee amidotere- benthene C,HI,*NH2 which again is lmvorotatory.J. T. Formation of Euxanthic Acid from Euxanthone by the Animal Organism. By S. v. ROSTANECKI (Ber. 19 291%-2920).- Spiegel has proved that euxanthic acid is deeornposcd by concentrated snlphuric acid into euxanthone and glycuronic aoid. From the phenolic character of euxanthone and the fact th& the magnesium salt of euxanthic acid known as Indian-yellow is prepared from urine the autbor has endeavoured with success to form euxanthic acid from euxanthone the glycuronic acid being supplied by the animal system. If euxanthone be administered to a dog the presence of euxanthic acid can be detected in the urine by means of its magnesium salt.This result is analogous to the conversion of phenol or naphthol into their corresponding glycuronic acids by the animal organism. V. H. V. Kamala. By A. G. PEREIN and W. !K. PERKIN sun. (Ber. 19 3109-3110).-Kamala a yellow dyestuff i u used in considerable quantity by the nativerJ (of India. I t is contained in the seed capsules of MaZZotus phiZZipensis and occurs in commerce as a yellowish-brown powder whieh under the microscope is seen to consist of transparent brown resinous globules mixed with woody fibres and seeds ; no crys- tals were observed. NaZZotoxin CllH1003 or CleHlsOa was obtained by shaking finely- divided kamala with carbon bisulphide concentrating the yellowish solution on the water-bath treating the yellowish-brown precipitate obtained with small quantities of carbon bisulphide to remove resinous impurities and finally crystallising from benzene or toluene.I t forms small flesh-coloured needles soluble in alkalis to a yellowish-red solu- tion from which acids reprecipitate the original substance ; it is nearly insoluble in water readily soluble in alcohol and acetic acid. A yellowORQANlC CHEMISTRY. 273 acetyl-derivative CllH803Ac2 or C,8H,,0,Ac3 was o b i n e d experiments are in progress to determine the correct formula. Further A. J. G. Synthesis of Pyrroline. By G. GIAMICIAW and P. SIEBER(R~~. 19 3027) .-The authors showed previously (Abstr. 1884 1115) that snc- cinimide may be readily converted in to tetrachloropyrroline but were unable to completely reduce the latter to pyrroline.This can be readily effected by Hepp's method which consists in boiling the chlo- ride with the corresponding amount of potassium iodide in a reflux apparatus. The iodide so obtained is very readily reduced to pyrro- line by warming with potash solution in presence of zinc-dust. N. H. M. Behaviour of Methylketole Constitution of Pyrroline. By G. CIAMICIAN (Ber. 19 302&-3029).-Ciamicinn and Dennstedt obtained (Abstr. 1882 1214) pyridine-derivatives by the action of chloroform or bromoform on the potassium compound of pyrroline. and suggested that quinoline-derivatives could probably be obtained in a similar manner from indole. Expcriments made by the author show that quinoline-derivatives can be obtained from methylketole by means of the chloroform reaction and also by heating with hydro- chloric acid a t 200" (compare Ber.14 1341). Both methylketole and in a less degree indole show all the colour reactions of pyrroline. The author considers the relation between indole and pyrroline to be established by these results. N. H. M. Synthesis of Pyrroline-derivatives. By C. PAAL and C. W. T. SCHNEIDER (Ber. 19 3156-3163).-This is a continuation of the auhhor's previous work (Abstr. 1886 559). EChyZene-~-tetramet~yZ~~~yrro~~~ie C2H4( C4NH2Me2)2 [ C2Ha Me = 1 2 53 was obtaiiied by the action of acetonylacetone on ethylene- diamine. It crystallises with 4 mols. H20 in glistening white scales melts a t 125-126" sublimes unchanged and is volatile in steam. It is insoluble in water soluble in alcohol et,her &c.It is soluble in mineral acids with red coloration colours pine shavings carmine and gives a purple-red with Laubenheimer's reagent. It forms a yellow y la t in 01 h lor id e . Trimethylene-a-tetramefh yldipyrroline C3H6( C,NH2Me2) is formed when trimethylenediamine is substituted for ethylenediamine in the above reaction. It forms it pale yellow crystalline substance melting at 76-7io insoluble in water soluble in alcohol and ether. It resembles the ethylene compound in properties. Pctrudi~ZLe.nylene-a-tetrainethyldipllr.1.oline C,2H8(C4NH2Me2)2 from benzidine and acetonylacetone crystallises in colourless tables soluble in alcohol ether &c. It is very unstable especially when in solution. It melts at 130" and is decomposed at a slightly hipher temperature.When ethyl acetophenoneacetoacetate is wed in place of acetonyl- acetone the ethers of a series of dipyrrolinedicasboxylic acids are obtained. Et li y 1 ct hy lene-a- dimeth y ldiphen y ldip yrroline- P-dicarbox~ late CLk14(C4NHMePh*COOEt) [1 2 5 31,a 74 ABSTRACTS OF CHEI\lIOAL PAPERS. crystallises with 4H20 in glistening scales melting a t 197". It dis- tils unchanged bnt is sensitive to light. It is insoluble in water and light petroleum soluble in alcohol benzene chloroforni and glacial acetic acid. It is insoluble in hydrochloric acid but dissolves in concentrated nitric or sulphuric acid and is reprecipitated un- changed on the addition of water. It shows Laubenheimer's reaction. On hydrolysis it yields the free crystalline acid which melts at 181" and a t a slightly higher ternperatu1.e evolves carbonic anhydride forming the pyrroline-derivative C2H4( C4NH2MePh),.The acid is insoluble in most solvents very sparingly soluble in alcohol and in glacial acetic and concentrated hydrochloric acids. P-Ethocarboxyl-a-nzethylphenylpyrroline-acetic acid COOHCH,*C4NHMePh*COOEt [l 2 5 31 formed on substituting amido-acetic acid for the diamine i n the last reaction crystallises in needles melting a t 131". It is almost insoluble in water soluble in alcohol ether and benzene. It dissolves in alkalis and alkaline carbonates and forms well-characterised salts When heated with alcoholic potash it yields the free bibasic acid COOH* C H,* C4NHMePh*C0 0 H. This forms small white needles which melt at 152" with evolution of carbonic anhydride.Ethyl metaphenylene-a-dimetl~yldiphenyld~yrroline-~-dicarboxylnte C,H4 ( C,NH MeP h* C 0 0 E t). crystallises in white needles which melt at 185". It is insoluble in water soluble in most other solvents and in concentrated sulphuric acid. Ethy 1 paradipheny lene-a-dimeih y ldiphtw y la$ yrrolins- p- dicarboxy latp C,2H,(NC4HMePh*COOEt)2 from benzidine aud ethyl acetophenone'- acetoacetate crystallises in thin needles melting at 178-1 i9". When saponified i t yields the corresponding potassium salt which however resinifies easily. The free acid could not be obtained. COOH*C6H4*NCpHMePh*COOEt crystallises in small yellow iieedles melting a t 160" and soluble in alcohol ether &c. It forms characteristic salts.When heated with alcoholic potash it yields the corresponding bibasic acid which forms colourless hairy needles melting at 210". When strongly heated cai*- bonic anhydride is evolved. ~E'thocarboxyl-oc-metkylp~~ny~~ yrrolinemetnbenzoic acid Ethyl azobelzzene-oc-metky~~en~~~yr~ol~ne-~-carbo~ylnte N2Ph*C6H4*C4NHMePh*COOE t from amido-azobenzene forms deep red crystals melting a t 123". It is easily soluble in alcohol ether &c. When saponified it yields the corresponding acid which forms large red crystals soluble in ether alcohol &c. It melts a t 195" and evolves carbonic anhydride a t a slightly higher temperature. A11 these substances show Laubenheimer's reaction. L. T. T.ORQANIC CHEMISTRY. 275 Synthesis by Means of Ethyl Acetoacetate.By L. KNORR (Annalen 236 290-332).-The author has already shown (Abstr. 1885 554) that ethylic diacetosuccinate reacts with ammonia and with primary amines yielding substituted pyrroline-derivatives. A similar action takes place with hydroxylamine. By heating an aqueous solution of hgdrosylamine hydrochloride (12 parts) and sodium acetate (24 parts) with ethyl diacetosuccinate (30 parts) dissolved in glacial acetic acid the ethyl hydroxydimeth ylppyrrolhze- dicarboxyzate OH44NMe2(COOEt) is obtained as a crystalline compound soluble in alcohol and ether and in dilute alkalis but insoluble in acids. This substance melts between 98" and 100". A precipitate of the coniposition CI2H,,KN05 is obtained on adding ether to an alcoholic solution of the ethyl salt and potassium e thoxid e.A mixture of hyd~ox~dimethylpyrrolinecarboxylic acid and movethy1 hydroxydimethylpyrrolirLedicarboxylate is formed when the ethylic salt is saponified by alcoholic potash. The latter compound CloH,,NO5 crystellises in needles soluble in alcohol. It melts a t 185" with decomposition yielding ethylie hydroxydimethylpyrroline- carboxylate. Hydroxydimethy~~rrolinecnrbox~l~c acid C7H,N0 [OH Me COOH Me = 1 2 3 51 decomposes at 138" yielding hydroxydimethylpyrroline [OH Me2 = 1 2 S ] . The acid crystnllises in needles and dissolves freely in alcohol It is decomposed by prolonged boiling with water. The metallic salts are notl characteristic. The formation of the ethyl salt has just been mentioned. Hydroxydimethplpyrroline exhibits the pinewood reaction.It is soluble in alcohol ether chloroform ben- zene and alkalis. It reduces ammoniacal silver solutions at the ordinary temperature and Fehling's solution on boiling The derivatives of trimethylpyrrollinedicarboxylic acid [Me3 (COOH) = 1 2 5 3 41 phenyldimethylpyrrolinedicnrboxylic and - naphthyldicarboxylic acid have been previously described by the author (Abstr. 1885 555). These acids are decomposed when heated yielding pyrrolines. Trintethylpyrroline [I 2 51 boils a t 17$ (corr.) ; phenyldirnethyl- pywoline [ P b Me = 1 2 51 melts at 51" and boils at 252" (corr ) and P-naphthyldinzethylpyrroline [C,,,H Mez = 1 2 51 melts a t 71" and boils at 341" (corr.). These compounds are freely soluble in alcohol ether chloroform and benzene. cc- A'npht h y ld inaet hglpyn.olinedicarbox ylic acid [ C,,HVa Me ( CO 0 H) = 1 2 5 3 41 crystallises in needles and decomposes a t 2M0 yielding a-naphthyldintethylpyrroline This substance melts a t 123' boils a t 310-315" (corr.) and dissolves freely in ether alcohol and chloroform.Ethyl a-nnpht7~~l~imethylpyrrol%neclicai.~oxylate melts a t 91-92' The potassium salt C18H13K2N04 is insoluble in alcohol The barium CIBH13BaNOd and silver Cl8N1,AgK 04 salts are crystalline. E t hy 1 naet hy lp heny 1 amidodimeth2/lpyrroZiize~~~ioarboxy late is obtained276 ABSTRACTS OF OHEMICAL PAPERS. as an uncrystallisable oil by the action of ethyl diacetosuccinate on methylphenylhydrazine. The free acid Cl5H1,N2Oa crystallises in prisms and decomposes at 231" into carbonic anhydride and methyl- pheizylamidodimethyl~rroline CI3Hl6N2 a crystalline aubstance which melts a t 41" and boils at 310" (corr.).Et h,yl metarnidotoly ldirn et h y 1pyrroEinedica doxy late is formed by boiling equivalent quantities of metatoluylenediamine and ethyl diacetosuccinate in acetic acid solution. The ethyl salt crystallises in prisms and melts at 134". The free acid Cl5H,,N?Oa + 3H20 crystallises in plates of a yellow colour. It is soluble in alcohol ether acids and alkalis. It decomposes a t 203" yielding rneta?nidotolyl- dzmethylpyrroline. This compound nielts at 73" and boils a t 322" (corr.) It is soluble in alcohol ether and acids and volatilises in a current of steam. Ethyl toluylenedidimethylpyrroliiaedicarbox~late is obtained as a heavy oil by the action of metatoluylenediamine (m.p. 99') on excess of an acetic acid solution of ethyl diaceto- succinate. The free acid C23Hz2N208 is sparingly soluble in alcohol and ether and insoluble in water and dilube acids. It melts at 248" with decomposition. D inz et h y lp y wolinedicarbox y lacetic acid C,HllNO = C,N~e,(COOH),.CH,.COOHE [2 5 3 4 11 splits up a t 214O yielding carbonic anhydride and an oily liquid probably diinef h y l p yrolin e- acetic acid C4RHzMe2*C H,*CO 0 H. The acid forms crystalline potassium and silver salts Cl,HLKK,N06 and (=10&,Ag206. The ethyl salt is prepared by boiling an acetic acid solution containing equivalent quantities of glycocirie and ethyl diacetosuccinate. Ethyl dimeth?/~yrrolinedicarboxylate C4NHXe,(COOEt),[2 :4 3 51 is most conveniently prepared by adding a strong solution of sodium nitrite (2 parts) to 7 parts by weight of ethyl acetoacetate dissolred in strong acetic acid.25 parts of zinc-dust is added to the well- cooled pioduct. On adding water to the mixture the ethyl salt is deposited in needle-shaped crystals. This substance melts a t 134- 135" and is distinguished from its symmetrical isomeride by the absence of basic properties. Many of the properties of this compound and of its derivatives have been already described by the author (Abstr. 1884 1368). MonethgldimethyIpyrrolinedicarboxylate niel ts with decomposition at 202" (not 200" as previously stated) forming e thy1 d imethy~py~rolineerboxylate Dimetbylpyrrolinedicarboxylic acid decomposes a t 260" into car- bonic anhydride and dimethylpyrroline [Me Me = 3 41 (Zoc.cit.). B t h y l dimeth y Zp yrrolineanilidocarhoxy late COOEt-C1?SH1\Ie,*CONHPh [5 2 4 31,ORGANIC CHEMISTRY. 277 is formed by the action of zinc-dust on equivalent quantities of aceto- acetic anilide and ethylic nitrosoacetoacetate dissolved in acetic acid. It melts at 216" and dissolves in hot alcohol and acetic acid. On treatment with strong sulphuric acid it yields 2 4 dimethylpyrroline and on boiling with alcoholic potash it is converted into the monaidide of difiwth y lpyrrolinedicrtrbox~lic acid C 0 0H.C ,NH*Me2*C ONHP h. This substance softens a t 180" and decomposes a t 198". It also splits up when boiled with dilute siilphuric acid yielding carbonic anhydride and dimeth y1pt~rrolinecarbox~la?~zlide C,NH,Me,*CONHPh. Ethyl d~rrcethylpyr~olineai~ilidocurboxylate [Me2 COOEt CONHPh = 2 4 3 51 is prepared by reducing with zinc-dust an acetic acid solution of ethylic acetoacetate and nitrosoacetoacetic anilide.It crystallises in needles melts a t 180" and yields 2 4 dimethyl- 1)yrroline on treatment with sulphnric acid. Dimethy lp yrrol hedicarboxy lanil i d e C4NH*Me2(CONHPh) [2 4 3 51 is formed by reducing a mixture of the anilides of acetoacetic and nitrosoacetic acids. It melta about 255" and mystallises in needles. It also yields 2 4 dimethyl pjrroline when warmed with sulphiirio acid. Action of Chlorine on Pyridine. By E IT. KEISER (Amer. Chem. J. 8 308-315).-Ande1-son has worked on this subject (AnnuZen 105 340). When anhydmus pyridine is treated with dry chlorine it finally solidifies and by distillation a white crystal- line solid boiling at 130" and a yellow solid boiling a t 218" are obtained.The first is purified by crystallisation from alcohol; it melts at 72" is very stable and with platinuim chloride gives a pre- cipitate having the composition (C,H,CI,N) ,,H,PtCl,. The second substance cannot be distilled withoat partial decompositioil ; it is very deliqixescent and is soluble in water ; with platinum chloride the solution gives a precipitate of pyridine platinochloride ; the yellow compound itself baa the composition C5HSNC1 and is evidently an unstable additive product. When chlorine is passed into pyridine diluted with its own bulk of water nitrogen and carbonic anhydride are evolved and on further dilution a white precipitate is thrown down which when dry smells like bleaching powder and with platinum chloride give3 a precipitate of pyridine platinochloride; i t is therefore an additive product of pyridine probably the hypochlorite and the carbonic anhydride and nitrogen are derived from the decomposition of this substance. When chlorine is passed into a pyridine solution containing free alkali nitrogen is evolved with explosive violence but if the con- tents of the flask be kept cool the action is more gentle and chloro- form and dichloracetic acid are to be found in the distillate.Thiq decomposition of pyridine by chlo~ine is far more readily explained by Riedel's formula (Abstr. 1883 1152) than by KGrner's. w. c. w. H. B.Tetrahydropicoline. By A. LIPP (Bey. 19 2843-2844) .-The base obtained by the action of alcoholic ammonia on w-bromobutyl methyl ketone (Abstr. 1886 219) proves to be a tetrahydropicaline,278 ABSTRACTS OF CHEMICAL PAPERS. probably CH2<g2-:ze>CH. Under similar conditions a pyrro- line-derivative is obtained from w-bromopropyl methyl ketone. w. P. w. Quinolinesulphonic Acids. By A. CLAUS and P. KCTPNER (Ber. 19 2886 -28Y6) .-Quinolineorthosulphonic acid i n cooled. aqueous solution forms a yellow crystalline precipitate with bromine an unstable probably additive compound ; at the temperature of the water-bath the acid is decomposed with formation of tribromo- quinoline which separates in glistening silky needles melting at 198" soluble in ether and alcohol insoluble in water.Quinolineparasulphoiiic acid under similar conditions yields a dibro- moquinoline crystallising in long needles melting a t 124-126" and yielding on oxidation with potassium permanganate a bromopyridine- dicxrboxylic acid identical with that described by Claus and Collischon. On adding more than two molecular proportions of hromine a tribromoquinoline is slowly produced isomeric with the compound described above. It crystallises in long silky needles melting at 170° and is sparingly soluble in cold ether soluble in alcohol. As regards the displacement of the sulphonio group concen- trated nitric acid resembles bromine in its action a mononitro- quinoline being produced. V. H. V. Reduction of Hydroxylepidine and Methyllepidone. By I;. KNOKR and C.KLOTZ (Bey. 19 3299-3303). -Hydroxylepidine arid methyllepidone resist the action of acid reducicg agents but are readily attacked and reduced by sodium arnalgam and alcohol or by sodium and alcohol. Reduction of HTycl,.oxyZe~idi~ze.-When hydroxy lepidine in alcoholic solution is shaken with an excess of sodium amalgam a compound (CloHloNO) is obtained insoluble in water alkrtlk and alcohol but crystallising from acetic acid in slender needles melting a t 280". It shows feebly basic properties and is most probably a diquinolyl- derivative. The reluction proceeds further when metallic sodium is employed and from the product after removal of the alcohol two compounds are obtained one of which tetrahydrolepidine CIIH13N is separated by distillation with steam.It is a colourless strongly refractive oil has a pungent odour and boils at 250-253" (thermometer iumersed in the vapour) at 740 mm. pressure. Dihydroh ydmzylepidijze CloHl,NO separates in needles from the residual liquor left after steam distil- lation melts at 101" and is insoluble in alkali sparingly soluble in water readily soluble in alcohol ether and chloroform. It shows feebly basic properties and its salts are decomposed by water. Nitrous acid is without action in the cold but on warming acts on it and forms an acid compound. 8ed.uctiol.L of MethyIlepidone.-Sodium amalgam reduces methyl- lepidone in cold alcoholic solution to the diquinolyl-derivative (C1,HIsNO) (this Val p. 159). It is insoluble in water alkalis and alcohol solublo in acetic and hydrochloric acids and melts at 268".When metallic sodium is employed as the reducing agent,ORGANIC CHERIISTRT. 279 dimethyltetr~hydro~ui~ioline Cl1HI5N is obtained. It is a colour- less oil speedily turning brown when exposed to air boils a t 255" (thermometer immersed in vapour) at 757 mm. pressure and is identical with the base obtained by the reduction of lepidine meth- iodide with tin and hydrochloric acid. It yields a yellow platino- chloride and an oily orange-red nitroso-compound. Redmtlon of Carl~ostyi-L'l.-Tetrahydroquinoline is obtained when carbostyril in alcoholic solution is reduced with metallic sodium. By L. REHER (Bw. 19 2995-3002). -When quinoline ethiodide is heated atl 280-290" for two hours a somewhat complicated reaction takes place resulting in the formation of hydrocarbons in addition to basic products.After acidifying the product is distilled with steam to remove the hydrocarbons then ren- dered alkaline and again steam-distilled. The mixture of bases SO obtained is fractionated and the portion boiling bet ween 240 and 280" after removing the unaltered quinoline is repeatedly fractioned ; in this way fractions boiling a t 255-260" and 270-275" are obtained which consist of a- atid yethylquinoline respectively but by this method the only feasible one a complete separation cannot be effected. u-Ethylpuiizoline is a very hygroscopic colourless liquid with a quinoline-like odour does not solidify a t low temperatures and is slightly soluble in water readily soluble in ether alcohol chloroform and carbon bisnlphide and quickly becomes coloured red on exposure to light.The hydrochloride and nitrate are readily soluble in water and effloresce in air. The rrzercuriochloride Cl1Hl1N,HHgCl3 melts at 118" and forms slender white needles ; the platinochloride (Cl,HllN)z,H,PtC16 melts at 190" and crystallises in dense tables ; the aurockloride C,lHl,N,HAuC14 melts a t 142" and forms canary-yellow needles ; the picrate CIIHllN,CsHz( N02)3*OH melts a t 146 -147" and crystallises in long yellow needles; and in addition a crystalline sfmmocldoride ( Cl,H11N)2,H2SnC14 + 2H20 and an oily chromate and zinc salt are described. On oxidation an acid was obtained agreeing in its properties with quinaldinic acid. Tetrahydro-ac-ethy ZyuirroZine Cl1H1,N is formed when a-etliylquinoline is reduced with tin and hydrochloric acid.It boils at 259-263" and resembles the parent base in appearance and odonr. The hydroclbloride crystallises in white needles which remain unaltered in air. The fraction boiling between 270" and 275" consisting chiefly of -1-ethylquinoline contained a diethylquinoline which was separated by means of its mercuriochloride ; this salt CSH,NEt,,HHgCl melts at 116" and crj stallises in needles. y-Ethylpuinoline resembles the a-base in appearance and odour and its salts show a great similarity to those of a-ethylquinoline but have a. higher melting point. The hydrochloride is very soluble in water and is deliquescent ; the Initrate C11HllN,HNOs melts a t 1 1 5 * 5 O and crystallises in white needles which become brown on exposure to air and are soluble in water and alcohol.The mercuriochloride CllHllK,H HgCl melts at 154" crjstallises in white needles and is readily soluble in water containing w. P. w. a- and 7-Ethylquinoline.280 ABSTRACTS OF CHE&IICAL PAPERS. hydrochloric acid ; the platinochloride (CllHl,N)z,H,PtC16 nielts at 204" and forms brown leaf-like crystals ; the picrate nielts a t 178- 186" with decomposition and forms long yellow needles ; and the aurochloride ClIH11N,HC1(A~C13)z forms slender yellow needles. The methiodide nielts a t 149" and formed yellow crystals. On oxidation cinchonic acid is obtained. y-Ethylyuinoline on reduction yields a base boiling between 271" and 275" the hydrochloride of which is not crystalline. ty-Ethy lquinolinssulpli onic acid C11HloN*S03H is obtained by heating y-ethylquinoline a t 260" with 10 times its weight of fuming sulphuric acid.It forms slender lustrous needles melts above 315" and is insoluble in alcohol but readily soluble in hot water. The hydrocarbon separated from the ethyl bases by steam distil- lation was fractionated and from the lowest fraction 210-240" white crystals were obtained which had a strong naphthalene-like odour By E. V. BRCCKE (Monatsh. Chem. 7 617-620).-It has long been known that guanine when evaporahed with nitric acid gives a yellow residue soluble in potash with yellow coloration ; the solution thus obtained on evaporation to dryness gives at first a purple then a violet coloration ; 011 exposure to air the original colour returns. In this paper it is shown that these changes are due not to the so-called metachroniatism but to the proportion of water present; thus there exist two compounds the one golden-red with the greater the other indigo-blue with the less proportion of water.It is not improbable that an intermediate purple-red compound is also formed. Experiments confirmatory of this view are described in which the eoloured solutions are exposed to conditions of the presence and absence of water respectively. Opium Alkaloids. By P. C. PPJJGGE (Awh. Phurrn. [3] 24 90:3-1014) .-Morphine codeine theba'ine papaverine narcotine and narceine are the most important opium alka€oids. Their physio- logical action varies from strongly narcotic or sleep-inducing to strongly exciting. or cramp-producing bvlt different observers are not agreed as to the exact order of the members of the series.In the arringement of the bases according to their poisonous nature different observers are more nearly in accord. The author exa- mined the reactions of salts of these alkalo'ids with alkaline salts of organic acids. Morphine codeine and theba'ine in neutral liquids react strongly alkaline to litmus and afford stable salts. Narcotine papnrerine and narce'ine on the contrary do not affect litmus-paper and combine only feebly with acids. Thus narce'ine sulphate and chloride are slowly decomposed by cold water more quickly by hot water. It appeared probable from this that solutions of salts of the stronger bases would give no precipitate with alkaline salts of organic acids whilst in the case of the weak bases the alkaloid would be precipitated as such.The following salts were employed ; sodium and ammonium acetate ammonium oxalate sodium salicylate sodium potassium tartrate sodium benzoate and hydrogen sodium carbonate. and were almost certainly naphthalene. w. P. w. Colour Reaction of Guanine. V. H. V.ORQANIC CHEJIISTRY. 281 Resides the six opium bases many other alkaloi'ds were examined in tbe course of the investigation such as caffeine cocaine atropine pilocarpine coniine strychnine brucine quinine cinchonine and cinchonidine the latter however only with sodium acetate. None of these bases were liberated and precipitated ; in the case of the cinchona bases however it was necessary to carefully neutralise the sodium acetate with acetic acid or precipitation took place.With a perfectly neutral solution of sodium acetate the only alkaloids precipitated are the three weak opium bases papaverine narcotine and nsrceine. These three bases are also precipitated both by slightly acid and by slightly alkaline acetate solution. Neither of the two solutions exerts any influence on the strong opium bases consequently the ordinary non-neutralised acetate solution can be used for the separation of the bases with advantage in point of time and perhaps completeness. Narcotine papaveriue and narceine were precipitated as pure bases by all the alkaline salts mentioned previously. The- baine was precipitated by sodium salicylate as sslicylate and by hydrogen sodium carbonate. Morphine and code'ine were not pre- cipitated by any of the salts.Arranging the alkaloids in series according to their molecular weights it will be seen that tohe first three are strong bases and the last three feeble ones morphine C,7Hl()NO3 ; codeine C,,H,NO ; thebai'ne CIgH2,NO3 ; papsverine C21H21N0d ; narcotine C2,H,,N07 ; narceine C22H29NOa. Slightly acidified sodium acetate solution will indicate as little as 1 40,000 of narcotine in solution. With papaverine the limit is 1 30,000. Narceine is not nearly so sensitive the limit being about 1 600. The precipita- tion of theba'ine as salicylate gave a limit of about 1 2000. For quantitative estimation narcotine k best precipitated by ammonia where it is the only substance thrown down by khis reagent; sodium acetate has however the advantage of precipitating it for qualitative purposes from faintly acid solutions in which all other alkaloids excepting papaverine and narce'ine remain in solution.Papaverine and narce'ine are also best precipitated quantitatively by ammonia. J. T. Cinchona Alkaldids. By W. 5. COMSTOCK and W. KOENIGS (Ber. 19 2853-2859) .-From considerations based on its chemical behaviour the authors have adopted the formula Cl,H,2Br2N20 for cinchoniiie dilwornide instead of that given in their previous paper (Abstr. 1885 910). A crystalline sulphute is obtained by allowing a solution of cinchonine dibromide in 7 to 8 parts of concentrated sulphuric acid to remain for several hours. It is soluble in hot water and dilute alkalis excess of alkali throwing out the salt but dilute acids dissolve it with difficulty.When heated :It 130" in a sealed tube with hydrogen bromide it is decomposed into cinchonine dibromide and sulphuric acid. Dehydrocinclmline CI9Hz0N2O is obtained in practically colourless needles by heating cinchonine dibromide with alcoholic potash in a reflux apparatus for 16 to 20 hours distilling off three-fourths of the alcohol and adding water to the residue. It is purified by pre- cipitating its hydrochloride with ammonia and crystallising from alcohol. The base melts at 202-203" and sublimes without decom-282 ABSTRACTS OF CHEMICAL PAPERS. position if the temperature be carefully raised. It dissolves easily in alcohol acetone and chloroform less easily in ether and hot benzene and is practically insoluble in water.The hydrobromide CIgHzoN20,HBr crystallises from water in colourless transparent prisms the hydrochloride in long silky needles. Dehydrocinchonine chloride ClgHl9N2C1 is prepared by treating dehydrocinchonine hydrochloride with phosphorus pentachloride and phosphoric oxychloride adding ammonia and crys tallisiiig from benzene. It melts at 148-149" and is readily soluble in benzene alcohol acetone chloroform and ether b u t insoluble in light petroleum. Dehydyocinchene Cl9H:I8NZ is obtained by boiling dehydrocin- chonine chloride with alcoholic potash for 16 hours and is purified by recrystallising its hydrogen tartrate. The free base crystallised from dilute alcohol forms long colourless needles which melt at about 60° and contain at least 3 mols. H,O. The hydrobromide C19Hl,N2,2HBr is obtained in small broad transparent concentrically- grouped prisms which dissolve readily in water but only sparingly in alcohol and ether.The pZatinochZoride ClgH,,N,,H2Pt Us a very sparingly soluble salt is obtained in bright red tables from the solution of the base in concentrated hydrochloric acid. Cinchene dibromide Cl9H2,Br2N2 is best prepared by gradually adding bromine to a solution of cinchene in chloroform uiitil the yellow perbromide begins to separate sodium hFdrogen sulphite and hydrochloric acid are added and the base precipitated from the separated aqueous layer by ammonia is purified by conversion into the hydrobromide &c. From its ethereal solution it is obtained in beautiful colourless crystals which begin to fuse a t 110" and melt a t 113". The hydrobromide crystdlises in cencentrically-grouped colourless needles ; the szitrate and zincocldoride also crystallise well.Boiling for 20 hours with alcoholic potash converts cinchene dibromide Strychnine. By W. F. LOEBISCH and P. SCHOOP (Jfonatsh. Chem. 7 603-616) .-The products obtained on distilling strychnine with zinc-dust vary according to the temperature ; at a lower tem- perature one atom of oxygen is removed from the molecule with formation of a compound C2,Hz,NzO a solid substance soluble in alcohol with a blue fluorescence sparingly soluble in dilute acids insoluble in water. It does not give the strychnine reaction with potassium dichromate and sulphuric acid. At a higher temperature the strychnine molecule is completely decomposed ; hydrogen ethylene acetylene and ammonia are evolved whilst carbazole distils over.Similarly brucine and the acid C16H,,N204 obtained by the oxidation of strychnine with chromic acid yield carbazole on distil- lation with zinc-dust. On dry distillation strychnine yields the same into dehydrocinchene. w. P. w. gaseous products but only coLparatively &di quantities of carbazole accompanied probably by pyrroline. V. H. V. Specific Rotation of Piperidine Bases. By A. LADENBURG (Ber. 19 2975-2977).-Completing his recent research on theORGANIC CHEMISTRY. 283 specific rotation of piperidine bases (this vol. p. 164) the author finds €or a-pipecoline [a]= = 21*74" and for a-ethylpiperidine [a]= = 6.75". a-Isopropylpiperidine and P-pipecoline do not yield optically active bases by conversion into dextrotartrates.From the mother- liquor of the a-pipecoline hydrogen tartrate the levorotatory base was obtained ; but this even after conversion into the hydrochloride and treatment with cadmium iodide to remove any accompanying dextrorotatory base gave only a specific rotation of -19" and probably contained either the dextrorotatory or the inactive base as impurity which could not be separated. Experiments show that the inactive piperidine bases are compounds and not mixtures of the optically active modifications ; and therefore it has been possible to effect a decomposition into two optically active salts only in those cases where the temperature employed in the crystallisation lay above or below the transition temperature of the inactive hydrogen dextro- tartrate (comp.Abstr. 1886 968). The unexnectedlv low specific rotation of the dextrorotatorv a-ethvI- piperidine ienders" it pribable that the specimen employe2 was i o t pure. w. P. w. Alkalo'ids of the Berberideae. By 0. HESSE (Ber. 19 3190- 319%).-The author has re-investigated the alkalojids in the root of Berberis vulgaris. He believes that there are therein at least four alkalojids besides berberine and describes especially oxyacanthine (Wacker Chena. Centr. 1861 321) and a new alkaloid he has obtained from the mother-liquors of oxyacanthine and which he names berbamine. He finds the true formula of oxyacanthine to be CIaH,,NO3 and not c,,H,1N03 as he has previously given. When crystallised from water and dried at loo" this alkaloid melts at 138-150" but when crystallised from alcohol or ether it forms needles melting at 208-214".It is easily soluble in chloroform and then gives [ a ] D = + 131.6" ( p = 4 t = 15'). In light petroleum and alkalis it is only slightly soluble and ether extracts it completely from the alkaline solutions. The hydrochloride CI8Hl9NO3,HCl + 2H20 forms small colourless needles which in aqueous solutions give [a]= = +163*6' ( p = 2 t = 15"). The pZatinochZoride is a yellow flocculent precipitate. The niirnte and suZphate are both crystalline. When heated with potash arid a little water the base melts to a brown mass which floats on the surface of the fused potash. This brown mass is the potassium compound of p-oxyacanthine. This conversion into a P-modification also takes place veiy readily even at ordinary temperatures when the alkaloid is acted on by alkalis o r barium hydroxide in the presence of alcohol.Ether now no longer extracts the alkaloid froni the alkaline solution. Hydrochloric acid precipitates P-oxyacanthine which is soluble both in alkalis and in excess of acid. If however the alkaline solution of the @compound is supersaturated with hydrochloric acid a-oxyacanthine hydrochloride crystallises out. The author believes the &modification is due to the alkaloid taking up an additional molecule of water. Oxyacanthine very closely resembles narcotine in properties.284 ABSTRACTS OF CHEMICAL PAPERS. Berbamine crystallises in small scales of the composition C,,H,,NO When anhydrous it melts a t The hydrochzoride crystallises in scales the nitrate in needles ; + 2H,O.156". the pZatinochZoride forms a yellow crystalline precipitate. It is easily soluble in ether. L. T. T. Colchicine. By S. ZEISEL (Monatsh. Chem. 7 557-597).- Previous observations on the composition and properties of colchicine ]lave for the most part been very discordant; in this paper a long summary is given. The principal results obtained by the author are as follows the composition of colchicine is expressed by the formula C2?H2,NOfi ; i t combines with chloroform to form A crystalline com- pound C22H25NOfi,2CH CI3 readily decomposed by water into its components. Colchicine is slightly basic but its salts with the exception of an aurochloride C?zH25N06,HAuCld cannot be obtained from their aqueous solutions.Colchiceine formed from colchicine when heated with a trace of hydrochloric or sulphuric acid has the composition 2C21H27NOfi,H?0. As the difference between the two compounds is one CH or methylene group and as methyl alcohol is produced in the decomposition it follows that colchiceine is a de- methyla ted colchicine. Colchiceine possesses at once the properties of a base as evidenced by the formation of an aurochloride Cz~H2~NO6,HAuCl4 and also those of a monobasic acid or more probably of a phenol as shown by the formation of a copper derivative ( C21H~~NOc)2Cu and by the readiness with which i.t dissolves in alkalis. As colchicine has no acidic properties i t is probably a methoxy-derivative of a compound of which colcbiceine is the corresponding hydroxy-derivative.It is suggclsted that the molecular formula of each of the above substances is the double of that given ; owing to the complex compo- sition of the substances the number of hydrogen-atoms is given with a certain reserve. V. H. V. Ecgonine. By C. E. MERCR ( B e y . 19 3002-3003).-The author has repeated an experiment made by Calmels and Gossin (Abstr. 1885 912) and finds that ecgonine when distilled with almost dry barium hydroxide yields methylamine and not ethylamine as one of the products ; this corresponds with the behaviour of tropine under like conditions. When ecgonine hjdrochloride is heated with an c qua1 weight of phosphorus pentachloride and 10 parts of chloroform a t 100" for 10 hours a base is obtained which yields a well crystallised a urochloride C9H13N@2,HAuC14 corresponding with ecgonine less the elements of 1 mol.HzO. The base has not yet been obtained in the pure state. M. P. w. A New PtomaYne producing Tetanus. By L. BRIEGER (Bey. 19 3119-321) .-The author has already described an alkalo'id tetanine obtained in the cultivation of Rosen bach's microbe. The beef extract in which the microbe had been cultivated for four to six weeks was acidified with hydrochloric acid boiled and filtered ; the filtratp evaporated and treated with lead acetate and alcohol filtered and the lead removed as far as possible a s chloride and finally asORGANIC CEUZMISTRT. 285 sulphide. The strongly alkaline filtrate was distilled with steam acidified with hydrochloric acid evaporated to dryness and treated with alcohol t o remove ammonium chloride.After removing the alcohol the new base was separated as its aurochloride. The free base C5H,,N is volatile boils about loo" but was not obtained free from water. The hydrochloride is crystalline melts at 205" and is very readily soluble in water and absolute alcohol. The aurochloride C,H,,N,HAnC& crystallises in plates and melts at 130". The pZatinochZoride ( C5E:,,N),,H2PtC1 crystallises in plates is decom- posed at 240° and is sparingly soluble in water. The picrate crystal- lises in readily soluble needles. The base gives a yellow precipitate with phosphomolybdic acid a white precipitate with phosphotungstic acid and a red crystalline precipitate wifh potassium bismuth iodide. Injected hypodermically in a comparatively large dose it produces the symptoms of tetanus.By R. NEUNEISTER (Zed. B i d 23,381-401).-The question investigated in this research was whether or not each albumose was converted into isomerides belonging to the anti- and hemi-groups of digestion products. The method previously described by Riihne and Chittenden of separating proto- from deutero-albumose is not a satisfactory one. Hetero-albumose is easily separated by its being precipitated when the salts are dialysed out from a mixture of the albumoses. It can also be separated from the mixture by saturating it with sodium chloride; part of the proto-albumose and the whole of the deutero-albumose remain in solution. In the precipitate hetero-albumose can be sepa- rated by dialysis as before.By acidifying the filtrate which contains the deutero-albumose and part of the proto-albumose the proto- albumose and about half the deutero-albumose are precipitated ; this is filtered off ; the deutero-albumose remaining in solution is not mixed with any other albumose; the sodium chloride is dialysed off the fluid is saturated with ammonium sulphate and thus the peptone alone is left in solution the precipitate of deutero-albumose is redissolved and obtained free from ammonium sulphate by dialysis and finally precipitated by alcohol. It gives no precipitate with copper sulphate ; previous statements that such a precipitat'e occurs were due to its admixture with proto-albumose. On prolonged heating of proto-albumose with 5 per cent. sulphuric acid deutero- albumose is formed. Hetero-albumose yields the same substance and also anti-slbumid.The same result is obtained on peptic digestion and also on tryptic digest'ion more rapidly in the latter case than the former. The formation of the so-called globulin- like substance does not occur in tryptic digestion. No deutero-albumose is formed directly from fibrin; but proto- and hetero-albumose are intermediate products in its formation both by acids and by ferments. Anti-albumid yields dentero-albumose also and seems to be largely a bye-product of the formation of hetero-albumose. The deutero- albumose obtained is an anti-product yielding only anti-peptone ; much insoluble anti-albnmid is left after prolonged digestion which will A. J. G. Albumoses. VOL.LII. '14286 ABSTRACTS OF GEEMICAL PAPERS. yield no more albumose. This insoluble substance swells with sodium hydroxide; it is turned yellow by nitric acid and orange on the subsequent addition of ammonia ; in its solubilities it much resembles keratin. The deutero-albumose formed from proto- and he tero-albumose is called ampho-deutero-albumose as it is subsequently converted into amphopeptone (that is hemi- and anti-peptone) ; the anti-products from proto-albumose are however exceedingly small in quantity md the author suspects that his method of preparing proto-albumose does not give him that substance quite free from traces of hetero-albumose ; and that perfectly pure proto-albumose will be found to be a pure hemi-albumose. The changes in the digestion of albumin are repre- sented in the following schemes. Albumin.-- Hemi-albumin. Anti-albumin. Proto-slbumoee. Hetero- (dys) -albumose. Anti-albumid. Amphodeutero-albumose. Amphodeutero-albumose. Antideutero-albumose. Amphopeptone. Amphopeptone. Antipep tone. W. D. H. Vitelloses. By R. NEUMEISTER (Zeit. Biol. 23 402411).- Following on the lines of Kuhne and Chittenden the products of the digestion of vitellin have been subjected to analysis. The variety of the proteid employed was plant vitellin (phytovitellin) prepared from pumpkin seed. Coagulated vitellin was found to be the best to employ ; ill peptic digestion syntonin WCLS formed a8 one product. This resembled ordinary acid albumin except that it was insoluble in strong nitric acid and gave the biuret reaction not the ordinary purple colour.A substance antivitellid corresponding with anti-albumid was also formed but no coagulable substance like that obtained in the peptic digestion of globulin. The ultimate products of digestion are peptones ; vitellose is the name given to the intermediate products proto- hetero- deutero- and dysvitellose which correspond with the albumoses with siinilar prefixes. These may be separated from one another and from pep- tones as the albumoses are. Protovitellose becomes deuterovitellose on further peptic digestion when subjected to the action of the tryptic ferment a trace of antivitellidPHYSIOLOGICAL CHEMISTRY. 287 is formed; the end products are antipeptone tyrosine leucine and the substance which becomes violet with bromine.Heterovitellose and dysvitellose derived from it do not differ in their properties from the analogous albumoses ; under tryptic diges- tion much antivitellid is formed the end product being antideutero- vitellose. Under prolonged peptic digestioli amphodeuterovitellose is formed. The anti- and ampho-varieties of deuterovitellose correspond with the similarly named albumoses. W. D. H.ORGANIC CHEMISTRY. 225Organic Chemistry.Russian Petroleum. By J. A. LE BEL (COW,@. remd. 103 1017-1019).-It is well known that American petroleum) consists mainlyof paraffins whilst BakQ petroleum consists mainly of naphthenes,ClrHfle and uaphthylenes C,H2,-2. Boussingault has shown thatAlsatian petroleum contains other hydrocarbons.At Tiflis a petroleum is obtained with a composition similar tothatt of the American oil and in the Crimea heavy and light petro-leums are obtained from neighbouring strata The followinq tablegives the sp.gr. of corresponding fractions of oil from differentsources :-Sp. gr.Pennsylvania ............ 236-240" 0.81BakQ .................. 240-241 0.83Alsace . . . . . . . . . . . . . . . . . . 235-24.5 0.86Tschungnelek (Crimes) . . 235-245 0.89The Crimean oil contains 87.4 per cent. of carbon and 12.5 percent. of hydrogen. The differences in sp. gr. are greater than thedifferences in the amount of carbon and these differences do notremain constant when the more volatile fractions are examined :226 ABSTRACTS OF CHEMICAL PAPERS.SP. gr.Pennsylvania ............ 92-94' 0.690BakQ ....................90-95 0.738BakQ .................... 90-91 0.747Tschungnelek. ............ 80-93 0,750Toluene hydride .......... 96-97 0.758The more volatile fractions of the Crimean oil are rely similar tothe correspondirig fractions of the oil from BakQ and differences onlybecome evident with t h e fractions boiling above 150". The sp. gr.of the Russian oils agrees with that of toluene hydride with whichBeilstein and Kurbatow regard them as identical. I t may also besupposed that the Russian oil contains naphthenes belonging to thetrimethylene series ; in this case it should contain a term C6H,0 boil-ing at 30-35" with a sp. gr. about 0.04 higher than thah of the cor-responding fraction of American oil. If on the other hand thesenaphthenes are hydrides of the benxene series the first term wouldbe CsHI2 boiling at 70".I t is found that fyactions of Baka oil boiling at 30-35" havea sp.gr. whieh agrees closely with that of the same fraction of-4merican oil and also with that of pentane boiling at 30". Thedifferences only become evident with the fractions above 60° andit may be taken that the Russian oils boiling above 60" contain nonaphthenes a result which confirms Beilstein and Rurbatow 's con-clusion as to their identity with the benzene hydrides.C. H. B.Action of Heat on Ethylene. By L. M. NORTON and A. A.NOYES (Amer. Chem. J. 8 362-364 ; compare Abstr. 1886 604 and781).-Ethglene was slowly passed through a hard glass tube heatedto dull redness the escaping gascs passed through condensing tubes,arnmoniacal cnprous chloride and bromine samples of the gases beingultimately collected.After a month 15 C.C. of liquid had been con-densed and was found to contain benzene naphthalene and anthra-cene ; only a very slight precipitate was formed in the cuprous solu-tion. There were about 300 grams of bromides of unsatiiratedhydrocarbons consisting largely of ethylene bromide ; but methylene,propylene and butylene bromides were also present as well as asolid bromide.The solid bromide is identical in composition and properties withthe crotonylene tetrabromide obtained from coal-gas from cro-tonylene from erythrol and from oil-gas it is therefore divinyl,CH2 CH-CH CH2. The escaping gases consisted of methane andethane. The author believes that the aromatic hydrocarbons areformed directly from the ethylene withoiit the intermediate forma-tion of acetylene.H. B.Reaction of Organic Bisulphides and Bisulphoxides withPotassium Sulphide. Bey R. OTTO and A. ROSSING (Ber. 19 3129-3132) .-When the bisulphides of ethyl smyl pbenyl pnratolyl orbenzyl are treated with potassium sulphide in alcoholic solution theyare converted into the corresponding mercaptides according to thORGANlC CHElllISTRY. 227equation X,S + 2K2S = 2XSK + KzSz the reaction thus seemingto be general for organic sulphides.Potassium bisulphide seems to be without action on these bisul-phides.I n like manner the thiosulphonates of the general formulaRS02*SR are decomposed by potassium sulphide into the potassiumsalts of the thiosulphonic acids and potassium mercaptides.I n a foot-note the following boiling points are given:-Pam-toluene hydrosulphide 190*2-191.7".Paratoluene bisulphide beginsto boil at 307" (thermometer in liquid) but is in great part de-composed during the distillation. Phenpl bisulphide beginsl to boilat 320° but is also in great part decomposed on distillation.By L.LINDET (Compt. rend. 103 1014-1017).-TriethyZ chlorazwophos-yhite EhPAuCZO3 is obtained by allowing absolute alcohol to dropon a mixture of dry aurous chloride and phosphorus both of whichare immediately dissolved. The product is mixed with water andthe insoluble oily ethereal salt is separated. Ethyl phosphite dis-solves aurous chloride and yields an oil identical in appearance withtriethyl chloraurophosphite but the product could not be purified.The ethereal salt is also obtained by dissolving aurous chloride in asolntion of ethyl phospliite in alcohol prepared by Railton's methodof allowing phosphorus trichloride to drop into a large excess ofabsolute alcohol.Triethyl chloraurophosphite is a liquid which solidifies to a white,crystalline mass at about -10".It is not volatile and is stablewhen exposed to air at the ordinary temperature but begins to de-compose at 100"; spa gr. = 2.025. It is insoluble in water but dis-solves in alcohol ether and benzene. Ammonia dissolves it readily,with formation of the compound Et3PAuC103 + 2NH3 which is ob-tained in Romewhat deliqnescent leaflets by evaporating the ammo-niacal solntion a t 40".This compound dissolves in water andwhen the solution is acidified the ethereal salt is precipitated. Tri-ethyl chloraixrophosphite also dissolves in potassium hydroxide soh-tion and is reprecipitated on adding an acid. If the solution isconcentrated on the water-bath or in a vacuum at the ordinary tem-perature the ethereal salt separates as an oil mixed with crystals ofpotassium hydroxide hut both dissolve on addition of water. AtlOU" potassium chloride and potassium aurite are formed but theetbereal salt is not completely decomposed unless evaporated to com-plete dryness in presence of excess of potassium hydroxide. Underthese conditions gold separates in the metallic state,Propyl butyl and amyl alcohols yield similar products.Trimethyl chloraurophosphite Me3PAuC103 is obtained by the actionof pure methyl alcohol on aurous chloride and phosphorus. It formsslender colourless needleB which melt at 1 00-lOl" alter slightlywhen exposed to air and do not volafilise without decomposition.Itis insoluble in water and is somewhat less soluble than the ethyl-compound in alcohol ether and benzene. It also dissolves in methylalcohol. C. H. B.A. J. G.Action of Alcohols on Aurophosphorous Chloride228 ABSTRACTS OF CHEMICAL PAPERS.Dextroratatory Hexyl Alcohol from Essence of Chamomile.Hg P. r. ROMIRURGH (Rec. Trav. Chim. 5 219-227).-By frequentf ractioual distillation of essence of Roman chamomile a dextrorotatoryalcohol (methethoprop y l cr Zcohol) CH31 eEt*CH,.CH,*OH is obtained,boiling a t 154"; sp.gr. 0.829 a t 15" ; [a]D = 8.2 a t 17". On oxidationwith chromic mixture the alcohol yields a dextrorotatory caproicacid (met hethopropion ic acid) C HMeEt*CH,*C 0 OH boiling a t 19 6-1%"; sp. gr 0.930 at 15"; = 8.92. I t s calcium and silver saltscrystallise in needles and its amide in long needles melting a t 124",soluble in water. A hexyl caproate is formed as a subsidiary productof oxidation. This boils a t 233-234" with slight decomposition ;sp. gr. 0.867 a t 15" ; [aID = 12.86 at 19". As both the alcohol and alsothe acid obtained therefrom are optically active substances accordingt; the hypothesis of Van't Hoff and Le Be1 they must contain anasymmetrical carbon-atom.Of the three possible hexy 1 alcoholssatisfying this condition two have been identified by Lieben and byZeisel and Silva. The alcohol now described must therefore hare theremaining formula $hat ascribed to it above. V. H. V.Thiodiglycol-compounds. By V. MEYER ( B e y . 19 3259-3266)..-Thiodiglycol is obtained by treating a concentra:ed aqueoiis solu-tion of potassium sulphide with glycol chlorhydrin. The product isevaporated on a water-bath and extracted with alcohol. It is a syrupalmost without odour.TltiodiglycoZ chloride S(CH2*CH,C1) is formed by gradnally mixingphosphorus chloride with thiodiglycol (kept cool) and ponring theproduct into water. It is an oil having a slighti sweet ethereal odour.When cooled in ice-water it solidifies to long prisms.It boils a t 217",and is almost insoluble in water. It has very poisonous properties arabbit exposed to air previously passed over filter-paper saturated withthe substance died in three dajfi.When ethylene bromide is heated to boiling for a long time withaqueous potassium sulphide an amorphouq insoluble product is ob-tained differing from the polymerised diethyleno disulphide (formedby adding ethylene bromide gradually to a solution of potassium sul-phide in alcohol). It remains unchanged when boiled for days withphenol. The polymeride which is decomposed by boiling with phenol,can also be prepared by adding ethylene bromide to the sodium salt,C,H4( SNa) covered with a little alcohol ; if 50 times the weight ofalcohol is used tbe whole well cooled and the bromide graduallyadded diethylene disulphide is obtained.The author is making experimenhs with a view to synthesise theethyl vinyl ether of thioglycol SEt*C2H4*S*CE€ CHz in order to com-pare it with the product obtained by the reduction of diethylenedisulphide ethyl iodide (Mansfeld this vol.p. 122). N. 11;. M.Preparation of Derivatives of Carbohydrates. By E. BAUMANN( B e y 19 3218-322'2).-Tetr~iberzzoyZ dextrose C6HQ06Bz1 is preparedby mixing a solution of 5 grams of grape-hugar in 15 C.C. of waterwith 210 C.C. of a 10 per cent. soda solution adding 30 C.C. of benzoiccliloride and shaking until the odour of the chloride disappears. IORGAAIC CHEMISTRY. 229is insoluble in water readily soluble in ether alcohol and benzene ; itmelts at 60-64".It is only slowly decomposed by boiling. acids o ralkalis. 0.001 or 0.002 gr,tm of grape-sugar dissolved in 100 C.C. ofwater can be detected by shaking with 2 C.C. of benzoic chloride andthe corresponding amount of soda solution ; the benzoyl- derivativeseparates as a flaky precipitate.Hexnbenzoyl sacchnrose ~ ~ 2 ~ 1 6 ~ l l ~ z 6 is obtained in a manner similarto the above compound.l'efrabenzoyl glucosa mine C6H9NO5BzP is prepared by shaking asolution of 5 grams of glucosamine in 20 C.C. of water with 140 C.C. of10 per cent. soda solution and 20 C.C. of benzoic chloride. I t is readilysoluble in chloroform insoluble in water sparingly soluble in alcohol,from which it separates in long needles melting a t 197-198".It iscompletely decomposed bx boilinq with alkali.Glycerol dibenzoate C3H502Bz,*OH crystallises from light petroleumin long colourless needles melting a t 70" ; it is very readily soluble inalcohol ether and chloroform insoluble in water. N. H. M.Formation and Composition of Humous Substances. ByM. CONRAD and M. GUTHZEIT (Ber. 19 2844-2850).-1n their pre-vious papers (Abstr. 1885 745; 1886 138; this vol. p. 25) theauthors have shown that when cane-sugar is inverted by diluteacids the lawulose is more quickly and completely decomposed andyields more humous substances than the dextrose. Ulmin is the chiefproduct from laevulose whilst from dextrose ulmic acid entirelysoluble in aqueous potash is obtained.If a more concentrated acidis employed the hurnous substances from dextrose are less soluble,and concentrated hydrochloric acid yields a product practically in-soluble in cold aqueous potash. The authors draw the following con-clusions from their experiments :-(1.) That when saccharoses and glucoses are decomposed by diluteacids the yield of humous substances stands in no direct relation tothat of formic and acetopropionic acids. (2.) Saccharoses by theaction of dilute acids first suffer hjdrolysis and the resulting glucoses,by the elimination of the elements of water yield on the one handformic and acetopropionic acids and on the other humous substances.(3.) Saccharoses and gliicoses with the exception of laevulose yieldmore humous substances by boiling with dilute (7-10 per cent.)hydrochloric acid than with sulphuric acid. (4.) The more concentratedthe acid the greater is the yield of humous substances. (5.) Withdilute acids laevulose yields more humous substances than dextrose.(6.) The percentage composition of the humous Substances variesbetween 62-3-66.5 C and 3.7-4.6 H ; those obtained by the action ofconcentrated acids containing the highest percentage of carbon.The authors have confirmed Sestini's observation that air-driedhumous substances when heated above 110" give off a vapour of acidreaction and capable of reducing silver from solutions of its salts.w. P. w.Arabinoae. By H. KILIANI (Ber. 19 3029-3036) .-Arabiaose isprepared by heating cherry gum (1 part) with 8 litres of 2 per cent.sulphuric acid fgr 18 hours in a water-bath neutralising with hot230 ABSTRACTS OF CHEMICAL PAPERS.saturated aqueous baryta and evaporating the solution (withoutfiltering) to a small bulk; it is then shaken with much 96 per cent.alcohol.The clear solution is decanted moat of the alcohol distilledoff and the residue evaporated down ; it is again shaken with alcohol,and the solution concentrated by distillation. On cooling crystalsseparate ; these are washed with alcohol and recrystallised from sixor seven times their weight of alcohol (sp. gr. 0.825); the product isthen pnre.Arabonic acid (Bauer Abstr. 1885 501) is prepared by shaking asolution of 20 grams of the sugar i n 100 C.C. of water with 40 gramsof bromine for an hour; the bromine is then removed by warmingand the hydrobromic acid by means of silver oxide. Analyticalresults show that it is a tetrahydroxyvaleric acid CliH1006 and notan acid of the formula C6H1207 (Bauer loc.cif.). The calcium salt,(CaH,06)&a + 5H20 and the barium salt which forms microscopicplates were analysed.Arabinosecarboxy lamide C1HI5o7N separates as a fine white crystal-line powder when a clear solution of arabinose (1 part) in water(1 part) is mixed with 60 to 70 per cent. hydrocyanic acid and keptfor eight days in a closed vessel. It dissolves readily in water but isinsoluble in strong alcohol and ether ; when heated it becomes yellowat 130° and decomposes completely a t 160° with evolution of gas,Boiling water and hot alkali solutions decompose it with evolution ofammonia.The lactoite of arabinosecarboxylic acid C7H,207 is prepared bydissolving the amide in the corresponding amount of hot baryta-water evaporating until the odour of ammonia has disappeared andprecipitating the barium exactly with sulphuric acid.The filtrate ismade clear by the addition of a few drops of hydrochloric acid andevaporated. It crystallises from water in very lustrous prisms (pro-bably rhombic) melting a t 145-150" ; it is very sparingly soluble inalcohol. It har nearly the same rotatory power a8 the lactone ofdextrosecarboxylic acid; [a]= = - 54.8. The calcium and bariumsalts are amorphous.The mother-liquor from the preparation of arabinosecarboxylamidecontained chiefly ammonium arabinosecar boxylate.Decomposition by Heat of the Nitrates of the Paraffinoi'dAmines.By P. v. ROMBURGH ( R e c . Trau. Chern. 5 246-251).-The decomposition of ammonium nitrate may be explained on thesupposition that the nitrite is at first formed on which the oxygenliberated acts to form an unstable combination NH,OH,NO*OH whichin its turn is decomposed into water and nitrous oxide. I f this werethe interpretation of the reaction the nitrates of the paraffino'id aminesshould yield a nitrossmine as a product of their decomposition thus :NNe2H,0HN02 = NMe.?H,OHNO + 0 = NMe2*N0 + H20 + 0 ;the liberated oxygen would partly oxidise either the salt or the nitros-amime formed.Dimethylamine nitrate decomposes at 150" with evolution ofnitrogen and carbonic anydride ; and from the residue dimethylnitros-nmine is obtained the yield of which is 50-54 per cent.of thatThe acid could only be obtained as a syrup.N. H. MORGANIC CHEMISTRY. 231required by the above theory. Similarly also diethylamine nitrate isdecomposed when heated a t 1 70° and the reaction becomes violent withrise of temperature ; carbonic anhydride and nitrogen together with aninflammable gas are evolved and from the residue diet hylnitrosaminemay be obtained.Experiments on the decomposition of methylamine ethylamine andtetrethylammonium nitrate were not so successful.V. H V.Action of Hydrogen Chloride on Mixtures of Aldehyde withAlcohols and Phenols respectively. By A. CLAUS and E. TRAINER(Ber.19 3004-3011).-When a mixture of aldehyde and methylalcohol (1 vol. 2 vols.) i8 treated with hydrogen chloride at a tem-perature below O" dried and treated with sodium isobutoxide thechief product is dimethylwetal ; methylisobutylacetal (from chlor-ether contained in the original product) is also formed; it boils at124-128". When equal mols. of aldehyde and methyl alcohol areused dimethylacetal methyl-isohutylacetal and di-isobutylacetal areobtained ; the last compound would be formed from a-dichloro-etherin the original product.Ethyl alcohol and aldehyde give a good yield of a-chlor-ethertogether with diethylacetal and a-dichlor-ether (compare Wurtz andFrapolli Anwalen. 108 226).Isoamyl alcohol and aldehyde (equal mols.) yielded a-chZorethy Iisoamyl ether ; when 2 mols.of the alcohol are used di-isoamylacetal,C,H402( C,H,,) alone is formed. It boils a t 209-211" jnncorr.).Isobutyl aloohol (1 mol.) gave a better yield of monochlorether thanamyl alcohol and in the reaction with 2 mols. of alcohol a smallamount of a-chlorethylisobutylacetal (boiling at 155-160") could beisolated.Bthy Zidene diphenyl CHMe( C6H4.0H) is obtained by passinghydrogen chloride through a mixture of aldehyde (1 mol.) withphenol (2 mols.). It is readily soluble in alcohol ether chloro-form &c. insoluble in water benzene and light petroleum ; it couldnot be obtained in the crystalline state. It softens a t loo" and becomesviscous at 125". Aqueous alkali dissolves it readily,Ethylidene-di-a-na~hthQZ is formed in a similar manner and iscompletely analogous in its properties to the diphenyl-derivative.When P-naphthol and aldehyde are treated with hydrogen chloride,a crystalline compound melting at 162-163" is formed having theformula C2H,0,(CloH,)2.It has none of the properties of a phenol,but corresponds with the acetals. The authors consider that thisdifferent lnehaviour of a- and /%naphthol (the one behaving like aphenol and the other like a fatty alcohol) is fresh evidence in favourof his unsymmetrical naphthalene formula. N. H. M.Acid Propionates and Butyrates. By W. G. MIXTER (Amer.Chem. J. 8 34%-346).-The following salts are described Acidbarium propionute ( C,H502)Ba,C3H602 + 3H20 forms tabularcrystals that very slowly lose water and acid in dry air.Acidstrontium propionate ( C3H502)2Sr,C3J3602 + 34$&0 forms long thi232 ABSTRACTS OF CHEMICAL PAPERS.crystals that lose acid on exposure to the air. Acid calciunt pro-pionate 2( C3H502)LCa,C3H602 + 5H20 forms long needles that havean acid reaction and decompose on heating. Acid bar?;lLm isobzhpate,(C,H,02)2Ba,C4H was obtained by heating a solution of thenormal salt with the excess of the acid a t 100" until constant.H. B.Preparation of pIodopropionic Acid. By V. MEYER (Ber. 19,3294-3295).-The author finds that /?-iodopropionic acid can bereadily prepared from the glyceric acid obtained by tbe oxidation ofglycerol with nitric acid since the accompanying products neitherform crystalline compounds with phosphorus iodide nor interferewith the crystallisation of the iodo-acid.The syrup obtained by theoxidation of glycerol and subsequent removal of nitric acid is dilutedwith water to a sp. gr. of 1.26 and 30 C.C. of the solution is theiipoured into a flask containing phosphorlis iodide prepared from50 grams of iodiue and 6.5 grams of yellow phosphorus. A vigorousaction takes place either in the cold or on gently warming and thecontents of the flask on cooling solidify owing to the separation of6-iodopropionic acid in large colourless lamina which after onecrystallisation fro= water are quite pure. w. P. w.Methylisopropylacetic Acid. By P. v. ROMRURGH ( B e e . T ~ a v .Chew. 5,228-239).-Kobig concluded that the caproic acid obtainedb y the oxidation of the hexyl alcohol from the essence of Romanchamomile was identical with that obtained by Narkownikoff from thenitrile derived fi-om methyl isopropyl carbinol. This view is not con-firmed in the present paper in which it is shown that mekhylisopropyl-acetic acid is not identical with the caproic acid obtained from theessence of chamomile.Two methods mere used for the syntheticalformation of methylisopropylacetic acid CHMePr*WOOH namely theconversion of ethyl sodiomaloiiate into the isopropyl-derivative andthis into the ethereal salt of methylisopropylmalonic acid fromwhich the acid itself was obtained by hydrolysis ; this when heated,readily decomposed into carbonic anhydride and the correspondingacetic acid; (ii) the conversion of ethyl acetoacetate into ethylicme thylisopropylacetoacetate and the decomposition of this by alkalisinto methylisopropyl acetone and methylisopropylacetic acid.Ofthese methods the former is preferable.The acid boils a t 189-191"; sp. gr. = 0.928 at 15"; its silversalt crystallises in delicate needles and its amide in micaceous scales.MethyZisopropy Zacetone CHMePrWOMe boila at 135-l$O" has astrong odour resembling menthol; sp. gr. = 0,815 af 20"; it doesnot seem to react with sodium hydrogen sulphite or with pheiiylhydrazine.Methy Zisopro~yZmrtZon~c acid CHMePr(COOH) is crystalline,melts though not very definitely at 124"; its silver and calciumsalts are sparingly soluble ; its ethyl salt is a colourless liquid boilingat 221"; sp.gr. = 0.990 a t 15" ; it has an agreeable odour. As asubsidiary product isopropylmalonic acid was obtained a substancepreviously described by Conrad and Bischoff. V. H. VORGANIC CHEMISTRY. 233Derivatives of Erncic and Brassic Acids. By C. L. REIMERand W. WILL (Ber. 19 3320-33:!7).-Erucic acid is best obtainedby saponifying rape oil with alcoholic potash distilling off thealcohol and dissolving the acid liberated on addition of sulphuricacid in three times its volume of 95 per cent. alcohol; on cooling to0" crystals of erucic acid separate in an alniost pure condition. Themelting point of the acid was found to be 34". Ethyt erucute,Cz2H4,0sEt is a colourless odourless oil boiling above 360" withoutdecomposition ; its vapour-density however could not be determined.The anhydride CJls203 is prepared by heating erucic acid andphosphorus trichloride in molecular proportions.It is an oil cry stallis-ing in a freezing mixture to a mass of scales and is very readily solublein ether benzene and chloroform sparingly soluble in alcohol. Theamide Cz2H4,0(NH,) crystallises in colourless needles melts at 84" ,and is readily soluble in ether and benzene sparingly soluble inalcohol insoluble in water. The anilide is c~ystalline melts at 55".and is readily soluble in ether and benzene sparingly soluble inalcohol.Dierucin C3HaOH( C22€&102)2.-When rape oil is allowed to standfor a long time a yellowish tallow-like deposit is frequently found inthe casks ; this by repeated solution in ether and subsequent additionof alcohol can be obtaitied in silky needles.Dierncin melts at 47",and is readily soluble in ether and light petroleum insoluble in coldbut soluble in hot alcohol. A trierucin could not be separated fromrape oil.Brassic acid is best prepared by warming erucic acid with dilutenitric acid to the melting point and then adding sodium nitrite ; theproduct is quite pure after two crystallisations from alcohol. Theethyl salt is obtained directly from the acid or by the action of nitrousacid on ethyl erucate; it crystallises in lamina showing a vitreouslustre melts at 29-30" and boils above 360" without decomposition ;the vapour-density could not however be determined. The u?thydir'de,ClaH,03 formed by heating the acid with phosphorus trichloride,orystallises in lustrous tables melts at 28-29" and is insoluble inwater and alcohol readily soluble in ether and benzene.The amidemelts at go" and resembles in its properties the amide of erucicacid; both atnides can be obtained by heating the correspondingethyl salts t o 230' with ammonia.Tribrassidiit is formed when rape oil (100 parts) is treated withnitric acid ofsp. gr. = 1.2 (5 parts) and sodium nitrite (1 part) ; aftersome time the resulting crystalline mass is washed dissolved in ether,and from the solution cooled to 0" a lustreless crystalline powder isobtained. Tribrassidin melts at 47" but when heated above itsmelting point and allowed to cool the melting point is subsequentlyfound to be 36"; it is insoluble in alcohol readily soluble in etherand chloroform. Dibrassidin C3H50H( CnH4102)2 is formed whendierucin is treated with nitrous acid ; it forms feebly lustrous crystals,melts at 65" and is less soluble in ether than tribrassidin.By distilling the calcium salts of erucic and brassic acids twoketones are obtained which seem to be different; they are both verysparingly soluble in alcohol.w. P. w234 ABSTRACTS OF CHEMICAL PAPERS.Dry Distillation of Calcium Tetramethylenecarboxylatewith Lime. By H. G. COLNAN and W. H. PERKIN Jun. (Uer.,19 3110-3115).-The products of this reaction are much ethylene(together with hydrogen and small quantities of carbonic anhy-dride and methane) ditetramethylene ketone and an oil boiling at136-137" and uniting with hydrogen sodium sulphite phenyl-hydrazine and hydroxylamine ; this is either tetramethylenealde-hyde or acetyltetramethylene but there is not suficient evidence tosay which.Ditstramethylene ketone CO(CoH,)2 is a colonrless oil of pepper-mint-like odour ; i t boils a t 204-205" gives a colourless crystallinecompound with hydrogen sodium sulphite and is acted on by brominewith evolution of hydrogen bromide.The phenylhydrazine compoundis obtained as a yellow oily precipitate. The oxime C19H15N0 formsa colourless syrup. A. J. G.Oxalimide. By H. OST and A. MENTE (Ber. 19 3228-3230).-Oxamic acid is best prepared by heating hydrogen ammonium oxalateat 140° stirring all the time extracting with aqueous ammonia andconverting into the sparingly soluble barium salt.This is eonvertedinto the ammonium salt and precipitated with hydrochloric acid.The yield is 16 per cent. co OaaZirnide <co>XH is obtained by treating 20 grams of oxamicacid with 50 grams of phosphorus pentachloride and 20 grams ofphosphorus oxychloride and heating a t 80-90". The product is putinto ice-water warmed at 40° filtered and extracted with water a t60". It is purified by dissolving in very dilute warm aqueousammonia precipitating with hydrochloric acid and recrystallising fromwater. It forms very lustrous prisms which seem to be monoclinic. Itis sparingly soluble in water more soluble in warm aqueous ammonia.Boiling water decomposes it into oxamide and oxalic acid. Concen-trated aqueous ammonia converts it into oxamide.When a cold satu-rated solution of oxalimide is treated with mercurous chloride acrystalline m ercnry salt C20,N.HgCI separates.Oxalimide is also formed by the action of nitrous acid on comenamicacid (dihydroxypyridinecarboxylic acid). This reaction togetherwith the results of experiments made by v. Pechman and others is infavour of the Tiew that meconic and cnmalinic acids are derivativesof pyridone C5H,0-NH.Ethyl Oxalacetate. By W. WISLICENUS (Ber. 19 3225-3228).-Ethyl oxnlacetnte COOEt.CO*CH,*COOEt is prepared by dissolving20 grams of ethyl oxalate in 100 grams of absolute ether adding3 grams of sodium wire and then gradually adding 12 grams o€ pureethyl acetate. After 12 hours the product is solid and is thenwashed with absolute ether and dried over sulphuric acid.Thesodium-derivative CaHl105Na ci~ystallises from absolute alcohol inmicroscopic matted needles ; it is decomposed by dilute sulphuricacid. The ethyl salt is a rather viscous oil almost without colourand odour ; it decomposes when heated. The dilute alcoholic solutionN. H. DiIORGAKIC CHEMISTRY. 233gives with ferric rhloride an intense dark red coloration. Whenboiled with dilute alkali or baryta-water it yields oxslic and aceticacids. Warm 10 per cent. sulphuric acid decomposes it with evolu-tion of carbonic anhydride and formation of pyruvic acid. Whensaponified by Ceresole's method for the preparation of acetoaceticacid monethyl oxalacetute C6H,0 is obtained. The latter crystallisesfrom benzene in stellate groups of needles melting a t about 90".It is readily soluble in alcohol ether and water and has a stronglyacid reaction.Phenylhydrazine ethyl oxalacetatp crystallises in plateu ; when boiledwith water it yields an acid C,,H,N,O (analogous to that obtainedby Knorr from phenylhydrazine ethyl acetoacetate (Abstr.1884,1377). This dissolves readily in alcohol sparingly in water. anddecomposes at about 250" without melting. N. H. M.Glycuronic Acid. By H. THIERFELDER (Ber. 19 3148).-Bromine converts glycuronic acid into saccharic acid thus showingthe presence in the former acid of an aldehydic group and also itsclose relation to dextrose. L. T. T.Fermentation of Citric Acid. By P. WATTS (J. XOC. Chen?.Ind. 5 215-218).-Warington (this Journal 1875 936) has madean attempt to ascertain the amount and nature of the volatile acids inconcentrated Sicilian lemon-juice with a view to determine the acidsother than citric which OCCUI' in concentrated juice.When perfectlyfresh juice is distilled the distillate is neutral and consists only ofwater with a small amount of essential oil derived from the peel.It is thus clear that volatile acids are not normal constituents of thejuice. When lemon-juice is allowed to remain for some days in aiiopen vessel a film of mould gradually forms on the surface consistingof a large number of minute cells of saccharomyws mycoderma. If thisjuice is now distilled the distillate is found to be acid. From anexamination of the distillate purified by redistillation the authorinfms the presence of acetic acid traces of formic acid and possiblysome propionic acid and indirectly the existence of el hyl alcohol,with possibly some propyl alcohol and minute quantities of methylalcohol in the original juice after fermentation.It is also shown byexperiment that under the influence of snccliaromyces mycoderma citrioacid is split up directly into carbonic anhydride and water oxygenbeing absorbed. It was found that the growth of this fungus ceasedshortly after air was excluded.Decomposition of Amides by Water and Dilute Acids. ByBERTHELOT and ANDRE (Compt. reid. 103 1051-1057).-Urea isdecomposed by hydrochloric acid at the ordinary temperature.100 C.C. of solution containing 1.0293 gram of urea was mixed with10 C.C.of hydrochloric acid containing 3.78 grams of HC1 allowedto remain 24 hours diluted with water neutralised with magnesia,and the ammonia estimated by Schloesing's method. After boilingfor one and a half hours about one-ninth of the tota! nitrogen in theurea was obtained in the form of ammonia (0.0523 gram). A similarD. B236 ABSTRACTS OF CHEMICAL PAPERS.quantiky of urea solution was boiled for an hour and a half with2 grams of magnesia and 0.0353 gram of ammonia was obtained theamount evolved being practically the same in each half hour. Thedifference between the two quantities represents the ammonia formedby the action of hydrochloric acid in the cold and is equivalent tothe conversion of about 4 per cent.of the total nitrogen into ammoniain 24 hours. The action of the acid increases with the concentration,arid also with the temperature.It is well known that urea is partially decomposed when boiled withiva ter. At the ordiiiary temperature however there is no appreciableclecomposi tion even after five days. Dilute &odium hydroxide solutiondecomposes urea slowly in the cold but the action is much lessmarked than that of hydrochloric acid.Asparagine is also decomposed by hydrochloric acid in the cold to Rsomewhat less extent than urea and the decomposition increases withthe concentration of the acid. It is decomposed by magnesia asBoussinpnult observed and also by boiling water although only to avery slight extent. The adion of soda is much more marked thanwith urea.0.5 gram of asparagine mixed with 50 C.C. of water andG gmms of sodium hydroxide loses one-third of the total nitrogen in24 hours and about half of the total nitrogen in five days or almostthe whole of the nitrogen which is evolved as ammonia in the ordinaryreaction.Oxamide when triturated with hydrochloric acid of 10 per cent.,loses 0.7 per cent. of the total nitrogen in the foi*m of ammonia intwo hours. When boiled with magnesia 6.3 per cent. of the totalnitrogen is evolved as ammonia in the first half hour and 3.4 per cent.in the second half hour. The first loss is due t,o the decomposition ofthe oxamide arid the second to decomposition of magnesium oxamatre.I n all these cases the action of acids varies with the nature of t h samicle is proportional to the time of action and increases with theconcentration of the acid and with the temperature.The action of acids or alkalis on the amides derived from thealcoholic amineR and from the hydroxg-acids will be different sincethese amines are reconverted into ammonia with great difficulty.Hydrochloric acid tends to regenerate the amines from theiia deriva-tives in consequence of the alkalinity of the amines.I n the case ofsubstances of complex function like glycollamine and the leucines,both acids and alkalis will tend to produce the same azotised andoxygenised derivative because each can combine with it.Aspartic acid is not sensibly affected either by boiling water or bymagnesia. Uric acid yields no ammonia when boiled with magnesiafor an hour but if triturated for two hours with hydrocliloric acid of10 per cent.it loses about 1 per cent. of the nitrogen in the form ofammonia. C. H. B.Derivatives of Acetothienone. By H. B RUNSWIG (Ber. 19,2890-2896).-B1.omacetothie?irone C4SHJ-CO*CH2Br prepared by thebromination of acetotbi6none dissolved in carbon bisulyhide is a paleyellow oil the vaFour of which affects the mucous membrane. Itcannot be distilled uiider ordinaery pressures without decomposition ORQ ANIC CHEMISTRY. 237n t a low temperature it forms small yellow crystals. The nnilide,C18H,*CO*CH,*NHPh crystallises in leaflets melting at 80" ; its acetylderivative C,SH,*CO*CH,*KPhAc forms hard brown crystals meltingat 141*5" and its nitroso-derivative rhombic crystals meltinq at 81",soluble in ether and alcohol sparingly soluble in water.The thio-cyanate CaH3S*CO*CH2*SCN ci~ystallises in colourless leaflets meltinga t 88" ; sparingly soluble in water and light petroleum readily solublein chloroform. Dibroniacetothierione C4SHJCO*CHBrz is a heavy,colourless oil solidifying in a freezing mixture and completelydecomposed when heated under ordinary pressure.Ciiznamyl thienyl ketone C,SH,*CO*CH CHPh pypared by satu-rating with hydrogen cliloride a mixture of acetothienone and benz-aldehyde in equimolecular proportions crystallises in grouped needlesor prisms very soluble in ether and chloroform sparingly soluble inwater. The di bromo-compound crystdlises in colourless leafletsmelting a t l57" and is soluble in alcohol.Isomerism of the Thiophenic Acids.Derivatives of p- Thio-phenic Acid. By A. DAMSKY (Ber. 19 3282-3286 ; compare thisvol. p. 129).-The ordinary method of preparing P-thiophenic acid bythe oxidation of P-thiotolen affording only a poor yield the a ithcrprepared p-ethylthiophen and oxidised it with potassium p arman-ganate ; no advantage however was derived thereby since theamount of P-acid obtained was not greater than that formed by theoxidation of 3-thiotolen. The besh yield 8 per cent. of the theoreticalquantity was obtained by oxidising @-thiotolen in quantities of1 gram with a mixture of 6.7 grams of sodium hydroxide and3-3 grams of potassium permanganate in 333 grams of water.Whendissolved in water a t 15" or 18" 100 C.C. of the soiution contain0.44 gram of /-l-th iophenic acid ; the solubility of the barium salt is11.54 a t 17" and that of the calcium salt is 7.92 a t 14.5". The amidecrystallises in slender colourless needles melts a t 177*5-178" and isvery sparingly soluhle in ether ; the phenylcarhamide crystallises inconcentrically-grouped needles melts at 206" and is sparinglysoluble in alcohol.p-E'th ylthiophen C4SH3Et. -When ethyl ethenyltricarboxylate(Abstr. 1883 45) is treated with the calculated quantities of sodiumethoxide and ethyl bromide a vigorous action takes place accom-panied by considerable development of heat and ethyl butenyltricar-boxylate is obtained as an oil. This is saponified and from the acid,by heating it a t 120-170" untd evolution of carbonic anhydrideceases p-ethylsuccinic acid is obtained which by distillation withphosphorus trisulphide yields P-ethylthiophen.This is an oil re-V. H. V.sembling a-ethylthiophen in properties. w. p. w.Reduction of aZ-Thiophendicarboxylic Acid. By Y. ERNST(Bey. 19 3;!74-33;!78).-'etra~~ydrothio~hendicarbo~~Zic acid,is prepared by adding 15 parts of sodium amalgam (4 per cent. Na)to 1 part of a-a-thiopbendicarboxylic acid and 0.5 part of sodiumhydroxide dissolved in water and heating at 100" for two hours; theCISH,(COOH)z [ = 2 51,VOL. LlI. 2 38 ABSTRACTS OF OBEBIICAL PAPERS.product is converted into the silver salt and from this by treatmentwith hydrogen sulphide the hydro-acid is obtained. It crystallises inyellowish-white probably monoclinic tables melts a t 162" (corr.) isreadily soluble in water less so in ether and shows all the propertiesof a hydro-acid.Thus it reduces an ammoniacal silver solution andwhen heated with sulphuric acid decomposes into thiophenic acid andcarbonic oxide. The barium salt C4SH6(C00)2Ba crystallises insmall lustrous scales ; and the silver salt CaSH6(COOAg) is a whitepowder. When an alcoholic solution of the hydro-acid is saturatedwith hydrogen chloride meth2/ltetrahydrothio~hendicarboxylate,C,SH6( CO OMe)2,is obtlained as an oil which cannot be distilled and does not solidify.a-Thiophencarboxylic acid on reduction yieldR an acid which crys-tallises in colourless needles melts at about 48O is readily soluble inwater and reduces ammoniacal silver solution.w. P. w.Synthetical Investigations in the Thiophen Series. ByF. ERKST (Bey. 19 32'78-3282).-The author has endeavoured toeffect the synthesis of an anthracene of the thiophen series but with-out success. The following compounds prepared in the course of thework are described :-OrthotolugZ thienyl ketone C6H4Me*CO*C4SH3 obtained by the actionof orthotoluic chloride on thiophen in the presence of aluminiumchloride is a colourless oil ; when boiled for some time it loses water,and is completely resinified.Phenyl thiotoZyZ ketone C6H,*CO*C4SH,Me is formed by treatingcoal-tar thiotolen with lnenzoic chloride in the presence of aluminiumchloride. The ketone is a syrup and on long boiling loses water andis resinified.The acetoxime was prepared but is not described.When thii3nylglyoxylic acid is reduced with sodium amalgam in thecold thieny7gZycoZZic acid C4SH3*CH( OH)*CO@H is obtained. 1 tcrystallises in white needles melts at 115" is readily soluble in water,alcohol ether and benzene and decomposes on distillation. Oxida-tion with manganese dioxide converts it into thiophenaldehyd e ; theyield however is small. The barium and caZcium salts are readilysoluble in water ; the silver salt is obtained as a white precipitate.Thienylncetic acid CaSH,*CH,*COOH is obtained by boiling tbi6nyl-glycollic acid with hydriodic acid and amorphous phosphorus. Itforms colourless crystals melts a t 7 6 O and is soiuble in hot water,alcohol and ether.The barium salt forms white crystals readilysoluble in water ; the sizzler salt is obtained as a white precipitate.The acetoxime is a non-volatile oil.w. P. w.Synthesis of &-Phenylthiophen. By W. KUES and C. PAAL( n e r . 19 3141-3144) .-Following out their previous work (Abstr.,1886 5:<6) the authors find that if p-benzopropionic or p- benzoiso-succinic acid is substituted for levulinic acid similar reactions occur.I n these cases however the intermediate hydroxy-product appears tobe less stable than thiotolen and traces only were obtained. Themain product was a-phenylthiophen C,SH,Ph [Ph = 11. With thORGANIC CHEUIbTRY. 239isosuccinic acid evolution of carbonic anhydride and formation of theketonic acid takes place before the reaction occurs. a-Phenylthiophencrystallises in plates melting a t 40-41" and is soluble in carbon bisul-phide and the usual organic solvents insoluble in water. It is volatilei n steam and has the characteristic odour of diphenyl.It dissolvesin cold concentrated sulphuric acid and is reprecipitated unchanged onthe addition of water. It shows the indophenin reaction but doesnot give cny characteristic coloration with Laubenheimer's reaction.When added to cold bromine it forms parabromophenyltribrorno-thiophen which crystallises in white needles melting a t 145 -146",sparingly soluble in alcohol and acetic acid easily in carbon bisulphideand benzene. It is a very stable compound may be heated withdilute nitric acid at 180" without change and is only oxidised bycontinued boiling with chromic acid in acetic solution and thenforms parabromobenzoic acid.Attempts made to form a phenyltri-bromothiophen were unsuccessful. A mixture of a compound crys-tnllising in white needles melting ak 55-56' (probably a phenyl-dibromothiophen) with a very soluble bromo-derivative melting at33-36" was produced.Pentathiophen-group. By K. KREKELER (Ber. 19 3266-3274).-The lactone of a-methylhydroxyglutaric acid (Block and Tollens,Abstr. 1886 533) is prepared by slowly adding 100 grams of levulicacid to 100 grams of potassium cyanide finely rubbed with 10 gramsof water the whole being well cooled. It is then kept for 24 hoursin a loosely-closed vessel treated with the necessary amount offuming hydrochloric acid and left for three or four days.It isextracted with ether saponified by heating for one hour on a water-bath with fuming hydrochloric acid and again extracted with ether.It is purified by means of the barium salt. The hydroxy-acid is con-verted into niethylglutaric acid by boiling with twice its volume ofhydriodic acid and amorphous phosphorus.p-~~ethylpentathiophen CHI<Ck-CH>S is obtained by distilling5 grams of sodium methylglutarate (dried a t 160') with 10 grams ofphosphorus trisulphide at 180-250". From 550 gram? of sodiumsalt 20 grams of crude oil were obtained; this is boiled for somehours with strong potash solution distilled the oily distillate treatedwith a little dilute permanganate solution and then re-distilled oversodium.It is a colourless very refractive oil boiling a t 134" andhas the odour of pure xylene. Sp. gr. = 0.9938 a t 19" (water at19" = 1). When the solution of the substance in glacial acetic acidis treated with a solution of isatin in the same solvent and thenwith sulphuric acid (keeping it cold) an intense dark-green colorationis produced. When poured into water a green flaky precipitate isformed soluble in ether. Laubenheimer's reaction jields a darkviolet coloration in sulphuric acid.l-l-iMethylaceto~entatliietrone C,SH,MeAc is prepared by treating asolution of 1 part of P-methylpentathihone in 10 parts of lightpetroleum with the calculated amount of acetic chloride and addingaluminium chloride until the evolution of hydrogen chloride ceases.L.T. T.CMe'CHr 240 ABSTRACTS OF CHEMICAL PAPERS.It is purified by steam distillation. It is a clear heavy oil having anodour resembling that of acetophenone; it boils a t 233-235" (uncorr.).The ketoaime C6SH4Me*CMe N*OH was prepared by Peter's method(Abstr. 1885 141). It crystallises from ether in long branchedneedles melting at 68" ; it dissolves readily in alcohol and ether.When /I-methylpentathiophen is treated with 0.3 per cent. alkalinepotassium permanganate solution the oxidation takes place veryquickly with formation of acetic and oxalic acids.When air saturated with methy lpentathiophen is passed throughfuming nitric acid a nitro-compound is formed. The alcoholic solu-tion of the latter treated with a drop of potash solution acquires anintense violet-red colour which disappears in a few minutes.N.H. M.Action of Light on Nitrobenzene in Alcoholic Solution.By G. CIAM~CIAN and P. SILBER (Ber. 19 2899-2900).-1n contiaua-tion of experiments on the transformation of quinone to qiiinol onexposing its alcoholic solution to sunlight (Abstr. 1886 695j theauthors have studied the chemical change induced in nitrobenzeneunder similar conditions. Among the products obtained were alde-hyde aniline and a quinoline base probably quinaldine.V. H. V.Orthoethyltoluene Oxidation of Orthodialkyl-derivativesof Benzene with Potassium Permanganate. By A. CLAUS andE. PIESZCEK (Ber. 19 3083-3O92) .-The common statement thatortho-xylene on oxidation with potassium permanganate yields firstorthotoluic acid and then phthalic acid is incorrect nothing butphthalic acid being formed; not even a trace of orthot)oluic acid isdetectable.By the oxidation of orthoethyltoluene with potassiumpermanganate ortho toluic phthalic and terephthalic acids were ob-tained according to the temperature and concentration of the solutions.At loo" in alkaline solution total combustion took place. The resultsobtained with cymene completely corresponded with those obtainedwith orthoethyltoluene.BromorthoRthllZtoZuene is a colourless oil boiling a t 220-221"(uncorr.) ; when heated with nitric acid sp. gr. 1.2 in sealed tubes at190-200" it is oxidised to a bvornorthotoluic a,cid [Me COOH Br =1 2 41.This forms snow-like flocks composed of slender needles,melts a t 118" (uncorr.) is sparingly soluble in cold water readilysoluble in alcohol ether and hot water and yields readily solublecrystalline salks with the alkali metals and with barium and calcium.It is not identical with the acid described by Jacobsen (Abstr. 1885,143) to which he assigned the same constitution ; the authors considerit more probable that his acid has the constitution [l 3 41.By the action of nitric acid on orthoethyltoluene in the cold awtono- and dinitro-derivatiye are formed ; the latter is a pale-yellowoil and does not solidify at 0".Orthoethyltoluene-~-,~ul~~onic acid C6H3MeEt*S03H [l 2 41 isobtained together with the a-acid which has not yet heen investigated,by the action of pyrosulphuric acid on orthoethyltoluene; it forms adeliquescent colourless crystalhe mass.The potassium sodiumORGANIC CHEMISTRY. 241barium calcium. lead comer and silrer salts are described. Thechloride is a yellow oil; the' lam& forms a yellow buttery mass.A. J. G.Oxidation of the Homologues of Phenol. By B. HEYMANN andW. KONIGS (Ber. 19 3304-3315) .-Continuing their experiments(Abstr. 1886 542) the authors find that the oxidation of the homo-logues of phenol can readily be effected if the phenols are converted intothe corresponding dipotassium phosphates ; these double salts axe pre-pared by heating the phenols (1 mol.) with phosphoric oxychloride(1 mol.) carefully adding water to the cooled product extracting the re-sulting chlorinated phosphorus compounds with ether and decompos-ing them with potassium carbonate.The double phosphates are thenoxidised with alkaline potassium permanganate acidified with hydro -chloric acid and boiled for a short time. The double phosphates of thepheriols are found to be more stable than the corresponding doublesulphates and a better yield is obtained when the former are oxidised.By this method orthocresol is readily oxidised t o salicylic acid.Thymol treated with potassium pyrosulphate yieldsadouble sulphate,C6H3MePra*SOaK [Me SOaK Pr = 1 3 41 crystallising in finesilky fibres which decomposes readily on keeping or when heated ona water-bath although it is stable in alkaline solution ; it is sparinglysoluble in 50 per cent.alcohol readily soluble in absolute alcohol andin water. When the double sulphate or double phosphate is oxidised,tthymohydroxycnmic acid COOH*C,H,Pr@*OH [COOH OH Pr =1 3 43 (Abstr. 1879 LSS) is obtained.Carvacry 1 potassium subhate C,H&lePr.SO& crystallises in silveryscales decomposes very readily on keeping or on gently heating,is stable in alkaline solution and is soluble in water andabsolute alcohol. Carvacryl dipotnssium phosphate CBH3MePr*P0,K2 + 5H20 crystallises in large silvery lamin= decomposinga t loo" readily soluble in water and in absolute alcohol. Sometricarvacryl phosphate was formed in the preparation of thedouble salt. When oxidised with permanganate both the doublesulphate and double phosphate yield paruhydrozyisoproivy lsalicylicacid COOH*C6H3(0H)*CMe,.0H [COOH OH CMe,*OH = 1 2 43,which crystallises from water in large flat needles and in slender,concentrically grouped needles from chloroform.The acid melts at130-1 35' ; a more exact determination was not possible owing to thetendency to dehydrate aEd form parapropenylsalicylic acid. Hydroxy-isoprop~lsadicylic acid is sparingly soluble in cold water readilysoluble in chloroform alcohol and ether insoluble in carbon bisul-phide and gives with ferric chloride an intense reddish-violetcoloration. 'l'he silver salt Cl,,Hl,OaAg crys tallises in colourlessneedles ; the copper salt (C,oHl,Oa),Cu + H,O crystallises in greenprisms which do not lose their colour on drying; it is sparingly solublein water.When heated with concentratcd hydriodic acid andamorphous phosphorus the acid is reduced to isohydroxycumic acid,OH.C6H3Prfl*COOH (Abstr. 1878 731).COOH*C6H3(OH)*CMe CH [COOH OH (CMe CH,) = 1 2 41,Yurapropeny lsalicy lic acid242 ABSTRACTS OF CEEMICAL PAPERS,.is readily obtained from hydroxyisopropylsalicylic acid by gentlywarming it on a water-bath with dilute hydrochloric acid. Itcrystallises in slender needles melts a t 145-146" is sparingly solublein cold water readily soluble in alcohol ether and boiling carbonbisulphide and gives an intense reddish-violet coloration with ferricchloride. It is volatile with steam and when heated at 1.50" sublimeswith slight decomposition. The silver salt CI0H9O3Ag forms acrystalline powder very sparingly soluble in water ; the copper salt,(C,0H903)2Cu + 2H20 forms small green crystals insoluble in water,the anhydrous salt is not hygroscopic.By reduction with sodiumamalgam in the cold an acid agreeing in its properties with Jacobsen'sisohydroxycumic acid (Zoc. cit.) was obtained ; the melting point,however was 96-97' instead of 93-94'.When a boiling aqueous solution of hydroxyisopropylsalicylic acidis treated with an equal volume of concentrated hydrochloric acid Rpolymeride propemylsnlicylic acid (C,OH,,O,) is obtained in small,white crystals which melt at 230" with evolution of carbonic anhydride.It is insoluble in water and carbon bisulphide soluble in hot aceticacid alcohol and ether and the alcoholic solution is coloured anintense reddish-violet with ferric chloride.The acid is not volatilewith steam nor is it reduced by sodium amalgam.Attempts to oxidise the ethyl isopropyl isobutyl and amylAction of Sodium Methoxide on Bromobenxene. By F.BLAU (Monatsh. Chem. 7 621-636).-When bromobenzene is heatedwith sodium methoxide in sealed tubes aniso'il is formed togetherwith phenol ; the sodium methoxide thus acting like a niixture of thealcohol and alkali a considerable proportion of the bromobenzene isunaltered. The reactions with di- and symmetrical tri-bromobenzenesare precisely analogous; thus from the former are obtained brom-aniso'il dimethylquinol and bromophenol ; from the latter a dibromo-phenol and dibromaniso'il. The dibromophenol forms white crjstnlsmelting at S6*5" readily soluble in alcohol and ether sparingly inwater and petroleum ; on fusion with alkali it yields phloroglucol ; itis therefore a symmetrical compound.Bisulphides with Mixed Organic Radicles.By R. OTTO andA. ROSSING (Ber. 19 3132-3138).-Hitherto no organic bisulphideswith mixed rsdicles have been obtained. The authors 6nd that suchcompounds are formed when a mixture of two mercaptans are treatedw-ith bromine and that the reactions take place the more readily themore closely allied are the radicles of the reacting mercaptans. Thereaction is R-SH + R'*SH + Br = 2HBr + R*S,*R'.YhenyZ pai-atoZyl bisadphide C7H7*S2*Ph is obtained by dissolvingmolecular proportions of pheriyl and paratolyl hydrosulphides in tentimes their volume of ether arid slowly adding a molecular proportionof bromine.It is insolublein water miscible in all proportions with alcohol and ether has anodour somewhat resembling that of tolyl hy drosulphide is heavier thanwater and scarcely volatile in steam. When heated with alcohol andzinc-dust it is decomposed into the corresponding zinc mercaptides.potassium sulphates led to no result. w. P. w.V. H. V.This substance is a thick pale-yellow oilORGANIC CHEMISTRY. 243Ethy'l amyZ biszcZp7~ide prepared in a similar way is a thin colourlessliquid of very strong and unpleasant garlic-like odour. It is insolublein water soluble in ether and alcohol lighter than water and volatilein steam.Ethyl plhenyl bisulphide.-The authors attempted to obtain thiscompound by the above method but it was only formed in verysmall quantity the principal products being diethyl and diphenylbisulphides.But by modifying Schiller and Otto's method for thepreparation of organic bisulphides (this Journal 1877 i 306) theauthors were successful. 10 grams of phenylsulphinic acid (1 mol.) and15 grams of ethyl mercaptan ( 3 mols.) in alcoholic solution were heatedin sealed tubes at 100". The action took place according to theequation PhS02H + 3EtSH = PhSz*Et + EtzSz + 2Hz0. Ethylphenyl bisulphide is a thick oily strongly refractive liquid heavierthan water and only very slightly volatile in steam. It is insolublein water soluble in ether and alcohol. Phenyl paratolyl bisulphidewas also prepared by the action of phenyl hydrosulphide on paratolyl-eulphinic acid.When the ethyl salts of the thiosulphonic acids are heated withmercaptans reactions similar to the above occur ; these are not how-ever of so simple a kind but take place simultaneously accordingto the two equations :-I R*SOZ*SR + 4R*SH = RzSz + 2R'zSt + 2HZO.11.R*S02*SR + 4R''SH = 2R.Sz.R' + R z S z .Phenyl disulphoxide /Ph.S,O,*Ph) and ethyl mercaptan thus yieldAction of Silicon Fluoride on Organic Bases. By C. L.JACKSON and A. M. COMEY (Ber. 19 3194-3195).-The authorsintend studying these reactions. When silicon fluoride is passed overaniline a compound of the formula 3NH2Ph,SSiF4 is formed. Thiscompound was obtained by Laurent and Delbos (Ann.Chirn. Phys.,22 l O l ) but its composition was not established. It forms white,microscopic needles and sublimes without fusion. It is insoluble inether benzene and light petroleum. With water or alcohol it formsaniline hydrosilicofluoride.Ortho- and para-toluidine diphenylamine and dibenzylamine formsimilar compounds. L. T. T.Aniline and Diphenylamine from Phenol. By V. MERZ andP. MGLLER (Ber. 19,2901-2917).-1n this paper the various methodsused and the conditions required for the conversion of phenol intoaniline and diphenylamine are fully described. Thus when phenol andammonium zinc chloride or simply ammonium chloride are heated at330" 70 to 80 per cent. of the phenol is converted into the amine theyield of which is dependent on an excess of the ammonium salt thetemperature and the time of heating.The same change may also beeffected with zinc oxide or magnesia and ammonium chloride thepresence of an excess of the latter preventing the formation ofdiphenylamine. Experiments in an autoclave were not so satisfactory ;ethyl bisnlphide phenyl bisulphide and ethyl phenyl bisulphide.L. T. T244 ABSTRACTS OF OHEMICAL PAPERS.the pressure when the mixture was heated at 320° was 20 to 25atmospheres. V. H. V.Action of Alcoholic Hydrogen Chloride on Nitrosamines.By 0. FISCHER and E. HEPP (Ber. 19 2991-2395).-The authorsfind that certain nitrosamines undergo intramolecular change by theaction o€ alcoholic hydrogen chloride thus ; for example methylphenyl-nitrosaniine is converted into 1 4 nitrosomethylaniline.1 4 N~trosniethyZatziline is prepared by adding alcoholic hydro-gen chloride to an ethereal solution of methylphenylnitrosamine ; a,vigorous action takes place after some time and small yellow needlesof the 1 4 nitrosomethylaniline hydrochloride separate in an almostpure state.The base is obtained by precipitation with sodiumcarbonate or ammonia either in yellowish-green laminae or from verydilute solutions in large steel-blue prisms; it is readily soliible iaalcohol ether and chloroform sparingly soluble i n benzene and onlyslightly soluble i n light petroleum and in water. It melts a t 118" andsuffers decomposition when more strongly heated. When heated withsolution of sodium hydroxide it is decomposed into 1 4 nitrosophenoland methylamine ; whilst by reduction methylparaphenylenediamineis obtained.Paranitrosomethylaniline is a secondary base and bythe action of nitrous acid yields 1 4 nitrosomethylpheny lnitrosamine,NO*C6H4*NMe*N0 ; this compound crystallises from alcohol in nodules,and melts at 101". Careful oxidation with nitric acid of sp. gr. = 1.13converts it into 1 4 nitromethy Zphenylnitrosamine; this forms yellowneedles melting a t 104".When methylaniline dissolved in alcoholic hydrogen chloride istreated in the cold with one molecular proportion of sodiuni nitrite,there separate after long standing two compounds 1 4 nitrosomethyl-aniline hydrochloride and 1 4 nitrosomethylphenylnitrosamine thelatter being formed in the greater quantity and a corresponding pro-portion of the methylaniline remaining nnacted on.1 4 NitrosoethyZaniZine obtained i n a manner similar to the methyl-deriva,tive crystallises in green lamina melts at 78" and is readilysoluble in alcohol ether and benzene sparingly soluble in water.Itshydrochloride crystallises i n stellate groups of needles. By reduction,ethy~al.aphen?/lendiamine is obtained; this base is a thick oil anddistils a t 270". Its hydrochloride forms colonrless narrow scalesreadily soluble in water less soluble in alcohol. From 1 4 nitroso-ethylaniline 70 per cent. of the nitrosophenol and 80 per cent. of theethylamine hydrochloride required by theory were obtained byheating it with sodium hydroxide solution.1 4 Nitrosoethylorthotoluidine melts a t 140" and crystallises ingreen scales fi-equen tly exhibiting a bluish shimmer.1 4 Nitrosodi~,henylamine obtained from Witt's diphenylnitrosamine,crystallises in green tables showing a bluish shimmer melts at 143",and dissolves readily in alcohol ether and chloroform giving brownsolutions and in sulphuiic acid with a red colour which at oncechanges to violet on warming.The 71 ydrochloride crystallises in browntables having a bronze lustre or in dark reddish-brown needles and isdecomposed by water with liberation of the base. w. P. wORGANIC CHEMISTRY. 245Preparation of Benzylamine and Phenethylamine. By S.HOOGEWERFF and W. A. VAN DORP ( R m Trau. Chiw. 5 252-254).-Hofmann has suggested the action of bromine on phenylacetamidein presence of dilute alkali as a convenient method for the preparationof benzylamine (Abstr.1886 45). It is here shown that the yield isconsiderably increased by preparing the alkaline hypobromite first andthen adding it subsequently to the amide.The preparation of benzylamine and phenethylamine by this methodis described. V. H. V.Isodinitrodimethylaniline. By P. V. ROMBURGH (Bec. Trav.Chim . 5 240-245) .-According to Mertens when dinitrophenyl-nitramine is heated with phenol tetranitrodimethylazobenzene a redcompound is produced reconvertible into the nitramine by treatmentwith nit'ric acid (Abstr. 1885 1022). As however trinitrophenyl-methylnitramine yields a similar red substance reconverti ble into thenitramine which has been shown to be trinitrophenylmethylaniline,i t is probable that the red substance obtained by Blertens is a dinitro-methylaniline. The analytical results support this view quite as wellas that of Mertens.As a confirmation the author by acting ontetrarnethyl benzidine with nitric acid obtained a product resemblingthe isodinitrodimethylaniline of Mertens which when boiled withnitric acid yielded the corresponding nitramine ; from this the redsubstance was obtained the analysis of which showed that it was atetranitrodimethylbenzidine. Wlien treated with nitric acid thisyielded the theoretical quantity of the nitramine. V. H. V.New Synthesis of Thiodiphenylamine. By A. BERNTHSEN (Ber.,19 3255-3256).-Tliiodiphen~lamine is obtained by heating orth-amidophenyl mercaptan and cntechol a t 220-240" for about 30 hours.The product is extracted with alkali and acid and crystallised fromether and light petroleum.This synthesis forms an important sup-port in favour of thiodiphenylaniine being a di-ortho-compound (corn-pare Bernthsen Abstr. 1886 53 and Mohlau Ber. 19 2013).N. H. M.Ethereal Carbonates. By G. BENDER (Ber. 19 2950-2952).-0xycarbimidopheno1 described by Halckhoff (Abstr. 1883 1 1 6 ~ )andpreviously by Groenvik (Bull. SOC. Chim. 25 177) and hydroxy-methenylamidophenol prepared by Sandmeyer (this vol. p. 135) areidentical with the author's anhydro-orthamidophenyl carbonate(Abstr. 1887 37) which melts a t 137-138'. Kalckhoff's compoundon further purification becomes white and its ncetyl-derivative issoluble in water like the corresponding substance obt.ained by theauthor.The ethyl salt prepared by Sandmeyer has the formula-nTC6H4<z>C*OEt that of the salt obtained by the author isNEt C,H,<-O->CO. In the existence of these two isomerides theparent substance exhibits a remarkable analogj to carbostyril andisatin; it also has st pseudo-form in addition to its ordinar216 ABSTRACTS OF CHEMICAL PAPERS.one although whether the latter is a lactim or lactam cannot yet bedecided.The author's ethyl salt melts at 29" and has a bitlter taste. Con-centrated hydrochloric acid is without action on it at loo" butdissolves it in the cold forming a highly unstable hydrochloride. w. P. w.Benzyl-derivatives of Hydroxylamine. By F.WALDER (Ber.,19 3287-3294).-Further investigation has shown that the con-clu sions respecting the composition of these compounds arrived at inthe author's previous paper (Abstr. 1886 796) are erroneous Acomplete analysis of the compound obtained by the action of methyliodide and sodium on dibenzylhydroxylamine and described as tri-benzylbenzoxyammonium iodide shows that it has the formulaN2(C7H,)40,HI. The hydriodide can be decomposed by alkalis but,since the base is soluble in water and only sparingly soluble in ether,a separation is better effected by employing moist silver oxide. Thebase crystallises over sulphuric acid distils with decomposition a thigh temperatures and is very deliquescent ; when heated with water,it yields dibenzylhydroxylamine whilst by the action of acetic anhy-dride acetyldibenzylh~droxylamine is obtained.The pZatinochZoride,Nz( C7H7)40,HzYtC16 crystallises in slender yellow needles melts at133" and is insoluble in cold water and ether. The sdphate,N2( C,H7)40,H,S04 forms transparent prisms melts a t 152" and isinsoluble in alcohol and ether readily soluble in water containingacid. The nitrate N,( C7H7)40,2HN03 crystallises in white feathery,flat needles melts at 159" and is sparingly. soluble in water.The hydrochloride N2( C7H7),0,2HC1 forms thick prisms showinga iiacreous lustre is insoluble in ether and only sparingly soluble iu.water after it has once separated from solution. 9 second hydriodide,Nz(CiH7)40,2HI crystallises in bright yellow aggregates melts at27" and is soluble in alcohol.From a black resinous mass formed in the preparation of thehydriodide N,(CiH,)aO,HI a black crystalline compound may be ob-tained ; it appears to be a periodide of the formula N,(C7H7)40,MeI,12.The base previously described as benzy lbenzenylamine proves to bedibenzylamine NH(C7H,)z.It is found that when dibenzylhydroxyl-amine is lieated with phosphorus trichloride and the productextracted with dry ether an unstable bright-yellow viscid oil con-taining phosphorus and chlorine is obtained which on addition ofwater yields dibenzylamine. The nitrosamine ( CiH7>,N*NO formsbrittle curved white crystals melts a t 61" and is readily soluble inalcohol ether and light petroleum insoluble in water.'the piatino-chloyide N( C7H7)zH,H2PtC1 crystallises in golden-yellow needles ;the nitrate N ( C,H7)zH,HN03 crystallises in slender glisteningneedles melts at 186" and is sparingly soluble in water. Whenheated with benzyl chloride a t loo" the base is converted into tri-benzy lamine.When dibenzylhy droxylamine hydrochloride is treated with potas-sium nitrite in the cold ~iit~osodibenxylh~jdroxylallzine N(C7H7)zO*N0,is obtained; this crystallises in flat white needles melts at 82-84"ORGANIC OHEMISTRT. 247and is soluble in alcohol and ether sparingly soluble in light petro-leum insoluble in water. If however cooling be omitted andthe nitrate be added rapidly to the hydrochloride nitrosodibensy 1-amine is obtained N(C7H,),0H + 2HN02 = HKO + H20 +The author finds that mono- di- and tri-benzylamine are also formedwhen dibenzylhydroxylamine is prepared by Schramm's methodN ( C H7) 2*NO.(Abstr.1884 51). w. I?. w.Correction. By L. KNORR (Bey. 19 3303).-In a previous paper(Abstr. 1884 1198) a compound C14Hl,N204 was stated to havebeen obtained by the action of ethyl acetoacetate on orthophenylene-diamine instead of on paraphenylenediamine. Sulphnric acid iswithout action on the compound iu the cold but a t 100" paraphenyl-enediamine is eliminated. w. P. w.Action of Ethyl Acetoacetate on Aromatic Diamines. By 0.N. WITT (Ber. 19 2977-2978 and 3299).-By the action of ethylacetoacetate on orthotoluylenediamine ethenyltoluylenediamidine isformed. This confirms the resdts obtained b Ladenburg andRiigheimer (Abstr.1879 915) the priority oP whor;le work isacknowledged by t4e author in the second communication.Condensation Products from Carbo-imides and Orthodi-amines. By C. DAHM and K. GASIOROWSKI (Ber. 19 3057-3060).-Carborthotoluylenedipkenyltetramine CTH,<NH> C (NHPh) is pre-pared by heating carbodiphenylimide and orthotoluylenediamine (mole-cular weights) for four hours at 130-lev. It crystallises frombenzene in needles melting at 161" and is readily soluble in alcoholand ether. It does not react with an excess of imide. The hydro-chloride 2CmH20N4,3HC1 crystallises in white needles melting at173-174"; it is very soluble in alcohol and ether rather sparinglyin water. The sulphate was also prepared.Carborthotolzcylenediparatoly ltetramine C,2H2JYa is prepared in amanner similarly to the above-mentioned compound. Tte product isextracted with boiling benzene and the white powder dissolved inalcohol from which it separates in needles melting at 196".The7ydrochEoride 2CzpHz4N4,3HC1 crystallises from tho strong acid solu-tion in needles melting at 143O.NHN. H. M.Derivatives of Parachlorazobenzene. By E. MENTELA and K.HEUYANN (Ber. 19 2970-2974 ; comp. Abstr. 1886 €3741.-ChZorodiainidodip~enyZ NH2*CsH,*CsHSC1*NHz.-When pnrachlorazo-benzene in dcoholic solution is treated with zinc chloride and sul-phuric acid and the solution after precipitating the zinc withhydrogen sulphide is made alkaline with caustic soda chlorodiamido-diphenyl is obtained and can be extracted with ether. It is abright yellow powder which very readily becomes oxidised.Thehydrochloride C12Hl,N,Cl,2HCl crystallises in tufts of white needles248 ABSTRACTS OF CHEMICAL PAPERS.Parn,nifrochlorazobpntene N02*C6H4*N2*C6H4C1 [4 1 41 is preparedby treating parachlorazobenzene with fuming ni trio acid. It formsslender pale-jellow needles melts at 132*S" and is insoluble in water,sparingly ,soluble in cold alcohol and ether readily soluble in aceticacid.Parac~~lorazobeizxenesi~lphonic acid SO3H*C6H4*N,*C6H4Cl [4 1 41,is obtained by heating parnchlorazobenzene with 10 per cent. fumingsulphuric acid a t 60-70" for some time. I t crystallises in brownneedles melts at 149" and is very soluble in water and alcohol.Thesodium and barium salts are described. The chloride C1,H,N2C1-SO,Cl,melts a t 1W0 and crystallises in glistening red prisms soluble inalcohol and ether; boiling with water converts i t into the acid. Theainide forms brownish-yellow prisms melts a t 211" and is insoluble inwater sparingiy soluble in ether and cold alcohol. w. P. w.Cyanazobenzene and Parazobenzenecarboxylic Acid. ByE. MENTHA and I(. H EUMANN (Be).. 19 3022-3W5) .-Paracyanazo-benxme CI3H9N3 is prepared by slowly adding a solution of diazoben-zene chloride (from 40 grams of nmido-azobenzene hydrochloride) to asolution of copper sulphate (100 grams) and potassium cyanide (90 percent. 112 grams) in ti00 C.C. of water a t 90". When cold it is filtered,well washed and dried ; it is then sublimed and recrystallised frombenzene from which i t separates in short brown nkedles.It melts a t100-101" is insoluble in water readily soluble in warm alcohol,ether and benzene.PiLrazobenxenscarbozylic acid NPh N*CsH4-COOH is obtained byboiling the above nitrile in the pure state for three hours with con-centrated aqueous potash. It crystallises from alcohol in long,lustrous brown prisms soluble in ether and warm benzene. Whenheated above 210" i t becomes dark and decomposes at a higher tem-perature. When heated with lime a sublimate is obtained whichmelts a t 170-171" and is probably azophenylene. The potassiumsaZt crystallises in brownish-yellow needles soluble in water and inalcohol; the barium salt forms needles sparingly soluble in water,rather readily soluble in alcohol.Several other salts were pre-pared. N. H. M.Chloroparazotoluene. Ry E. MEETHA (Bey. 19 3026) .-Chloro-pnrazotoluene C1,HI3N3C1 is prepared by treating 4.5 grams of amido-pnrazotoluene (obtained by Nolting and Witt's method Abstr. lF84,742) with 200 C.C. of water and 150 C.C. of strong hydrochloric acid,and adding a solution of 5 grams of cuprous chloride in 45 C.C. ofhydrochloric acid. It is then heated to go" and a solution of2.5 grams of sodium nitrite in 25 C.C. of water gradually added.The product is filtered treated with hydrochloric acid and withsoda solution and ultimately crystallised from alcohol. It formsbrown plates which melt at 97' dissolves readily in et>her alcohol,arid benzene and closely resembles parachlorazobeuzene (compareAbstr. 1886 874).N. H. MORGANIC CHEMISTRY. 249Reduction of Aldoxirnes and Acetoxirnes. By H. GOLDSCHMIDT(Bey. 19,3232-3234).-Cart.yZumine CIOH17N is obtained by reducingcarvoxime in alcoholic solution with sodium amalgam in presence ofacetic acid.Benzylamine can be conveniently prepared by gradually adding160 grams of 24 per cent. sodium amalgam to a solution of 5 grams ofbenzaldoxime in 20 C.C. of alcohol a t 50-60"; the solution must bekept acid by addition of acetic acid. It is poured into water satu-rated with ether made alkaline and again extracted with ether. Theethereal extract is dried and treated with hydrogen chloride ; benzyl-amine hydrochloride then separates as a white precipitate.Benz-hydrylamine and isobntylamine were prepared in a similar mannerfrom benzophenoxime and isobutylaldoxime respectively.N. H. M.Pyrogenic Formation of Phenazine. By A. BERNTHISEN (Rw.,19 3256-3258) .-The author succeeded in isolating phenazine fromthe product obtained by passing aniline through a red-hot tube(Abstr. 1886 471). The product was repeatedly exhausted withmoderately dilute hot hydrochloric acid the brown solution precipi-tated with ammonia extracted with ether and the ethereal solutionshaken several times with dilute hydrochloric acid. I n this waty thestronger bases were dissolved but not the phenazine. The ether wasdistilled off the residue extracted with hot dilute hydrochloric acid,filtered when cold and precipitated with ammonia.I t was then sub-limed and the lustrous yellow needles identified as phenazine. Thispyrogenic formation of phenazine corresponds with that of anthracenefrom toluene. N. H. M.Safranine Dyes. By R. NIETzKI (Ber. 19 301'7-3022).-Pre-vious experiments (Abstr. 1883 731) made it probable that safraninecontains two amido-groups and that the third nitrogen-atom istertiary or quaternary.When phenosafranine ClaH14N4 is boiled with alcohol sulphuricacid and sodium nitrite the compound C,Jl,3N3 is formed. Thisis a dye of a bluer shade than safranine from which i t is also distin-guished by the absence of fluorescence of its alcoholic solut,ion and inits behaviour towards strong sulphuric acid :-safranine dissolves witha green colour which changes to blue and red on addition of water ;the new compound dissolves yielding a yellowish-brown solution,which when diluted becomes first green and then red.The monacetyl-deriuative is violet and yields crystalline yellow salts.The second amido-group in safranine can be removed only withdifficulty and in strongly acid solution. A reddish-violet base "asobtained which yields brownish-yellow salts. It shows the same re-actions as the acetyl-derivatives of safranine.The two constitutional formula for safranine lately proposed byBernthsen (this vol. p. 139) are shown by the author to be incorrect.With the one the existence of the two isomeric diethylsafrani~lesobtained by the author (Zoc. cit.) cannot be accounted for ; the otIierformula permits the existonce of the two isomerides but only one o250 ABSTRACTS OF CHEMICAL PAPERY.the latter could be diazotised.It has been shown tlint both thediethylsafranines very readily yield diazo-compounds. N. H. M.Constitution of the Safranines. By 0. N. WITT (Ber. 19,3121-3124) .-The author criticises the constitution assigned to thephenosafranines by Andresen (Abrtr. 1855 1026) and by Bernthsen(this vol. p. 139) and suggests the following :-NLencosafranine. Phenosafranine hydrochloride.A. J. G.Constitution of Safranine. By R. NIETZKI (Bey. 19 3163-3166).-The author supports the correctness of the formula suggestedby Witt (see preceding Abstract). 0. Lehmnnti has examined crys-tallogrsphically the nitrates of the two dimethylsafranines previouslydescribed by the author and the non-identity of which has been latelycalled in question by Bernthsen (this vol.p. 139). Lehmann de-elares the two compounds to be undoubtedly different.The author has carried out the idea mentioned in his last paperon this subject and tested the safranine-forming power of the sixisomeric xylidines C6H,Me,*NHz and of the three isomeric com-pounds ( C6H2Me3*NHz) cumidine mesidine and isocumidine whenheated with paradiamidodiphenylamine. The results-takiny NH,as always occupying the position l-may be expressed a8 follows :-The xylidines 1 3 4 and 1 2 4 gave safranine; 1 2 5,1 2 6 and 1 3 5 gave no safranine; and 1 2 3 gave onlytraces which were probably due to traces of the 1 3 4 compoundpresent as impurity in the xylidine used.Ordinary cumidine,[l 2 4. 51 gave a safranine whilst mcsidine [l 2 4 61 andisocumidine [l 3 4 51 gave none. It is therefore clear that theposition of the meth yl-groups in the monamine plays a determiningpart in the formation o r non-formation of safranines.The author considers that Witt’s formula is much more in har-mony with the above and other facts known about safranine than iseither Andresen’s or Bernthsen’s formula. L. T. T.Paranitroformanilide. By T. B. OSBORN and W. G. MTXTER(Aimer. Chew. J. 8 346-347) .-This substance NO,*C,H,*NH*COH,was prepared b-j adding formanilide to fuming nitric a d sp. gr. 1-53,in a freezing mixture and pouring the product into cold water; itwas washed with water and ether then cryatalliscd from alcohol.IORGANIC CHEMlST RY. 251melts at 187" or 194" according as it has been crystallised from alcoholor from hot water. When boile3 with caustic potash it yields para-nitraniline. Attempts to obtain azo-compounds by its reduction wereunsuccessful. H. B.Orthazoparabromacetanilide. By C. H. MATTHIESS EN and W.G. MIXTER (Arner. Chem. J. 8 347-349).-Parabromacetanilide wasconverted into orthonitroparabromacetanilide and then treated inwarm alcoholic solution with zinc and strong aqueous ammonia forhalf an hour. The red precipitate mas wasbed with water diluteacid and alcohol. During the reduction a portion of the bromine isdisplaced with formation of azoacetanilide which is only removed byheating with concentrated hydrochloric acid at 100".The productthus purified is orthazoparabl.omacetcrnilide N,( C6H3Br-NHAc),. Itis a pale red substance melting a t 280-282" and is acted on bypotash with great difficulty.Halogen-derivatives of Oxanilide. By J. 0. DYER and W. G.MIXTEE (Amer. Chem. J. 8 349-357).-Tetrachloro3anilide,C20,(NH*C6H3C1)2 [l 2 41,is obtained by passing chlorine into an acetic acid solution of oxan-ilide. It separates in slender white fibres melting at about 255" andis difficult to obtain quite pure. On decomposition it yields meta-dichloraniline melting a t 63".Paradibromoxanilide C202(NH.C,H,Br)2 is obtained by adding bro-mine in excess to a boiling acetic acid solution of oxanilide.I t meltsabove 300". Treated with alcoholic potash it yields parabromaniline.Paradiiodozanilide is prepared by the action of iodine and strongnitric acid ; crystallised from aniline it is quite white. It decomposesbefore melting.Boiling alcoholic potash converts oxanilide into oxanilic acid andthcn into oxalic acid and aniline. The substituted oxanilides behavesimilarly Metadichlorozanilic acid (=6H3C12*NHmCO*C001 is formedalong with metadichloraniline by the hydrolysis of the tetrachlor-oxanilide. It dissolves in 808 parts of water a t 25" and melts a t 122" ;the potassium salt crystallises from hot water in fine fibres.Parabromoxanilic acid C6H4Br*NH*CO*COOH is readily soluble inhot water and in 515 parts of water at 25"; i t melts a t 198".Thepotassium salt is anhydrous and forms tabular monoclinic crystals ;the calcium barium and silver salts are also anhydrous and sparinglysoluble in water. Paraiodoxclnilic acid C6HJ.NH*C0.COOH meltswith decomposition at 197-200° and dissolves in 1385 parts of watera t 25" ; the potassium salt is anhydrous.Action of Concentrated Sulphuric Acid on Aromatic Ke-tones. By A. CLAUS (Bey. 19 2879-2881).-1n this paper pre-liminary experiments are described on the decomposition of aromaticketones by fuming sulphuric acid. The reaction consists in the de-composition of the ketone and formation of a carboxylic acid and Asulphonic acid thus mesitpl phenyl ketone yields mesitylsnlphonicand benzoic acids. It is proposed to carry on a series of investiga-H.B.Treated with potash it yields paraiodaniline.H. B252 ABSTRACTS OF CHEMICAL PAPERS.tions to determine in the case of mixed ketones containing a simpleand a replaced pbenyl-group whether in all cases the former remainscombined with the carbonyl grouping and the latter yields the sul-phonic acid as also to investigate the changes produced in the case ofa ketone containing the subptituted phenyl groupings of differingdegrees of complexity. At a low temperature a sulphonic acid of theketone is formed ; thus barium salts of mesitqlphenylketonemono-sulphonic and para-xylylphenylketonedisulphoni~ acids are described.V. H. V.Aromatic Ketones. Ry 0. PAMPEL and G. SCHMIDT ( B e y . 19,2896-2899) .-PhenyZ e t h y l ketone (propiophenone) COEtPh is ' con-veniently prepared by Friedel and Crafts' aluminium chloride reaction.I t s acetoxime- and phenylhydrazine-compounds are colourless oils ;with bromine i t yields a monobromo-derivative as a dark oil whichgives an anilide COPh*C?H,*NHPh separating in yellow glisteningcrystals me1 ting a t 38" ; its acetyl-derivative crystallises in colourlessneedles melting a t 103".Naphthyl methyl ketoue C,,,H,*COMe prepared by amid of t'bealuminium chloride reaction is a pale-yellow oil boiling at 296-299".Its acetoxime- and phenyl hydrasine-derivatives are crystalline com-pounds melting a t 101" and 146" respectively.C,H,*CO*CH,*NHPh,separates in golden-red crystals melting at 130" ; its thiocvnnate crys-tallises in micaceous crystals.Its anilide,V.H. V.Benzene-derivatives of High Molecular Weight By F.KRAFFT (Bey. 19,2982-2988).-PentadecyZphenyZ ketone C15H3,*COPh,is obtained by gradually adding aluminium chloride (16 parts) to acooled solution of palmitic chloride (1 part) in benzene (2 parts) andafterwards gently warming; the product is poured into water excessof benzene removed by distillation and by fractional distillationunder 15 mm. pressure the ketone is approximately separated from theregenerated palmitic acid the last traces of which are removed froman alcoholic solution of the distillate by precipitation as barium palmi-tate. The ketone crystallises in large glistening laminae melts a t 59",boils a t 250.5-251" under 15 mm. pressure and is very sparinglysoluble in cold alcohol soluble in ether and hot alcohol.On oxidationwith chromic acid it yields benzoic and pentadecylic acids.Eeradeay Zbenzene CIGHBBPh is prepared by the action of sodium ona mixture of cetyl iodide and iodobenzene. It crystallises i nglistening tables which subsequently become opaque melts a t 27",and boils at 230" under 15 mm. pressure. When dissolved infuming eulphuric acid hexadecylbeiizene yields a nzonosuZphonicacid and by fusing its sparingly soluble sodium salt with potas-sium hydroxide a t 250" hezadecyZphenoZ ClsH33*C6H4*OH is obtained.This is a colourless odourless and tasteless compound melting a t'77.5" and boiling a t 260-261" under 16 mni. pressure. E e x a -derylnitrobenzene is a crystalline powder melts a t 3.5-36" andwhen reduced yields hexadecylan,idobenzene which melts a t 53" anddistils without decomposition a t 254-255" under 14 mm.pressure ORQANIC CBEMIYTRT. 253its phtinoch Zoride ( C16H3,*C,H,*NH,)2,H,PtC16 is soluble in ether andalcohol.Octndecylbenzene CIsH,,Ph is obtained by the action of sodium on asolution of octadecyl iodide and iodobenzene in benzene. It formseither an oil which soon solidifies 01- crystallises in colourless odonr-less and tasteless silvery scales melts a t 36" and boils at 249" under15 mm. pressure. Octa,decylbenzenesulpho~ic acid is prepared bytreating octadecylbenzene with fuming sulphuric acid and gentlywarming ; the sodium salt when heated with eight times its weight ofpotassium hydroxide a t 250-270" for 10 to 12 hours yields octadecyl-phenol C,,H,,*C,H,*OH almost quantitatively.This cr~stallises inglistening lamins melts a t 84" and boils without decomposition a t277" under 15 mm. pressure. Octadecylbenzene is converted byfuming nitric acid into an almost colourless mononitro-compoundmelting at about 48" ; by reduction this yields octcrdecylamidobenzene,which melts a t about 61" and boils a t 274" under 15 mm. pressure.HexyldiplienyZmethane c6Hl3*CHPh2 is formed when 0.2 part ofaluminium chloride is slowly added to 1 part of oenanthylidene chlo-ride dissolved in 4 parts of benzene ; after standing for two days thewhole is heated at 30" for a short time. It melts a t 14" and boils a t186" under 10 mm. or 193" under 15 mm.pressure. By the actionof nitric acid hexyldinitrodipheiiylmetharLe CsH1,'CH(C6H,*NO,) isobtained and this on reduction yields T~exyld iamidodiphenylnlethane.Hex~lltetranzefhljldi~~idoaipheny Zmetl~ane can be prepared either fromthe latter or by the condensation of oenanthaldehyde and dimdhgl-aniline with zinc chloride. It melts a t 59.5" boils a t 272-278" andyields a platinochloride C23'113N2,H2PtCl~ sparingly soluble in wateraud ether-alcohol.When a larger proportion of aluminium chloride is added toenanthylidene chloride in benzene heptylbenzene C7H,,Ph is obtained.It boils a t 108-110" under 10 mm. pressure. The correspondinglwxyl phenql ketone C6H13*COPh is prepared by the action of 0 5 partof aluminium chloride on 1 part of heptoic chloride in 2-3 parts ofbenzene.It melts a t 17" boils at 155" under 15 mm. pressure andyields ail acetozime which melts a t 55" and crystallises from alcoholin stellate groups of needles. By the action of zinc chloride onhcptoic chloride and dimethylaniline a base melting a t 72.5" andboiling at 278" under 15 mm. pressure is obtained together withhexyl dirnetlranzidophenyl ketone C6H,,*CO*CsH4*NMe,. The ketonemelts at 48*5" boils a t 190" under 20 mm. pressure and yields anacetoxime which crystallises in silvery glistening scales.Paraxylyl Ethyl Ketone and its Oxidation to Orthometa-dimethylbenzoylacetic Acid. By A. C ~ a u s and E. FICKERT (Rer.,19 3182-3184) -paraxy7yZ ethy! ketone C)GH~M~~'COE~ obtainedfrom parxxylene and propionyl chloride is am colourless mobile highlyrefractive liquid having an aromatic odour and strong bitter taste.Itis lighter than water and boils a t 237-2:38" (uucorr.). When oxidisedwith dilute solution of potassium permanganate it yields a mixture ofxsly 1 car box y li c aci d and par ax y ly 1-p- ketonic (or t h ome t ad inz et h y Ib mi xoy 1acetic) acid CsH3Me2*CO*CHz*COOH. The acids are best separatedw. P. w.VOL. L11. 254 ARSTRACTS OF CHEMICAL PAPERS.by means of their barium salts the ketonate being very sparinglysoluble. The ketonic acid is sparingly fioluble in water and lightpetroleum easily in alcohol ether benzene &c. It crystallises inneedles melting at 132" (uncorr.). The sotlizm salt (with 1H,O) iseasily the calcium ( + 2$H20) barium (+ 4H20) and silver salts verysparingly soluble.Similar reactions have been obtained with aromatic ketones contain-ing the ethyl and propyl &c.groups and are now being investigated.Nitrophenyl Benzoates and Nitrobenzoates and their Pro-ducts of Decomposition. By G. NEUMANN (Ber. 19 2979-2982).-Continuing his previous work (Abstr. 1886 350 939) the authorprepared metunitrophenyZ benzoate by heating metanitroplienol withbenzoic chloride. It is readily soluble in acetic acid alcohol and hotlight petroleum and forms pale yellow crystals which melt at 95".When treated with nitric acid of RP. gr. 1.48 it yields metanitrophenylwrtanitrobenzoate. This compound forms white crptals melts at129" and is readily soluble in cold chloroform and hot alcohol ether,and light petroleum.Metaparadinitrophenyl metanitrobenzoate is obtained by the action ofnitric acid of sp.gr. 1-53 on metanitrophenyl benzoate. It crystallisesin bright yellow needles melts at 149" and is sparingly soluble inmost ordinary solvents especially in ether and light petroleum.Metanitrophenyl benzoate when dissolved in a mixture of equalparts of nitric acid of sp. gr. 1.51 and sulphuric acid of sp. gr. 1.82,yields trinitroresoroinol and metanitrobenzoic acid.L. 1'. T.W. P. W.Method for the Introduction of Carboxyl into AromaticHydrocarbons. By E. LELLMANN and 0. BONHOFFER (Ber. 19,3.231) .-Benzoic acid can readily be prepared by acting with diphenyl-carbnmide chloride on benzene in presence of aluminium chloride,and heating the benzoyldipheuylarnine so obtained with hydrochloricacid. Paratoluic and xylic acids [COOH Mez = 1 2 41 wereobtained in a similar manner from toluene and metaxylene respec-tively.Paraxylene does not react with the chloride ; hence it wouldseem that the group CO*NPhi can only take up the para-position withrespect to methyl.By J. PLOCHL (Ber. 19 3167-3172) .-Inanswer to the colninunications of Lipp (this vol. p. 142) and E. Erlen-meyer jun. (ibid.) the author upholds the correctness of his view(Abstr. 1884 604) that his acid C9H80 is the true phenylglycidicN. H. M.Phenylglycidic Acid./"\ acid CHPh.CH*COOH and that Glaser's acid is p-hjdroxycinnamicacid.The author finds that paranitrobenzaldehyde forms with hippuric acid8 condensation-derivative corresponding with benzoylimidocinnamicanhydride. This substance when heated with fuming nitric acidfirBt forms paranitrobenzoylimidocinnamic acid but at 120-130" it iORQANIC CHEMISTRY.255decomposed yielding a brownish-red compound (a polymeric nitro-phenylethylene oxide) whilst carbonic anhydride is a t the same timeevolved. Lipp's paranitrophenylglycidic acid gives the same decom-position-products. The author points out that in many other casesalso the introduction of a nitro-group into the benzene nucleus causesa variation in the behaviour of the side-chain in reactions.E. Erlenmeyer jun. objects to the author's formula bxause thelatter's phen~lglycidic acid yields a phenylhydrazine and a hydroxyl-amine compound and shows the thiophen reaction.The author statesthat with ammonia his acid gives a compound C,H,NO. He believesthis compound to have the constitution CHPh< I >CO and thinksthat Erlenmeyer's compounds have probably analogous structures.As further strongly supporting the correctness of his formula theauthor cites-( 1) the gradual decomposition of the acid when exposedto moist air into benzaldehyde and a new acid ; (2) the formation ofa polymeric phenylethylene oxide (and not Erlenmeyer and Lipp'spolymeric phenylethylaldehyde) by the action of hydrochloric acid ;and (3) the easy convertibility of the acid into pheizylpyruvic acid;the latter is easily soluble in boiling water crystallises in tables andmelts a t 160-161".CHN -It is still under investigation.L.T. T.Benzoquinonecarboxylic Acids. By J. U. NEF (Annalen 237,1-39).-This paper contains a description of the derivatives ofdurene durylic acid and quinonetetracarboxylic acid which hasalready been published by the author (Abstr. 1886 64 241 5.50).The following substances have not been previously mentioned :-Theacetic derivative of diamidodurylic acid prepared by the action ofacetic anhydride on the amido-acid a t 140" crystallises in quadraticplates and melts a t 275'.Dihydroxydurylic acid C,Me,(OH)2*COOH (Abstr. 1886 24l) issoluble in alcohol ether and in hot water. The acid forms an amor-phous lead salt and reduces ammoniacal silver nitrate solution. Theethyl salt C6Me3(OH)2*COOEt forms colourless needles.It melts at1@9" and is soluble in hot water alcohol and the usual solvents withthe exception of light petroleum. The alcoholic solution is oxidisedby ferric chloride ethyl duroqui?l.onecarboxyZate C6*@zMe,GOOE t beingformed. This substance is best prepared by the action of an etherealsolution of ethyl iodide on silver duroquinonecarboxylate. It crystal-lises in golden needles melts at 51" and Hublimes easily. It is in-soluble in cold water but dissolves freely in alcohol ether and in (warm)light petroleum. On reduction with sulphurous acid i t yields ethyldihy droxydurylate. Duroquinonecarboxylic acid is co .npletely con-verted into nitropsewdocumenequinone C,O2Me3.NO2 by the action ofwarm strong nitric acid. The nitroquinone crystallises in goldenscales soluble in ether chloroform benzene light petroleum alcohol,and nitric acid. It melts a t 113" and sublimes readily.Thecorresponding quinol c6Me,( OH),*N02 is obtained by the action ofsulphurous acid on the alcoholic solution of the nitroqninone a t 100".s Ethyl succinosuccinate . . . . . . . . . .Ethyl paradiketohexamethylenetetra.carboxylate.Ethyl paradihydroxyphthalate . . . .Ethyl quinoltetracarboxylate . . . . .Paradihjdroxyterephthalic acid . . . .Quinoltetracarboxylic acid . . . . . . .Ethyl paradiamidoterephthalate.. . .Ethyl diamidopyromellitate.. . . . . . .Properties.--:olourless needles,m. p. 126-127":olourless needles,m. p. 142-144"pale yellow nee-dles or prisms,m.p. 133"yellow needles,m. p. 126-128"yellow scalespale yellow broadneedlesgolden needles,m.p. 168',strong baeered prisms m. p.134' feeble bas(Solutions.--pale blue fluores-cencepale blue fluores-cencestrong blue fluo-rescencestrong blue fluo-resenceyellowish-green,with green fluo-rescenceyellow with greenfluorescencebrown with gold-en yellow fluo-rescencered yellowish-redfluorescenceColour mithFe2CI,. -cherrycherryblue-greenblue-greenintense blueintense bluORGANIC CHEMISTRY. 257It crystallises in golden needles melts at 106" and is soluble in ether,alcohol chloroform acetic acid and in hot water.The compound obtained by the reduction of ethyl dinitropyromelli-tate and described by the author as ethyl azopyromellitate (Abstr.,1886 64) ib now foiind to be ethyl dianzido~yronzellitate,By reducing the alcoholic solution with zinc-dust and mlphnric acid,ethyl paradiketohexamethylenetetracarboxylate is produced.Ethyldiamidopyromellitate yields a diacetic derivative,C ( NH Ac) 2 ( C 0 0 E t) 4,which crystallises in colourless plates and melts at 149". It is freelysoluble in acetone chloroform acetic acid and hot alcohol. It is notdecomposed by boiling with alkalis or with hydrochloric acid.Ethyl quinoltetracarbo;lute C,(OH)-(COOEt)4 (Abstr. 1886 550),bears a striking resemblance in its properties to Herrmann's ethylquinonedihydrodicarboxylate which Baeyer has shown (Abstr. 1826,445) to be ethyl paradihydroxyterephthalate. &uinoZtetracarboxyZicacid crystallises with 14 mols. H,O which it retains a t 100".Itdissolves freely in hot water forming a fluorescent solution fromwhich it is precipitated by mineral acids. Ferric chloride gives a bluecoloration. The soluble salts of this acid form yellow solutions whichexhibit a green fluorescence. Attempts to oxidise quinoltetracarbo-xy lic acid to quinonetetracarboxylic acid were unsuccessful.E thy1 quinoltetracarboxylate is converted in to ethyZ paradiketo-hezamethyZAnetetracarboxyZlLte by shaking the alcoholic solution withzinc-dust and hydrochloric acid (Abstr. 1886 551). This substanceyields ethyl quinoltetracarboxylate on treatment with bromine andcarbon bisulphide and it readily enters into reaction with ammoniumacetate and with phenylhydrazine.The resemblance between the derivatives of ethyl diamidopyrornelli-tate and etbyl succinosuccinate is shown in the table (p.256). w. c. w.Constitution of Azo-opianic Acid. By C. LIEBERMANN (Bar.,19 2920-2922) .-Although the so-called azo-opianic acid has beenrecognised as the anhydride of orthnmidohemipinic acid yet hithertoit has not been found possible to convert the latter into the former bythe abstraction of the elements of water. In this paper however itis shown that both orthnmidohemipinic and azo-opianic acids yieldan identical acetylazo opianic acid. The last acid when warmedwith alkali and subsequently acidified yields acetylorthamido-hemipinic acid CsH( OMe)P( COOH),*NHAc + HzO which crystallisesin colourless needles melting at 160-1 i O O with complete decomposi-tion. The acetyl-group is still retained when the acid is heated withconcentrated sulphuric acid ; a result to be explained by the formerresearches of the author and Kleemann which have proved t h a t theacetyl-group in acetylazo-opianic acid is attached to the nitrogen andnot to the oxygen-atom. V.H. V2.58 ABSTRACTS OF CHEMICAL PAPERS.An Isomeride of Hemipinimide. By C. LIEBERMANN (Ber. 19,29234927) .-The author has recently shown that hemipinimide isproduced by boiling a mixture of opianic acid with hydroxylaminehydrochloride in equiinolecular proportions. If however the changebe effected a t ordinary temperatures a substance isomeric with hemi-pinimide is produced which it is proposed to call opianoxzrnic anhy-dride.It crystallises in long colourless needles melting a t 114-115"; its alcoholic solution unlike that of hemipinimide is notfluorescent. When melted the substance is converted with con-siderable development of heat into hemipinimide. This anhydrideonly displays feeble acidic properties but on protracted heating withwater it is converted into hemipinic acid.Similarly when ethyl opianate and hydroxylamine hjdrochlorideare heated the above anhydride is also formed; all attempts to pre-pare opianoximic acid have hitherto failed. V. H. V.Isomeric Aldehydophenoxyacetic Acids. By T. ELKAN ( B e y ,19 3041-3054) .-Paraldehydophenoxy acetic acid,CHO*C,H4*OCH,*COOH [CHO OCH = 1 41,is obtained by heating equivalent amounts of parahydroxgbenzalde-hyde and monochloracetic acid in a silver dish on a water-bath andadding sufficient caustic soda to give an alkaline 1-eaction.When itbegins to solidify a slight excess of chloracetic acid is added thesolution being always kept alkaline ; it is then treated several timeswith water and evaporated to dryness. The product is dissolved inhot water precipitated when cold with hydrochloric acid and theyellowish acid so obtained purified by boiling with calcium carbonate.I t crystallises from water in small plates melting at 198" is verysparingly soluble in cold water more soluble in alcohol ether,benzene and chloroform and shows aldehydic properties. It yieldsa sparingly soluble double compound with hydrogen sodium sulphtte,and reduces ammoniacal silver solution but not E'ehling's solution.The silver salt C9H701Ag crystallises in needles.Bromine-wateracts on the acid with formation of a brorniize-dei*ivative C3H,01Br;this crystallises from hot water in slender branched needles meltingat 185". Ethyl paraldehydophenoxyacetate is a crystalline substancewhich begins to decompose at IOO" and melts at 155". The hydroxyl-arnine-derivative C9H901N forms large spear heads melting a t 145".Metaldehydophenoxyacetic acid CgH,04 is prepared in a mannersimilar to the para-compound. It crystallises from warm water inslender needles which melt a t 148" and shows the same aldehydicreaction as the isomeride; it is rather more solub!e than the latter.The silver and ethyl salts were prepared.The monobromo-derivativeforms lustrous plates melting at 154". The hydl.oxylanaiiie-comp~,undcrystallises in sleuder needles melting a t 168'. When oxidised withpotassium permanganate both isomerides yield the correspondingdicarboxylic acids.C 0 0 H*C6H4*0 CH2* CO 0 H[ = 1 41 crystallises in white needles melting at 278" ; it dissolvesPhenozyacetic-paracarbozy lic acidORGANIC CHEMISTRY. 259readily in alcohol ether and glacial acetic acid less in benzene andchloroform and only very sparingly in water. The siher salt wasanalysed. The pheii y Zhydraaine-deTivatiue C15H14N203 forms slender,yellowish-white needles which melt a t 159" and dissolve sparinglyin water readily in alcohol and ether.Phe.rzoxyacetic-n~etacarboxyZic acid melts at 206O and is analogous inits solubility &c.to the para-acid. The pheny lhydrazine-compoundforms slender needles which melt a t about 140'.Pheizoxz~acetic-paracrz~lic acid COOH CH CH*C6H4*OCHz*COOH isprepared by gently boiling equal parts of paraldehydophenoxyaceticacid and dry sodium acetate with acetic anhydride (3 parts). Itmelts a t 625" dissolves readily in alcohol ether and glacial aceticacid ; i t is also soluble in benzene and light petroleum.Phenoxyacetic-metnc?yZic acid CllHI0O5 is obtained in like mannerto the para-compound and crystallises in needles melting a t 219".OTthacrylaldehydophenoxyacetic acid,CHO'CH CH*C6H4*OCHz*COOH,is prepared by exactly neutralising a dilute solution of orthaldehydo-plienoxyacetic acid heating it at 50" to 60° and gradually addingsimultaneously an aqueous solution of acetaldehyde and 5 per cent.soda solution so as to keep the solution always slightly alkaline.Itis then warmed on a water-bahh cooled down and acidified withdilute sulphuric acid. The acid crystallises from hot water in trans-parent plates which melt at 153".The rneta-acid crystallises (with 1 mol. H,O) in long yellowishneedles which melt a t 100".The para-acid forms a crystalline yellowish precipitate melting at182". All three isomerides show aldehydic properties ; they combinewith hydrogen sodium sulphite reduce ammoniacal silver solutions,and condense with phenylhydrazine.P hsnox y acetic- ort hacry lic acid met hy 1 ketone,COMe*CH CH*CsH4*O*CH2GOOH,is obtained by adding pure acetone (from the hydrogen sodiumsulphite compound) to the warm slightly alkaline solution of sodiumorthaldehydophenoxyacetate. It melts a t 108".The meta-compound,Cl2HI2O4 crptallises in well-formed anhgdrous prisms which becomeopaque when kept. The para-compoud melts at177-li8".The hlldroxl/lami.re-deriz~ative of orthaldehydophenoxyacetic acid(Rbssing Abstr. 1885 388) crystallises in plates very readily solublein hot water alcohol and ether more sparingly in benzene chloro-form &c. It melts at 138". N. H. M.It melts at 122".Vanillinoxyacetic Acid. By T. ELKAN (Ber. 19 3054-3056).-VaniZZinozyncetic acid CHO*C6H3(OMe)*0*CHl~COOH [ = 4 2 11,is prepared by fusing monochlo~*acetic acid with vanillin in a silverdish and adding an excess of caustic potash until the solution isdistinctly alkaline.After four hours (during which the water lost b2 60 ABSTRACTS OF CHEMICAL PAPERS.evaporation must be from time to time replaced) the reaction iscompleted. It crystallises from hot water in slender yellowish-whiteneedles melts at l88" and dissolves readily in ether alcohol chloro-form &c. It combines with phenylhydrazine and with hydrogensodium sulphite and reduces ammoniacal silver solution. The copperand silver salts were prepared.Vanillic-ozyacefic acid COOH*CsH3(OMe)*O*CH:,.COOH [ =4 2 11,is formed in the preparation of vanillinoxyacetic acid when the trent-ment with potash and chloracetic acid is too prolonged.It crystal-lises from water in slender branched needles which melt a t 256" ; itdissolves in ether benzene chloroform; &c. The copper salt has afine green colour; it is insoluble. N. H M.Derivatives of Pyruvic Acid. By G. GERSON (Ber. 19 2963-2969). - When ethyl a-cyano-a-hydroxypropionate is treated withphenylhydrazine a compound melting at 116" and identical a-ithFischer's ethyl phenylhydrazinepyruvate (Abstr. 1884 52) is ob-tained.E t h y l a-anilido-a-cyanopro~ioiaate NHPh*CMe(CN).COOEt is pre-pared by treating ethyl a-cyano-a-hydroxypropionate with aniline inalcoholic solution. It crystallises in large transparent cubes be-longing to the rhombic system with the axial ratio a b c =0.79063 1 1.56366 ; the followi!g faces were observed mP pre-dominating mPm mP00 narrow Po= fairly large Pm smaller thanf'm.It melts at 101*5" and is insoluble in water but readily solublein alcohol and ether.Ethyl anilidoisosuccinamate NHPh. CMe(CONH,) COOEt isformed when ethyl a-anilido-a-cyanopropionate is dissolved in con-centrated sulphuric acid poured into water and neutralised withammonia. It crystallises from benzene in slender white needles,melts a t 86" is sparingly soluble in cold water readily soluble inhydrochloric acid alcohol and benzene but insoluble in light petro-leum. The crystalline hydrochloride is very soluble in water. Onboiling ethyl anilidoisosuccinamate with a solution of soda as long asammonia is evolved acidifying with acetic acid converting into leadsalt and decomposing it with hydrogen sulphide a-aniliilopropionicacid NHPhGMeH-COOH (Tiemann and Stephan Abstr.1883 1991,is obtained in white crystals meltling at 160".E t h y l a-orthotoluido-a-cyn.noprop~~~~~te C,H,-NH*CMe( CN)*COOE t,prepared in a similar manner to the anilido-compound crystallises inrosettes of small whito needles melts a t 93" and is insolnbIe in water,sparingly soluble in cold alcohol readily soluble in hot alcohol andbenzene. On treating i t with concentrated sulphuric acid and neutral-ising with ammonia it yields ethyl orthofoluidoisosucci.namate,C7H7*NH*CMe( CONH,) *COOEt,which crystallises in long transparent needles and resern bles theanilido-compound in all its properties. By boiling the isosuccinamatewith potash solution &c.orthotoluiLZopropionic acid,C7H7*NH* CMeH- C OOHORGANIC C;HE&IISTRT. 261is obtained in slender white needles which melt a t 116" and dissolvereadily in water alcohol and benzene.E t h y l a-paratohido-a-cyanopropiowate crystallises in light brown,glistening spangles melts a t 80*5" and is insoluble in alcohol amdbenzene sparingly soluble in water.E t h g l aa - naphtli y lavnido-a-cyanopropionate forms slender whitescales which melt at 134" and are readily soluble in alcohol andbenzene sparingly soluble in cold water. By treatment with sul-phuric acid &c. ethyl a-na~htl~ylnmidoisosucctnumate is obtained inlong white needles melting at 159". It dissolves readily in alcoholand benzene sparingly in cold water.Etlzy 1 ap-n apht h y 1 am ido-a- cy asiopropion a te cry stallises in smallrosettes is almost insoluble in water and cold alcohol soluble in hotalcohol and benzene and decomposes a t 200" without melting.w. P. v7.Two New Diketonic Acids. By W. KUES and C. PAAL (Bey.,19 3144--3148).-The authors have examined the insoluble crystal-line substance obtained by them during the hydrolysis of ethylbenzoylisosuccinate (Abstr. 1886 354) and find it to be ethyl cli-phenncylmalonate C( CHBZ)~ COOEt),. Its formation must be duet o the formation of some ethyl disodiomalonate and the action of thebromacetophenone thereon. This substance forms large colourlessprisms melts at 118-119" and distils almost without decomposition.It is easily soluble in water benzene acetic acid and carbon bisul-phide more sparingly in alcohol and is irisoluble in light petroleum.i t reacts strongly with phenylhydrazine b u t no homogeneous sub-stance could be isolated from the product.Hydroxylamine is with-out action on it as are also aqueous solutions of the alkalis. Whendigested with strong alcoholic potash it is saponified and yieldsdipheiracy Zmnlonic acid cryatallising in colourless prisms melting withevolution of carbonic anhydride at 134". I t is spa~ingly soluble inwater easily so in ether alcohol and acetic acid insolable inbenzene. It forms a compound with phenylhydrazine. When care-f u l l y melted carbonic anhydride is evolved and diphenacglncstic arid,CH (CH,Bz),*COOH is formed. This crjstallises in silky needles,easily soluble in ether alcohol and benzene and mells a t 132-133".When heated with an acetic solution of phenylhydrazine it yieldsa compound of the formula C30H26N40 crystallising iii white needleswhich melt a t 164-166" and are soluble in alcohol and acetic acid,insoluble in alkalis.The hydrazine-compound is not decomposed bydilute acids. Adopting the views of the composition of such com-pounds advocated by E. Fischer and W. Roser the authors considerthe following as the most probable formula for this substance :-NzHPh CPh*CH,*CH<CH CO*NPh- Cph>N.L. T. T.Action of Zinc Alkyl Compounds on Ethyl Malonate. By E. LANG (Bey. 19 2937-293Y).-Zinc methyl or zinc ethyl acts atordinary temperatures on ethyl malonnte with evolution of methaneand ethane and formation of a crystalline magma of ethyl phloro262 ABSTRACTS OF CHEMICAL PAPERS.glucinoltricarboxylate C,(OH),(COOEt),.The reaction thus con-sists of the abstraction of the elements of alcohol and subsequentcondensation. V. H. V.Furfurane-derivatives from Resorcinol. By A. HANTZSCH(Ber.,19 2927-2934).-1t has been shown that the sodium compoundsof the monohydric phenols when treated with ethyl chloracetate yieldat first ethyl phenoxyncetoacetate and finally ethyl furfurocarboxylate.The dihydric phenols undergo a similar but more complicated reac-tion according as the mono- or di-sodium compound reacts with oneor two molecules of the ethereal salt. In the former case hydroxy-cumarones are obtained in the latter benzodifurf uro-derivatives thenature of the isomerism of which is dependent on the relative positionof the carbon-atom to which the furfuryl-ring is attached.Thus inthe case of resorcinol two such isomeric hydroxy- and difurfuro-derivatives are possible precisely as two quinolines the meta- and theana-series are synthetically formed from amines of the metn-series.E t h y l metahydroaycuwiarilate OH*C,OH,*COOEt [OH COOEt Me= 2 2' 3'1 formed from mono-sodium resorcinol and ethyl chlor-acetate crystallises in white needles melting a t 178" readily solable inether. The corresponding acid crystallises with + mol. H,O in needleswhich melt a t 226" with evolution of carbonic anhydride and forma-tion of hydroxymethy Zcumarone CsOH4Me*OH.This compoundcrystallises in needles melting at 96-97' soluble in water alcohol,and ether.From disodium resorcinol and ethyl chloracetate two isomeric ethylbenzodimethylfurfurodicarboxylates are formed the nature of theisomerism of which is analogous to that of anthracene and phenan-threne. These are provisionally designated the a- and @-series asthe experimental results are insutiicient to fix the formula of eachcorn po imd.E t h y 1 metabenzodimethyl-a-difurfurocarboxylate C,0,H2Me2(C00Et),,crystallises in needles melting a t 186" and its isomeride in moresoluble aggregates melting a t 140-141". Both isomeric etherealsalts are readily saponified ; the corresponding acids melt above310" with decomposition and are sparingly soluble in water but moresoluble in alcohol. Both the acids and their salts are difficult todistinguish one from the other. Only one of the isomeric difurfuranes,C H e 0 CMe ->C,H2<- CM :>CH is described corresponding with theethereal salt which melts a t 186" ; it is a clear brown oil boiling at270" solidifying in a freezing mixture aiid melting at 17"; witliconcentrated sulphuric acid i t gives a light blue coloration resemblingthat obtained with coeruglignone.Furfurane-derivatives from Phloroglucinol.By E. LANG(Bey. 19 2934-2937).-The reactions between the butyric alcohol,phloroglncinol and ethyl chloracetate in presence of sodium ethylate,are analogous to those of resorcinol described in the precedingAbstract. The three series of compounds are formed in a similarway yet the presence of alcohol is necessary for the production ofV.H. VORGANlG CHEVISTRY. 263the dihydroxy-product and its absence for that of the trif urfuralde-hy de-derivatives.Ethyl metu-dihydroxymefhylcumarilate C,OH,Me(OH),*COOEt,forms small white needles melting at 242" readily saponitied andconverted into the corresponding acid which crystallises with8 mol. HpO and melts a t 281" with evolution of carbonic anhydride.obtained by treating trisodium phloroglucinol with 3 mols. ofethyl chloracetate crystallises in satiny needles melting at 296-298" sparingly soluble in all menstrua. The corresponding acidseparates with 1 mol. H,O in a gelatinoua form. On distillationwith alkali the benzotrimetbyltrifurfurane c6( <-o ->CH) isobtained ; it crystallises in needles melting a t 115-120" and is verysoluble in most menstrua.CMeV. H.V.Sulphobenzidedisulphonic Acid. By R. OTTO and A. ROSSING(Bet-. 19 31 24-3129).-Su~I~obenzidedi~uiphonic acid,is prepared as already described (Abstr. 1879 649) by the action ofsulphuric hydroxychloride (2 mols.) on sulphobenzide. It is veryprobably the dimetasulphonic acid. It forms a yellowish fibro-crystalline deliquescent mass readily soluble in alcohol and water,but insoluble i n ether and benzene. It forms only normal salts.The potassium salt crjstallises with 1 mol. H,O ; the sodium with3 mols. H20 calcium with 6fr mols. H20 barium 5 mols. H20 copperwith 3; mols. H,O and the lead salt with 3 mols.H20. The chZoriclecrystallises in smali fatty plates and melts a t 175-176'. The umideforms white needles melts a t 240" is nearly insoluble in ettier acdbenzene sparingly soluble in boiling water more soluble in alcohol.The a n i l i d e forms lustrous white plates and melts at 212'. Theethyl salt melts a t 81-82". The diphcmyZsuZphone S02(C6H4*S02Ph),,is obtained in small quantity by heating the disulphonic acid withbenzene and phosphoric anhydride ; it melts a t 192-193".Experiments to obtain a trisulphonic acid from sulphobenzide wereunsuccessful . A. J. G.Non-existence of Claesson's Phenylsulphineacetic Acid.By R. OTTO and E. ENGELHARDT (Ber. 19 3138-314l).-Claefisonstates (this Journal 1876 i S67) that he obtained the above acid (aceto.phenylsulphinic acid) Ph*SO*CH2*C00H by the partial oxidation ofphenylthioglycollic (pbenylthiacet'ic) acid.The authors have carefullyrepeated these experiments and find that the substance described byClaesson was not a homogeneous compound but a mixture of phenyl-sulphonacetic acid Ph*S02.CH2*COOH with nnoxidised phenyl-thioglycollic acid. L. T. T.Metatoluenesulphonic Acid and its Salts. By K. VALLIN(Her. 19 2958-2953) .-The metatoluenesulphonic acid employed inthe previous research (Abstr. 1880 256) contained para-acid as anso2 C12H*(SOsH)2264 ABSTRACTS OF CHEMICAL PAPERS.impurity; the author has therefore repeated the work with puremeta-acid obtained from toluidinesulphonic acid [CH3 S0,H NH,= 1 3 41 by diazotising and boiling with alcohol.The acidcrystallises in slender needles or thin scales. The potassium sodium,silver calcium barium lead magnesium zinc cadmium and coppersalts are described. The chloride C7HI,*SOzC1 has not been solidified ;the amide crystallises from water in lamina melting a t 107" fromalcohol in moiioclinic crystals melting a t 108". At 14" 1 part of theariiide dissolves in 376.7 parts of water and 5.74 parts of alcohol.The hydrosubhide C,H7*SH boils at i95-205" and does not solidifyat -20".S o d i u m paratoluenesubphonate does not crystallise with 3 mols. ofH20 but either with 2 mols. in laminated masses or a t low tempera-tures in rectangular tables with probably 4 mols. H,O. The hydro-sulphidc of the para-acid melts at 43-44' and boils at 194" that ofthe ortho-acid melts a t 15" and boils a t 193".w. P. w.Tolwnedisulphonic Acids. By P. KLASON (Ber. 19,2887-2890).-Toluenemetasulphonic acid is convertible into a rriixture of twodisnlphonic acids separable by the difference in solubility of theirbarium salts the less soluble separating with 1 mol. H,O as acrystalline powder. Its potassium salt crystallises with 1 mol. H,Oin pointed prisms the acid chloride in rhombic tables melting at 96",and the arnide in minute prisms melting at 224". This acid is iden-tical with one obtained by Hgkausson from the mother-liquors ofpotassiiim a-toluenedisulphonate. The more soluble barium saltcrystallises in prisms containing 3& mols. HpO the chloride in trun-cated prisms melting at 95" ; the amide melts at 214".This acid isidentical with one obtained by Limpricht from toluidinedisulphonicacid. V. H. IT.Cumene-orthosulphonic Acid and Orthocumic Acid. ByA. CLAUS and J. A. SCHULTE IM HOF (Ber. 19 3012-3017) -Whencumene-P-sulphonic acid (Abstr. 1885 903) is oxitiised withchromic mixture. it is destroyed without formation of intermedidteproducts ; it is therefore concluded that the acid has the constitution[C3H7 S03H = 1 21.Orthocumic m i d CHMez*C6H4*COOH is obtained by fusing thepotassium or barium salt of the above sulphonic acid with sodiumformate ; it is insoluble in cold water readily soluble in alcohol ether,glacial acetic acid &c. When heated at 200° it becomes brown andpartly sublimes and does not melt a t 300". It distils with steam.The barium and caZcium salts (each with 2 mols.HzO) and thenzagnesium salt (with 6 mols. H,O) crptallise in needles readilysoluble in water. The alkali salts are crystalline but Fery hygroscopic.The chloride forms a yellow oil readily soluble in ether chloroform,&c. ; when treated with dry ammonia it is converted into the nmide.The latter crystallises from alcohol in small needles melting a t124" (uncorr.) .Orthocumic acid is not acted on by chromic mixture of ordinarystrength. When oxidised with potassium permanganate it is conORGASIC CHEMISTRY. 2 fi5verted into phthalic acid; no hydroxycumic acid is formed. Thereaction is of interest as showing that the reaction by whichisopropyl in paracumic acid is oxidised to hydroxyisopropyl does nothold good when the isopropyl-group is in the ortho-position tocarboxyl (R.Meyer Abstr. 1878 878).Action of Aldehydes Anhydrides and Diazo-compounds onthe three Methylindoles. By E. FISCHER (Ber. 19 2988-2991).-When benzaldehyde (1 part) is heated with methylketole (2 parts)at loo" an almost quantitative yield of be~azyli~enemethy172etole,Ph-CH (C9H,N) is obtained. This substance crgstallises well fromacetone and most probably has the constitutionN. H. M.With paraldehyde and zinc chloride methylketole yields a crystallinecompound soluble in hot alcohol and in acetone. 1' Methylindolecombines slowly with benzaldehyde a t loo" the reaction however ishastened by the addition of a small quantity of zinc chloride; theproduct crystallised from acetone melts at 197" and is isomeric withthat obtained from methylketole.Skatole and benzaldehyde on thecontrary combine only slowly in the presence of zinc chloride a t 100",and the resulting compound which forms colourless crystals differsfrom the preceding derivatives in its much greater solubility andlower melting point.Equal parts of phthalic anhydride and rnethylketole heated a t 100"with zinc chloride yield a compound C9HgN.C8H4O3 which whenheated to about 200" is converted into an acid C9H8N*CO*C6H4*COOH,with loss of carbonic anhydride. From I' methylindole at 100" a com-pound having different properties is obtained. The action of aceticanhydride on methylketole in the presence of sodium acetate hasalready been studied (Abstr.1881 734) ; since however the acetylderivative reacts with phenylhydrazine to form a compound CI7Hl7N3,and is therefore a ketone Jackson's formula C6&<NAc>CMe,must be regarded as incorrect ; the substitution of acetyl GCcurringprobably in the position 3'. When 1' methylindole is heated a t lo()"with acetic anhydride and zinc chloride a ketone is obtained whichis probably identical with Baeyer's acetylindole (Abstr. 1879 938).Methylketole readily reacts with diazobenzene chloride in the presenceof acetates dissolved in weak alcohol and forms an azo-compound ofthe composition C6H5*N N.C9HsN. It crystallises in yellow needles,melts at 115-116" and by reduction with zinc and hydrochloric acidCHyields aniline and amidomethylketole. w.P. w.Hydrocarrotene and Carrotene. By F. REINITZER (iUonat&.Qhem. 7,59'7-608).-Two crystalline substances have been extractedfrom carrots the one colourless hydrocarrotene the other dark red,carrotene ; these have been more recently examined by Huseman andArnsud the latter of whom has found carrotene associated withchlorophyll in the leaves of various plants and assigns to it the formul2 66 ABSTRACTS OF OHEMTCAL PAPERS.of an unsaturated hydrocarbon c26H38 whilst hydrocarrotene is con-sidered to be allied to cholesterin.The method used for the extraction of these substances is fullydescribed as also their separation from one another by frequentrecrystallisation from boiling acetone and methyl alcohol.Hydro-carrotene is insoluble in water sparingly soluble in cold more readilyin boiling alcohol very soluble in acetone from which it crystallisesout in long needles but from methyl alcohol in micaceous leaflets.I t contains 5 per cent. of water melts at 137.4" ; [a]= = -37*4" t =21" C = 4.131 in chloroform. I n these physical properties as alsoin various chemical reactions it resembles cholesterin a view furthercoilfirmed by the formation of its acetate and benzoate the meltingpoints and specific rotatory powers of which at*e compared with thoseof other cholesterins. Hydrocarrotene appears t o be more nearlyidentical with phytosterin although i t is thought advisable for thepresent to retain its particular name. From cholesterin itself hydro-carrotene differs in its behaviour with bromine which is a t firstabsorbed and subsequently the change is accompanied with evolutionof hydrobromic acid.The bromide formed crystallises in long,colourless transparent needles moderately soluble in alcohol readilysoluble in ether and carbon bisulphide. Husemann's observation thathydrocarrotene is converted into carrotene by bromine is apparentlyerroneous. The improbability that carrotene a coloured substance isa hydrocarbon is pointed out although no experiments are described,but allusion is made to the similarity of carrotene to a colouringmatter present in the paradise apple Lycopersicum esculentum.Diphenylmetaxylylmethane and Diphenylorthoxylylme-thane. By W. HEMILIAN (Ber.19,3061-3075).-Diphenylmetax~ZyZ-methane CHPh2*C6H3Me2 [Me Me CHPh = 1 3 61 is preparedin a manner similar to diphenylparaxylylmethane (Hemilian Abstr.,1884 321) by heating benzhydrol dissolved in pure metnxylene,with phosphoric anhydride for four hours a t its boiling point. Theproduct is treated with water and with aqueous soda and the oil dis-tilled. It solidifies when kept for a few days and is pnrified bytreating a warm saturated solution in glacial acetic acid with twicethe amount of ethei. and allowing it to evaporate slowly. It formslarge six-sided prisms which melt a t 61.5" and distil above 360". Itdissolves readily in alcohol ether benzene &c. When boiled for along time with chromic mixture and the product extracted withboiling soda solution an insoluble residue i8 obtained consisting ofdipl~enylmethy~l~thal~de CPh2<- ha&- _> ; this crystallises fromalcohol in lustrous prisms which melt at 147Oand distil a t above360" without change ; it is soluble in ether benzene &c.insoluble inaqueous alkalis.MethyZtr~p~~enyl~~~ethaneearbory7~~ acid CHPh2*C6H3Me*COOH isobtained by boiling diphenylmet,hylphthalide with alcoholic sodasolution and reducing the sodium salt of the hydroxy-acid so formedby boiling with zinc in alkaline solution. It forms large lustroustabular crystals which melt at 203" and distil without change. It isv. H. v.C €3 MORGANIC CHESIISTRY. 267rather readily soluble in hot alcohol ether and acetic acid. Thebariihm salt (with 3 mols.H,O) crystallises in slender needles almostinsoluble in water rather readily soluble in boiling 70 per cent. alcohol.Other salts were prepared. When carefully oxidised it is reconvertedinto diphenylmethylphthalide. When the solution of the acid instrong sulphuric acid is poured into water a precipitate is obtainedconsisting of meth ylpheizy Zanthranol C2,H160. It crystallises fromalcohol in small yellow plates which soften a t 150" and melt at 170" ;when oxidised it is converted into methy~henylhydroxanthranol,C6H&te< -CO.CoH,->. The latter forms large colourless prismsmelting at 213" ; it is insoluble in aqueous alkali; the solution insulphuric acid has an intense purple-red colour. When distilled withan excess of alkali paramethyltriphenylmethane is obtained identicalwith that prepared by E.and 0. Pischer from phenylparatolglcarbiiioland benzene (Abstr. 1879 384).Dip hen y lp h t ha lidecarb oxy 1 ic acid 0 < !:;:> C6H3- C 0 OH is con-tained as sodium salt in the alkaline extract from the oxidationexperiment with diphenylmetaxylylmethane. It crystallises fromwarm alcohol in large tabular crystals (with 1 mol. EtOH) ; it isinsoluble in water readily soluble in alcohol ether benzene &c. ; itmelts a t 228" and distils unchanged. The calcium salt (with 3 mols.H20) crystallises from 70 per cent. alcohol in slender lustrousneedles ; the silver salt crystallises from the same solvent in hair-likeneedles insoluble in water. When the acid is distilled with excess ofbaryta benzophenone and barium isophthalate are formed.Tripheny Zmefl~a~edicarboxyl~c acid CHPh2*C6H3(COOH) [ =1 2 41is prepared by the action of zinc-dust on the alcoholic solution of theanhydro-acid.It forms slender lustrous needles readily soluble inalcohol and acetic acid. It melts a t 2 B 0 and partly sublimes a t a highertemperature. The calcium salt (with 2 mols. H20) forms matted micro-scopic needles ; the barium and silcer salts are also described. Whendistilled with excess of haryta it is converted into triphenylmethane.Diphenylortho-xylylmethane C6H3Me2*CHPh2 [ 1 2 51 was preparedfi-om ortho-xylene (from orthobromotoluene). It crystallises in long,lustrous needles melts at 68.5" and distils at above 360". It isreadily soluble in alcohol ether benzene &c.When oxidised withchromic mixflure a mixture of acids is obtained but no indiiferentphthalide-derivative. When the mixed acids are treated with potas-sium permanganate triphen ylcarbinol-dicarboluy lic acid,OH*CPh,*C6H3(COOH),,is formed. The latter forms silky matted slender needles veryreadily soluble in alcohol ether and glacial acetic acid rather solublein boiling water and sparingly soluble in benzene. The salts withthe exception of the alkali salts are very sparingly soluble. The acidmelts a t 180" with effervescence and is converted into the anhydride,Cz,Hl40,. This is a transparent amorphous substance readily solublein alcohol ether and benzene. Boiling water has no action on it.When the acid is distilled with an excess of baryta it is convertedinto triphenylcarbinol.N. H. M.C Ph (0 H268 ABSTRACTS O F CHEMICAL PAPERS.Diamidostilbene and Diamidostilbenesulphonic Acid. By p.BESDER and G. SCHULTZ (Ber. 19. 3234-3239).-By reducing ortho-nitrotolueneparasulphonic acid Neale obttined an azosulphonic acid,which when treated with stannous chloride yielded R compoundwhich he described as hydrazotoluenesulphonic acid (Abstr. 1880,806). The authors show that this compound is toluiclinedisul phonicacid as it yields toluidine when distilled with lime,DinmidostilbenePul~honic acid,is obtained by dissolving 50 grams of sodium paranitrotolueneortho-sulphonate in boiling water gradually adding 100 C.C. of 33 per cent.soda solution.The soliition is diluted 50 grams of zinc-dust are thengradually added and the whole boiled until the colourless solutionno longer becomes coloured on exposure to air. It is filtered preci-pitated with hydrochloric acid again filtered and dried. It is almostinsoluble in water. The salts are readily soluble. When distilled withsoda-lime i t yields stilbene. The base obtained by Klinger by theaction of zinc chloride on the condensation product from paranitro-toluene and sodium methoxide (Bey. 16 943) and described by himas diamidnbenzyltoluene is shown by the authors to be diparamido-stilbene ; the same base was also prepared by the reduction of dinitro-stilbene from paranitrobenzyl chloride. The properties of the baseare as described by Klinger (loc.cit.) except that the acetyl-deriya-tive melts a t 312" (not 212').By combining tetrazostilbene chloride with 2 mols. of a-naphthol-sulphonic acid a blue-violet dye is formed. With /3-naphthol-disulphonic acid (R) a-naphthylaminesulp honic acid and salicylicacid (each 2 mols.) blue red and yellow azo-dyes are formed respec-tivel y. N. H. M.By A. CLAUSand M. ERLER (Ber. 19 3149-3156).-Bromine even in the nascentstate acts exceedingly slowly at ordinary atmospheric temperature ondiphenic acid but a t 60" and upwards reaction takes place readily. Ifless than 2 mols. of bromine are employed to 1 mol. acid a part ofthe acid remains unacted on. At temperatures from 60-120° theproduct consists of a mixture of bromodipheiiic acid aiid bromodi-phenic acid dibromide ; at temperatures ranging from 120-3OO" part,of the latter derivative is converted into dibromodiphenic acid andabove 200" only mono- and di-bromodiphenic acids are found in theproduct of bromination.Bromodip henic acid CO OH*CsH4*CGH3Br*C 0 OH crys tallises inacicular prisms melting a t 235-236" (uncorr.).I t is not volatile insteam and sublimes only with considerable decomposition the smallsublimate (melting slightly lower than the acid) appearing to be theanh7ldride. The acid is very sparingly soluble in boiling water,easily in alcohol ether and benzene. The neutral and acid sodizcmsalts are very soluble the brcrium (with 3H,O) silver and copperneutral salts are very sparingly soluble in water. The ethyl salt formscrystals melting at 65" (uncorr.).Bromodiphenic acid dibromide isBrominated Derivatives of Diphenic AcidORGANIC CIIE \lISTRT. 269always formed (sometimes to the extent of 15 per cent.) in the bromi-nation below 200" of diphenic acid but its production from the bromo-acid already formed appears only to take place to a very slight extent.It is sparingly soluble in alcohol and cold chloroform and crystal-lises in colourless glistening needles having a very bitter taste. Itturns brown a t 200° and melts at about 256" (uncorr.) with decom-position. Heated in closed tubes a t 200" it undergoes decomposition,di bromodiphenic acid being formed. The dibromide is very sparinglysoluble in the usual solvents but dissolves readily in alkalis andalkaline carbonates to form solutions of unstable salts which,especially when warmed rapidly decompose into salts of dibromo-diphenic acid. It is soluble in concentrated sulphuric acid and infuming nitric acid and is reprecipitated unchanged on the additionof water.The neutral sodium salt forms glistening scales but itssolution is rapidly decomposed if boiled.Dtbromodiphenic acid ClzH6Br2(COOH) is easily soluble in alcohol,ether and glacial acetic acid. It crystallises in needles melts a t245" (uncorr.) and is not volatile in steam. It sublimes with diffi-culty yielding the anhydride. Its alkali salts are easily soluble thecalcium (with 3H20) silver and lead salts sparingly soluble. The ethyEsalt is crystalline and melts at 105-106". This dibromodiphenicacid is evidently isomeric but not identical with that (melting a t295" obtained by Ostermayer Ber.7 1091) from dibromophen-ant hraquinone.When the bromo-acids are subjected t o dry distillation with lime,brominated diphenylene ketones are formed. Bromodiphenylene EetoNe,CI2H,Br CO forms yellow scales melting a t 122" (uncorr.) and iseasily soluble in alcohol ether benzene &c. very sparingly in wster.When heated with zinc-dust it yields flnorene. No hydroyen sodiumsulphi te compound could be obtained. Uibromodiphenyleae ketone formsyellow scales melting a t 133" (uncorr.).p-Naphthol-p-Disulphonic Acid. By A. CLAUS and 0. SCHMIDT(Ber. 19 3172-3179).-The authors have endeavoured to determinethe constitution of this acid by the action of phosphoric chloride onit.The material used was the commercial sodium salt (the so-calledG-salt). Reaction takes place readily but if only the temperature of thewater-bath is used p-naphtholdisulphonic chloride is produced. This isa thick reddish-brown liquid and neither it nor the correspondingamide could be obtained in a crystalline form.If the sodium salt is heated at 100-200° with more than twoinolecu ar proportions of the pentachloride the principal productsare ethereal phosphates corresponding with those obtained byClans and Zimmermann from @-naphtholsulphonic acid (Abstr.,1881 914).If the reaction is carried out above 200" (nnder pressure) and withR large excess (5 mols.) of the pentachloride dichloronaph tho1 and tri-chloronaphthalene are formed.The yield is however small 100grams of salt only yielding about 6 to 8 grams of chloro-derivatives.Dichloronaph t halene (probably from impurity of rnonosulplionate inthe salt) and tetrschloronaphthalene are also alaays present in smallL. T. T.VOL. LIT. 270 ABSTRACTS OF CHEMICAL PAPERS.quantity. The dichloronaphthol is easily isolated as it alone of theproducts is soluble in alkalis. It cryatallises in colourless needles,which melt at 125' (uncorr.) and sublime with partial decomposition.It is moderately soluble in boiling water easily in alcohol ether,&c. The trichZol.o?zaphthnZene is readily soluble in ether benzene,chloroform glacial acetic acid and boiling alcohol. It cryatallises inwhite needles melts at YO" (uncorr.) and may be sublimed.It isnot identical with the trichloronaphthalene of the same melting pointobtained by Claus and Knyrim (Abstr. 1886 156). When heatedwith dilute nitric acid at 210° it yields a dichlorophthalic acid a,yellow syrup which could not be obtained in a crystalline form. Thepotassiunt sodium and barium salts are easily soluble the silver saltsparingly soluble the lead salt insoluble. This acid is being furtherinvestigated. When heated with chromic acid in acetic solution thetrichloronaphthalene yields a trichloronaphthapuilzone which how-ever is very readily further oxidised to a chlorinated phthalic acid.Attempts to separate the quinone from the unchanged trichloro-naphthalene were unsuccessful but alkalis removed it in form of asalt of a chlorinated hydroxyquinone.The best result was however,obtained by treating the mixture with aniline when dichloronayhthn-quinone anilide CloH,C1,O,*NHPh was obtained. This is almostinsoluble in water sparingly soluble in ether. It crystallises in darkreddish-violet scales melts at 228" and may be sublimed. Theformation of this anilide by the displacement of a chlorine-atom (thecorresponding quantity of hydrochloric acid being formed) leavesno doubt that the original quinone is a trichlorinated compound.But as experience teaches that if in a chlorinated naphthalene achlorine-atom is present in the a-position that chlorine-atom isexpelled in the formation of an a-naphthaquinone the above tri-chloronaphthalene must have the constitution [Cl = 2 3 2'3.Which of the chlorine-atoms represents the hydroxyl and which thesulphonic groups in the original acid cannot yet be decided.By L.CLAISEN (Ber. 19,3316-3320).-When a-naphthol is treated with benzaldehyde a whitepulverulent compound benxaZdi-a-naphthol CHPh(C,oH6*OH)z is ob-tained which turns brown on exposure to the air and dissolves readilyin alkalis t h e alkaline solution assuming a dark reddish-violet butunstable colour when oxidised.The reaction however proceeds differently when P-naphthol istreated with benzaldehyde. When an acetic acid solution of the two,t o which a few drops of hydrochloric acid has been added is main-tained at a low temperature benzalglycoldina~hth ylacetal,CHPh(OCioH,)z,separates as a crystalline compound melting at 203-205" andsparingly soluble i n ordinary solvents almost insoluble in aqueousalkalis.Heated with acetic acid and a few drops of hydrochloricacid a t looo it is converted into benzaldi-clAaphthyl oxide,L. T. T.Action of Aldehydes on PhenolsORGANIC CHEMISTRY. 271this melts at 189-190° crystallises well and is insolubIe in alkalis.Benzaldi-naphthyl oxide is also obtained when the acetic acid solutionof benzaldehyde and P-naphthol with a little hydrochloric acid orsulphuric acid is heated at looo or in Che absence of the acids a t200".The author has also obtained results which are not in completeaccordance with those published by Claus and Trainer (this vol. p.231) and points out that the ethylidenediphenol described by themhas already been prepared by Fabinyi (Ber.11 283). With acet-aldehyde p-naphthol yields compounds similar to those formed whenit is treated with benzaldehyde; thus either ethylidenedinaiul~thnJlacetal,C2Ha( OC10H7)2 melting at 20O-2Ol0 or ethyZidene-P-dinaphtl~?/Z oxide,C2H (C10H6)2 0 melting at 173" is obtained ; both crystallise welland are insoluble in alkalis. The compound described as dinaphthyl-acetal by Claus and Trainer but melting at 162-163" was not obtainedin the author's experiments.The remainder of the paper is devoted to a theoretical discussion inwhich the author states his views as to the cause of the difference inbehaviour of a- and p-naphthol under these conditions and arrives atconclusions at variance with those put forward by Claw and Trainer(loc.cit.). w. P. w.a-Naphthyl Methyl Ketone. By A. CLAUS and P. FE~ST (Ber.,19 3180-3182) .-The authors have also independently obtainedthis ketone lately described by Pampel and Schmidt (this vol. p. 252),but some of their results differ from those of the latter authors.They find that the ketone solidifies if cooled below O" and the crystalsthen melt at 34". They find the melting point of the acetosime tobe 145" (uncorr.) that of the hydrazine 173" (nncorr.).When this ketone is treated in the cold with a dilute aqueoussolution of the theoretical quantity of potassium permanganate,a-naphthylglyoxylic (a-naphthoylformic) acid CloH7"*CO*COOH isformed. This acid is a thick oil which only solidifies slowly andwith difficulty. It is very unstable and is easily oxidised by dilutenitric acid or warm permanganate to a-naphthoic acid and carbonicanhydride.The calcium and barium salts (each with 4&H,O) areeasily the silver salt very sparingly soluble. The formation ofa-naphthoic acid proves this acid to be an a-naphthyl-derivative. Itis probably identical with Bossneck's acid melting at 113.5" (Abstr.,1883 808) ; the diEculty experienced in crystallising it being in allprobability due to traces of oily impurity.Pyrene. By E. BAMBERGEK. and M. PHILIP (Ber. 19 3036-3040).- Nuphthalenetetracarboxytic diunh ydride C14H406 is obtained byslowly heating naph thalenetetracarboxylic acid (Abstr. 1886 948)t o 150-170" or by recrystallising the acid from glacial acetic acid.I t does not change when heated at 300° at a higher temperature itsublimes in lustrous needles an inch long.When naphthalenetetra-carboxylic acid is suddenly heated to 200-250" it is convertedpartly into the anhydride and partly into naphthalenetricarboxylicacid.L. T. T.t 2 72 ABSTRACTS OF OHEXICAL PAPERS.~~2)l~thalenetetracarbozylic diirnide Cl4H6OPN2 is formed when theanhydride is treated with aqueous ammonia and separates in groupsof branched needles. It is very sparingly soluble does not alter inappearance at 270" and sublimes at a higher temperature in yellow,lustrous needles. The formation of the above dianhydride anddiiinide shows that the two pairs of carboxyl-groups in naphthalene-tetracarboxylic acid have the ortho-position.Pyrene ketone CuH80 crystallises from alcohol in gold- colouredlustrous plates melting at 142" ; when oxidised with potassium per-nianganate it ia converted into Behr and Van Dorp's naphthalic acid(Annalen 172 266).N. H. &I.Terebenthene - derivatives. By PESCI and BETTEILLI (Arch.Pharm. [3] 24,1037) .-The preparation of the hydrocarbodn phelland-rene of nitrophellandrene phellandrendiamine and amidophellandrene,from OZeum phellandrii was recently described (dbstr. 1886 1038).Subsequently by similar treatment with nitrous acid lmvorotatoryterehenthene has yielded a dextorotntory nitroterebenthena CloH15*N02,from which nascent hydrogen produces the primany baee amidotere-benthene C,HI,*NH2 which again is lmvorotatory.J. T.Formation of Euxanthic Acid from Euxanthone by theAnimal Organism. By S. v. ROSTANECKI (Ber. 19 291%-2920).-Spiegel has proved that euxanthic acid is deeornposcd by concentratedsnlphuric acid into euxanthone and glycuronic aoid. From the phenoliccharacter of euxanthone and the fact th& the magnesium salt ofeuxanthic acid known as Indian-yellow is prepared from urine theautbor has endeavoured with success to form euxanthic acidfrom euxanthone the glycuronic acid being supplied by the animalsystem. If euxanthone be administered to a dog the presence ofeuxanthic acid can be detected in the urine by means of itsmagnesium salt. This result is analogous to the conversion ofphenol or naphthol into their corresponding glycuronic acids bythe animal organism.V. H. V.Kamala. By A. G. PEREIN and W. !K. PERKIN sun. (Ber. 19,3109-3110).-Kamala a yellow dyestuff i u used in considerablequantity by the nativerJ (of India. I t is contained in the seed capsulesof MaZZotus phiZZipensis and occurs in commerce as a yellowish-brownpowder whieh under the microscope is seen to consist of transparentbrown resinous globules mixed with woody fibres and seeds ; no crys-tals were observed.NaZZotoxin CllH1003 or CleHlsOa was obtained by shaking finely-divided kamala with carbon bisulphide concentrating the yellowishsolution on the water-bath treating the yellowish-brown precipitateobtained with small quantities of carbon bisulphide to remove resinousimpurities and finally crystallising from benzene or toluene.I t formssmall flesh-coloured needles soluble in alkalis to a yellowish-red solu-tion from which acids reprecipitate the original substance ; it is nearlyinsoluble in water readily soluble in alcohol and acetic acid. A yelloORQANlC CHEMISTRY. 273acetyl-derivative CllH803Ac2 or C,8H,,0,Ac3 was o b i n e d ,experiments are in progress to determine the correct formula.FurtherA. J. G.Synthesis of Pyrroline. By G. GIAMICIAW and P. SIEBER(R~~. 19,3027) .-The authors showed previously (Abstr. 1884 1115) that snc-cinimide may be readily converted in to tetrachloropyrroline but wereunable to completely reduce the latter to pyrroline. This can bereadily effected by Hepp's method which consists in boiling the chlo-ride with the corresponding amount of potassium iodide in a refluxapparatus. The iodide so obtained is very readily reduced to pyrro-line by warming with potash solution in presence of zinc-dust.N.H. M.Behaviour of Methylketole Constitution of Pyrroline.By G. CIAMICIAN (Ber. 19 302&-3029).-Ciamicinn and Dennstedtobtained (Abstr. 1882 1214) pyridine-derivatives by the action ofchloroform or bromoform on the potassium compound of pyrroline.and suggested that quinoline-derivatives could probably be obtainedin a similar manner from indole. Expcriments made by the authorshow that quinoline-derivatives can be obtained from methylketoleby means of the chloroform reaction and also by heating with hydro-chloric acid a t 200" (compare Ber. 14 1341).Both methylketole and in a less degree indole show all the colourreactions of pyrroline.The author considers the relation betweenindole and pyrroline to be established by these results. N. H. M.Synthesis of Pyrroline-derivatives. By C. PAAL and C. W. T.SCHNEIDER (Ber. 19 3156-3163).-This is a continuation of theauhhor's previous work (Abstr. 1886 559).EChyZene-~-tetramet~yZ~~~yrro~~~ie C2H4( C4NH2Me2)2 [ C2Ha Me =1 2 53 was obtaiiied by the action of acetonylacetone on ethylene-diamine. It crystallises with 4 mols. H20 in glistening white scales,melts a t 125-126" sublimes unchanged and is volatile in steam.It is insoluble in water soluble in alcohol et,her &c. It is soluble inmineral acids with red coloration colours pine shavings carmine andgives a purple-red with Laubenheimer's reagent.It forms a yellowy la t in 01 h lor id e .Trimethylene-a-tetramefh yldipyrroline C3H6( C,NH2Me2) is formedwhen trimethylenediamine is substituted for ethylenediamine in theabove reaction. It forms it pale yellow crystalline substance meltingat 76-7io insoluble in water soluble in alcohol and ether. Itresembles the ethylene compound in properties.Pctrudi~ZLe.nylene-a-tetrainethyldipllr.1.oline C,2H8(C4NH2Me2)2 frombenzidine and acetonylacetone crystallises in colourless tables solublein alcohol ether &c. It is very unstable especially when in solution.It melts at 130" and is decomposed at a slightly hipher temperature.When ethyl acetophenoneacetoacetate is wed in place of acetonyl-acetone the ethers of a series of dipyrrolinedicasboxylic acids areobtained.Et li y 1 ct hy lene-a- dimeth y ldiphen y ldip yrroline- P-dicarbox~ late,CLk14(C4NHMePh*COOEt) [1 2 5 31a 74 ABSTRACTS OF CHEI\lIOAL PAPERS.crystallises with 4H20 in glistening scales melting a t 197".It dis-tils unchanged bnt is sensitive to light. It is insoluble in waterand light petroleum soluble in alcohol benzene chloroforni andglacial acetic acid. It is insoluble in hydrochloric acid but dissolvesin concentrated nitric or sulphuric acid and is reprecipitated un-changed on the addition of water. It shows Laubenheimer's reaction.On hydrolysis it yields the free crystalline acid which melts at 181",and a t a slightly higher ternperatu1.e evolves carbonic anhydride,forming the pyrroline-derivative C2H4( C4NH2MePh),.The acid isinsoluble in most solvents very sparingly soluble in alcohol andin glacial acetic and concentrated hydrochloric acids.P-Ethocarboxyl-a-nzethylphenylpyrroline-acetic acid,COOHCH,*C4NHMePh*COOEt [l 2 5 31,formed on substituting amido-acetic acid for the diamine i n the lastreaction crystallises in needles melting a t 131". It is almost insolublein water soluble in alcohol ether and benzene. It dissolves in alkalisand alkaline carbonates and forms well-characterised salts Whenheated with alcoholic potash it yields the free bibasic acid,COOH* C H,* C4NHMePh*C0 0 H.This forms small white needles which melt at 152" with evolutionof carbonic anhydride.Ethyl metaphenylene-a-dimetl~yldiphenyld~yrroline-~-dicarboxylnte,C,H4 ( C,NH MeP h* C 0 0 E t).,crystallises in white needles which melt at 185".It is insoluble inwater soluble in most other solvents and in concentrated sulphuricacid.Ethy 1 paradipheny lene-a-dimeih y ldiphtw y la$ yrrolins- p- dicarboxy latp,C,2H,(NC4HMePh*COOEt)2 from benzidine aud ethyl acetophenone'-acetoacetate crystallises in thin needles melting at 178-1 i9". Whensaponified i t yields the corresponding potassium salt which however,resinifies easily. The free acid could not be obtained.COOH*C6H4*NCpHMePh*COOEt,crystallises in small yellow iieedles melting a t 160" and soluble inalcohol ether &c. It forms characteristic salts. When heated withalcoholic potash it yields the corresponding bibasic acid which formscolourless hairy needles melting at 210".When strongly heated cai*-bonic anhydride is evolved.~E'thocarboxyl-oc-metkylp~~ny~~ yrrolinemetnbenzoic acid,Ethyl azobelzzene-oc-metky~~en~~~yr~ol~ne-~-carbo~ylnte,N2Ph*C6H4*C4NHMePh*COOE t,from amido-azobenzene forms deep red crystals melting a t 123". Itis easily soluble in alcohol ether &c. When saponified it yields thecorresponding acid which forms large red crystals soluble in ether,alcohol &c. It melts a t 195" and evolves carbonic anhydride a t aslightly higher temperature.A11 these substances show Laubenheimer's reaction. L. T. TORQANIC CHEMISTRY. 275Synthesis by Means of Ethyl Acetoacetate. By L.KNORR(Annalen 236 290-332).-The author has already shown (Abstr.,1885 554) that ethylic diacetosuccinate reacts with ammonia andwith primary amines yielding substituted pyrroline-derivatives. Asimilar action takes place with hydroxylamine. By heating anaqueous solution of hgdrosylamine hydrochloride (12 parts) andsodium acetate (24 parts) with ethyl diacetosuccinate (30 parts),dissolved in glacial acetic acid the ethyl hydroxydimeth ylppyrrolhze-dicarboxyzate OH44NMe2(COOEt) is obtained as a crystallinecompound soluble in alcohol and ether and in dilute alkalis butinsoluble in acids. This substance melts between 98" and 100". Aprecipitate of the coniposition CI2H,,KN05 is obtained on addingether to an alcoholic solution of the ethyl salt and potassiume thoxid e.A mixture of hyd~ox~dimethylpyrrolinecarboxylic acid andmovethy1 hydroxydimethylpyrrolirLedicarboxylate is formed when theethylic salt is saponified by alcoholic potash.The latter compound,CloH,,NO5 crystellises in needles soluble in alcohol. It melts a t 185",with decomposition yielding ethylie hydroxydimethylpyrroline-carboxylate.Hydroxydimethy~~rrolinecnrbox~l~c acid,C7H,N0 [OH Me COOH Me = 1 2 3 51,decomposes at 138" yielding hydroxydimethylpyrroline [OH Me2 =1 2 S ] . The acid crystnllises in needles and dissolves freely inalcohol It is decomposed by prolonged boiling with water. Themetallic salts are notl characteristic. The formation of the ethyl salthas just been mentioned. Hydroxydimethplpyrroline exhibits thepinewood reaction.It is soluble in alcohol ether chloroform ben-zene and alkalis. It reduces ammoniacal silver solutions at theordinary temperature and Fehling's solution on boiling,The derivatives of trimethylpyrrollinedicarboxylic acid,[Me3 (COOH) = 1 2 5 3 41,phenyldimethylpyrrolinedicnrboxylic and - naphthyldicarboxylicacid have been previously described by the author (Abstr. 1885,555). These acids are decomposed when heated yielding pyrrolines.Trintethylpyrroline [I 2 51 boils a t 17$ (corr.) ; phenyldirnethyl-pywoline [ P b Me = 1 2 51 melts at 51" and boils at 252" (corr ),and P-naphthyldinzethylpyrroline [C,,,H Mez = 1 2 51 melts a t71" and boils at 341" (corr.). These compounds are freely soluble inalcohol ether chloroform and benzene.cc- A'npht h y ld inaet hglpyn.olinedicarbox ylic acid [ C,,HVa Me ( CO 0 H)= 1 2 5 3 41 crystallises in needles and decomposes a t 2M0,yielding a-naphthyldintethylpyrroline This substance melts a t 123',boils a t 310-315" (corr.) and dissolves freely in ether alcohol andchloroform.Ethyl a-nnpht7~~l~imethylpyrrol%neclicai.~oxylate melts a t 91-92',The potassium salt C18H13K2N04 is insoluble in alcohol The barium,CIBH13BaNOd and silver Cl8N1,AgK 04 salts are crystalline.E t hy 1 naet hy lp heny 1 amidodimeth2/lpyrroZiize~~~ioarboxy late is obtaine276 ABSTRACTS OF OHEMICAL PAPERS.as an uncrystallisable oil by the action of ethyl diacetosuccinate onmethylphenylhydrazine.The free acid Cl5H1,N2Oa crystallises inprisms and decomposes at 231" into carbonic anhydride and methyl-pheizylamidodimethyl~rroline CI3Hl6N2 a crystalline aubstance whichmelts a t 41" and boils at 310" (corr.).Et h,yl metarnidotoly ldirn et h y 1pyrroEinedica doxy late is formed byboiling equivalent quantities of metatoluylenediamine and ethyldiacetosuccinate in acetic acid solution.The ethyl salt crystallisesin prisms and melts at 134". The free acid Cl5H,,N?Oa + 3H20,crystallises in plates of a yellow colour. It is soluble in alcohol ether,acids and alkalis. It decomposes a t 203" yielding rneta?nidotolyl-dzmethylpyrroline. This compound nielts at 73" and boils a t 322"(corr.) It is soluble in alcohol ether and acids and volatilises in acurrent of steam.Ethyl toluylenedidimethylpyrroliiaedicarbox~late,is obtained as a heavy oil by the action of metatoluylenediamine(m. p.99') on excess of an acetic acid solution of ethyl diaceto-succinate. The free acid C23Hz2N208 is sparingly soluble in alcoholand ether and insoluble in water and dilube acids. It melts at 248"with decomposition.D inz et h y lp y wolinedicarbox y lacetic acid,C,HllNO = C,N~e,(COOH),.CH,.COOHE [2 5 3 4 11,splits up a t 214O yielding carbonic anhydride and an oily liquid,probably diinef h y l p yrolin e- acetic acid C4RHzMe2*C H,*CO 0 H. Theacid forms crystalline potassium and silver salts Cl,HLKK,N06 and(=10&,Ag206. The ethyl salt is prepared by boiling an acetic acidsolution containing equivalent quantities of glycocirie and ethyldiacetosuccinate.Ethyl dimeth?/~yrrolinedicarboxylate C4NHXe,(COOEt),[2 :4 3 51,is most conveniently prepared by adding a strong solution of sodiumnitrite (2 parts) to 7 parts by weight of ethyl acetoacetate dissolredin strong acetic acid.25 parts of zinc-dust is added to the well-cooled pioduct. On adding water to the mixture the ethyl salt isdeposited in needle-shaped crystals. This substance melts a t 134-135" and is distinguished from its symmetrical isomeride by theabsence of basic properties. Many of the properties of this compoundand of its derivatives have been already described by the author(Abstr. 1884 1368). MonethgldimethyIpyrrolinedicarboxylate niel tswith decomposition at 202" (not 200" as previously stated) forminge thy1 d imethy~py~rolineerboxylate,Dimetbylpyrrolinedicarboxylic acid decomposes a t 260" into car-bonic anhydride and dimethylpyrroline [Me Me = 3 41 (Zoc.cit.).B t h y l dimeth y Zp yrrolineanilidocarhoxy late,COOEt-C1?SH1\Ie,*CONHPh [5 2 4 31ORGANIC CHEMISTRY. 277is formed by the action of zinc-dust on equivalent quantities of aceto-acetic anilide and ethylic nitrosoacetoacetate dissolved in acetic acid.It melts at 216" and dissolves in hot alcohol and acetic acid. Ontreatment with strong sulphuric acid it yields 2 4 dimethylpyrroline,and on boiling with alcoholic potash it is converted into the monaidideof difiwth y lpyrrolinedicrtrbox~lic acid C 0 0H.C ,NH*Me2*C ONHP h.This substance softens a t 180" and decomposes a t 198".It also splitsup when boiled with dilute siilphuric acid yielding carbonic anhydrideand dimeth y1pt~rrolinecarbox~la?~zlide C,NH,Me,*CONHPh.Ethyl d~rrcethylpyr~olineai~ilidocurboxylate [Me2 COOEt CONHPh= 2 4 3 51 is prepared by reducing with zinc-dust an acetic acidsolution of ethylic acetoacetate and nitrosoacetoacetic anilide. Itcrystallises in needles melts a t 180" and yields 2 4 dimethyl-1)yrroline on treatment with sulphnric acid.Dimethy lp yrrol hedicarboxy lanil i d e,C4NH*Me2(CONHPh) [2 4 3 51,is formed by reducing a mixture of the anilides of acetoacetic andnitrosoacetic acids. It melta about 255" and mystallises in needles. Italso yields 2 4 dimethyl pjrroline when warmed with sulphiirio acid.Action of Chlorine on Pyridine.By E IT. KEISER (Amer.Chem. J. 8 308-315).-Ande1-son has worked on this subject(AnnuZen 105 340). When anhydmus pyridine is treated withdry chlorine it finally solidifies and by distillation a white crystal-line solid boiling at 130" and a yellow solid boiling a t 218" areobtained. The first is purified by crystallisation from alcohol; itmelts at 72" is very stable and with platinuim chloride gives a pre-cipitate having the composition (C,H,CI,N) ,,H,PtCl,. The secondsubstance cannot be distilled withoat partial decompositioil ; it is verydeliqixescent and is soluble in water ; with platinum chloride thesolution gives a precipitate of pyridine platinochloride ; the yellowcompound itself baa the composition C5HSNC1 and is evidently anunstable additive product.When chlorine is passed into pyridine diluted with its own bulk ofwater nitrogen and carbonic anhydride are evolved and on furtherdilution a white precipitate is thrown down which when dry smellslike bleaching powder and with platinum chloride give3 a precipitateof pyridine platinochloride; i t is therefore an additive product ofpyridine probably the hypochlorite and the carbonic anhydride andnitrogen are derived from the decomposition of this substance.When chlorine is passed into a pyridine solution containing freealkali nitrogen is evolved with explosive violence but if the con-tents of the flask be kept cool the action is more gentle and chloro-form and dichloracetic acid are to be found in the distillate. Thiqdecomposition of pyridine by chlo~ine is far more readily explainedby Riedel's formula (Abstr.1883 1152) than by KGrner's.w. c. w.H. B.Tetrahydropicoline. By A. LIPP (Bey. 19 2843-2844) .-Thebase obtained by the action of alcoholic ammonia on w-bromobutylmethyl ketone (Abstr. 1886 219) proves to be a tetrahydropicaline278 ABSTRACTS OF CHEMICAL PAPERS.probably CH2<g2-:ze>CH. Under similar conditions a pyrro-line-derivative is obtained from w-bromopropyl methyl ketone.w. P. w.Quinolinesulphonic Acids. By A. CLAUS and P. KCTPNER(Ber. 19 2886 -28Y6) .-Quinolineorthosulphonic acid i n cooled.aqueous solution forms a yellow crystalline precipitate with bromine,an unstable probably additive compound ; at the temperature of thewater-bath the acid is decomposed with formation of tribromo-quinoline which separates in glistening silky needles melting at 198",soluble in ether and alcohol insoluble in water.Quinolineparasulphoiiic acid under similar conditions yields a dibro-moquinoline crystallising in long needles melting a t 124-126" andyielding on oxidation with potassium permanganate a bromopyridine-dicxrboxylic acid identical with that described by Claus andCollischon. On adding more than two molecular proportions ofhromine a tribromoquinoline is slowly produced isomeric with thecompound described above.It crystallises in long silky needles,melting at 170° and is sparingly soluble in cold ether soluble inalcohol. As regards the displacement of the sulphonio group concen-trated nitric acid resembles bromine in its action a mononitro-quinoline being produced.V. H. V.Reduction of Hydroxylepidine and Methyllepidone. By I;.KNOKR and C. KLOTZ (Bey. 19 3299-3303). -Hydroxylepidine aridmethyllepidone resist the action of acid reducicg agents but arereadily attacked and reduced by sodium arnalgam and alcohol or bysodium and alcohol.Reduction of HTycl,.oxyZe~idi~ze.-When hydroxy lepidine in alcoholicsolution is shaken with an excess of sodium amalgam a compound,(CloHloNO) is obtained insoluble in water alkrtlk and alcohol butcrystallising from acetic acid in slender needles melting a t 280". Itshows feebly basic properties and is most probably a diquinolyl-derivative.The reluction proceeds further when metallic sodium is employed,and from the product after removal of the alcohol two compoundsare obtained one of which tetrahydrolepidine CIIH13N is separated bydistillation with steam.It is a colourless strongly refractive oil hasa pungent odour and boils at 250-253" (thermometer iumersed in thevapour) at 740 mm. pressure. Dihydroh ydmzylepidijze CloHl,NO,separates in needles from the residual liquor left after steam distil-lation melts at 101" and is insoluble in alkali sparingly soluble inwater readily soluble in alcohol ether and chloroform. It showsfeebly basic properties and its salts are decomposed by water.Nitrous acid is without action in the cold but on warming acts on itand forms an acid compound.8ed.uctiol.L of MethyIlepidone.-Sodium amalgam reduces methyl-lepidone in cold alcoholic solution to the diquinolyl-derivative(C1,HIsNO) (this Val p.159). It is insoluble in water alkalis,and alcohol solublo in acetic and hydrochloric acids and meltsat 268". When metallic sodium is employed as the reducing agentORGANIC CHERIISTRT. 279dimethyltetr~hydro~ui~ioline Cl1HI5N is obtained. It is a colour-less oil speedily turning brown when exposed to air boils a t 255"(thermometer immersed in vapour) at 757 mm. pressure and isidentical with the base obtained by the reduction of lepidine meth-iodide with tin and hydrochloric acid. It yields a yellow platino-chloride and an oily orange-red nitroso-compound.Redmtlon of Carl~ostyi-L'l.-Tetrahydroquinoline is obtained whencarbostyril in alcoholic solution is reduced with metallic sodium.By L.REHER (Bw. 19 2995-3002).-When quinoline ethiodide is heated atl 280-290" for two hours asomewhat complicated reaction takes place resulting in the formationof hydrocarbons in addition to basic products. After acidifying theproduct is distilled with steam to remove the hydrocarbons then ren-dered alkaline and again steam-distilled. The mixture of bases SOobtained is fractionated and the portion boiling bet ween 240 and 280",after removing the unaltered quinoline is repeatedly fractioned ; inthis way fractions boiling a t 255-260" and 270-275" are obtained,which consist of a- atid yethylquinoline respectively but by thismethod the only feasible one a complete separation cannot beeffected.u-Ethylpuiizoline is a very hygroscopic colourless liquid with a,quinoline-like odour does not solidify a t low temperatures and isslightly soluble in water readily soluble in ether alcohol chloroform,and carbon bisnlphide and quickly becomes coloured red on exposureto light.The hydrochloride and nitrate are readily soluble inwater and effloresce in air. The rrzercuriochloride Cl1Hl1N,HHgCl3,melts at 118" and forms slender white needles ; the platinochloride,(Cl,HllN)z,H,PtC16 melts at 190" and crystallises in dense tables ; theaurockloride C,lHl,N,HAuC14 melts a t 142" and forms canary-yellowneedles ; the picrate CIIHllN,CsHz( N02)3*OH melts a t 146 -147" andcrystallises in long yellow needles; and in addition a crystallinesfmmocldoride ( Cl,H11N)2,H2SnC14 + 2H20 and an oily chromate andzinc salt are described.On oxidation an acid was obtained agreeingin its properties with quinaldinic acid.Tetrahydro-ac-ethy ZyuirroZine Cl1H1,N is formed when a-etliylquinolineis reduced with tin and hydrochloric acid. It boils at 259-263",and resembles the parent base in appearance and odonr. Thehydroclbloride crystallises in white needles which remain unalteredin air.The fraction boiling between 270" and 275" consisting chiefly of-1-ethylquinoline contained a diethylquinoline which was separated bymeans of its mercuriochloride ; this salt CSH,NEt,,HHgCl melts at116" and crj stallises in needles. y-Ethylpuinoline resembles thea-base in appearance and odour and its salts show a great similarityto those of a-ethylquinoline but have a.higher melting point. Thehydrochloride is very soluble in water and is deliquescent ; the Initrate,C11HllN,HNOs melts a t 1 1 5 * 5 O and crystallises in white needles,which become brown on exposure to air and are soluble in waterand alcohol. The mercuriochloride CllHllK,H HgCl melts at 154",crjstallises in white needles and is readily soluble in water containingw. P. w.a- and 7-Ethylquinoline280 ABSTRACTS OF CHE&IICAL PAPERS.hydrochloric acid ; the platinochloride (CllHl,N)z,H,PtC16 nielts at204" and forms brown leaf-like crystals ; the picrate nielts a t 178-186" with decomposition and forms long yellow needles ; and theaurochloride ClIH11N,HC1(A~C13)z forms slender yellow needles.Themethiodide nielts a t 149" and formed yellow crystals. On oxidation,cinchonic acid is obtained. y-Ethylyuinoline on reduction yields abase boiling between 271" and 275" the hydrochloride of which is notcrystalline. ty-Ethy lquinolinssulpli onic acid C11HloN*S03H is obtainedby heating y-ethylquinoline a t 260" with 10 times its weight of fumingsulphuric acid. It forms slender lustrous needles melts above 315",and is insoluble in alcohol but readily soluble in hot water.The hydrocarbon separated from the ethyl bases by steam distil-lation was fractionated and from the lowest fraction 210-240" whitecrystals were obtained which had a strong naphthalene-like odour,By E. V. BRCCKE (Monatsh.Chem. 7 617-620).-It has long been known that guanine whenevaporahed with nitric acid gives a yellow residue soluble in potashwith yellow coloration ; the solution thus obtained on evaporation todryness gives at first a purple then a violet coloration ; 011 exposureto air the original colour returns.In this paper it is shown that thesechanges are due not to the so-called metachroniatism but to theproportion of water present; thus there exist two compounds theone golden-red with the greater the other indigo-blue with the lessproportion of water. It is not improbable that an intermediatepurple-red compound is also formed. Experiments confirmatory ofthis view are described in which the eoloured solutions are exposedto conditions of the presence and absence of water respectively.Opium Alkaloids.By P. C. PPJJGGE (Awh. Phurrn. [3] 24,90:3-1014) .-Morphine codeine theba'ine papaverine narcotine andnarceine are the most important opium alka€oids. Their physio-logical action varies from strongly narcotic or sleep-inducing tostrongly exciting. or cramp-producing bvlt different observers are notagreed as to the exact order of the members of the series. In thearringement of the bases according to their poisonous nature,different observers are more nearly in accord. The author exa-mined the reactions of salts of these alkalo'ids with alkaline saltsof organic acids. Morphine codeine and theba'ine in neutralliquids react strongly alkaline to litmus and afford stable salts.Narcotine papnrerine and narce'ine on the contrary do not affectlitmus-paper and combine only feebly with acids.Thus narce'inesulphate and chloride are slowly decomposed by cold water morequickly by hot water. It appeared probable from this that solutionsof salts of the stronger bases would give no precipitate with alkalinesalts of organic acids whilst in the case of the weak bases thealkaloid would be precipitated as such. The following salts wereemployed ; sodium and ammonium acetate ammonium oxalate sodiumsalicylate sodium potassium tartrate sodium benzoate and hydrogensodium carbonate.and were almost certainly naphthalene. w. P. w.Colour Reaction of Guanine.V. H. VORQANIC CHEJIISTRY. 281Resides the six opium bases many other alkaloi'ds were examinedin tbe course of the investigation such as caffeine cocaine atropine,pilocarpine coniine strychnine brucine quinine cinchonine andcinchonidine the latter however only with sodium acetate.None ofthese bases were liberated and precipitated ; in the case of the cinchonabases however it was necessary to carefully neutralise the sodiumacetate with acetic acid or precipitation took place. With a perfectlyneutral solution of sodium acetate the only alkaloids precipitated arethe three weak opium bases papaverine narcotine and nsrceine.These three bases are also precipitated both by slightly acid andby slightly alkaline acetate solution. Neither of the two solutionsexerts any influence on the strong opium bases consequently theordinary non-neutralised acetate solution can be used for theseparation of the bases with advantage in point of time and perhapscompleteness. Narcotine papaveriue and narceine were precipitatedas pure bases by all the alkaline salts mentioned previously.The-baine was precipitated by sodium salicylate as sslicylate and byhydrogen sodium carbonate. Morphine and code'ine were not pre-cipitated by any of the salts. Arranging the alkaloids in seriesaccording to their molecular weights it will be seen that tohe first threeare strong bases and the last three feeble ones morphine C,7Hl()NO3 ;codeine C,,H,NO ; thebai'ne CIgH2,NO3 ; papsverine C21H21N0d ;narcotine C2,H,,N07 ; narceine C22H29NOa. Slightly acidifiedsodium acetate solution will indicate as little as 1 40,000 of narcotinein solution. With papaverine the limit is 1 30,000.Narceine isnot nearly so sensitive the limit being about 1 600. The precipita-tion of theba'ine as salicylate gave a limit of about 1 2000. Forquantitative estimation narcotine k best precipitated by ammonia,where it is the only substance thrown down by khis reagent; sodiumacetate has however the advantage of precipitating it for qualitativepurposes from faintly acid solutions in which all other alkaloids,excepting papaverine and narce'ine remain in solution. Papaverineand narce'ine are also best precipitated quantitatively by ammonia.J. T.Cinchona Alkaldids. By W. 5. COMSTOCK and W. KOENIGS(Ber. 19 2853-2859) .-From considerations based on its chemicalbehaviour the authors have adopted the formula Cl,H,2Br2N20 forcinchoniiie dilwornide instead of that given in their previous paper(Abstr.1885 910). A crystalline sulphute is obtained by allowing asolution of cinchonine dibromide in 7 to 8 parts of concentratedsulphuric acid to remain for several hours. It is soluble in hot waterand dilute alkalis excess of alkali throwing out the salt but diluteacids dissolve it with difficulty. When heated :It 130" in a sealed tubewith hydrogen bromide it is decomposed into cinchonine dibromideand sulphuric acid.Dehydrocinclmline CI9Hz0N2O is obtained in practically colourlessneedles by heating cinchonine dibromide with alcoholic potash in areflux apparatus for 16 to 20 hours distilling off three-fourths of thealcohol and adding water to the residue. It is purified by pre-cipitating its hydrochloride with ammonia and crystallising fromalcohol.The base melts at 202-203" and sublimes without decom282 ABSTRACTS OF CHEMICAL PAPERS.position if the temperature be carefully raised. It dissolves easily inalcohol acetone and chloroform less easily in ether and hotbenzene and is practically insoluble in water. The hydrobromide,CIgHzoN20,HBr crystallises from water in colourless transparentprisms the hydrochloride in long silky needles.Dehydrocinchonine chloride ClgHl9N2C1 is prepared by treatingdehydrocinchonine hydrochloride with phosphorus pentachloride andphosphoric oxychloride adding ammonia and crys tallisiiig frombenzene. It melts at 148-149" and is readily soluble in benzene,alcohol acetone chloroform and ether b u t insoluble in lightpetroleum.Dehydyocinchene Cl9H:I8NZ is obtained by boiling dehydrocin-chonine chloride with alcoholic potash for 16 hours and is purifiedby recrystallising its hydrogen tartrate.The free base crystallisedfrom dilute alcohol forms long colourless needles which melt atabout 60° and contain at least 3 mols. H,O. The hydrobromide,C19Hl,N2,2HBr is obtained in small broad transparent concentrically-grouped prisms which dissolve readily in water but only sparinglyin alcohol and ether. The pZatinochZoride ClgH,,N,,H2Pt Us a verysparingly soluble salt is obtained in bright red tables from thesolution of the base in concentrated hydrochloric acid.Cinchene dibromide Cl9H2,Br2N2 is best prepared by graduallyadding bromine to a solution of cinchene in chloroform uiitil theyellow perbromide begins to separate sodium hFdrogen sulphite andhydrochloric acid are added and the base precipitated from theseparated aqueous layer by ammonia is purified by conversion into thehydrobromide &c.From its ethereal solution it is obtained inbeautiful colourless crystals which begin to fuse a t 110" and melt a t113". The hydrobromide crystdlises in cencentrically-grouped,colourless needles ; the szitrate and zincocldoride also crystallise well.Boiling for 20 hours with alcoholic potash converts cinchene dibromideStrychnine. By W. F. LOEBISCH and P. SCHOOP (Jfonatsh.Chem. 7 603-616) .-The products obtained on distilling strychninewith zinc-dust vary according to the temperature ; at a lower tem-perature one atom of oxygen is removed from the molecule withformation of a compound C2,Hz,NzO a solid substance soluble inalcohol with a blue fluorescence sparingly soluble in dilute acids,insoluble in water.It does not give the strychnine reaction withpotassium dichromate and sulphuric acid. At a higher temperature,the strychnine molecule is completely decomposed ; hydrogen,ethylene acetylene and ammonia are evolved whilst carbazole distilsover. Similarly brucine and the acid C16H,,N204 obtained by theoxidation of strychnine with chromic acid yield carbazole on distil-lation with zinc-dust. On dry distillation strychnine yields the sameinto dehydrocinchene. w. P. w.gaseous products but only coLparatively &di quantities of carbazole,accompanied probably by pyrroline.V. H. V.Specific Rotation of Piperidine Bases. By A. LADENBURG(Ber. 19 2975-2977).-Completing his recent research on thORGANIC CHEMISTRY. 283specific rotation of piperidine bases (this vol. p. 164) the authorfinds €or a-pipecoline [a]= = 21*74" and for a-ethylpiperidine [a]= =6.75". a-Isopropylpiperidine and P-pipecoline do not yield opticallyactive bases by conversion into dextrotartrates. From the mother-liquor of the a-pipecoline hydrogen tartrate the levorotatory basewas obtained ; but this even after conversion into the hydrochlorideand treatment with cadmium iodide to remove any accompanyingdextrorotatory base gave only a specific rotation of -19" andprobably contained either the dextrorotatory or the inactive base asimpurity which could not be separated.Experiments show that theinactive piperidine bases are compounds and not mixtures of theoptically active modifications ; and therefore it has been possible toeffect a decomposition into two optically active salts only in thosecases where the temperature employed in the crystallisation lay aboveor below the transition temperature of the inactive hydrogen dextro-tartrate (comp. Abstr. 1886 968).The unexnectedlv low specific rotation of the dextrorotatorv a-ethvI-piperidine ienders" it pribable that the specimen employe2 was i o tpure. w. P. w.Alkalo'ids of the Berberideae. By 0. HESSE (Ber. 19 3190-319%).-The author has re-investigated the alkalojids in the root ofBerberis vulgaris.He believes that there are therein at least fouralkalojids besides berberine and describes especially oxyacanthine(Wacker Chena. Centr. 1861 321) and a new alkaloid he hasobtained from the mother-liquors of oxyacanthine and which henames berbamine.He finds the true formula of oxyacanthine to be CIaH,,NO3 andnot c,,H,1N03 as he has previously given. When crystallised fromwater and dried at loo" this alkaloid melts at 138-150" but whencrystallised from alcohol or ether it forms needles melting at 208-214".It is easily soluble in chloroform and then gives [ a ] D = + 131.6"( p = 4 t = 15'). In light petroleum and alkalis it is only slightlysoluble and ether extracts it completely from the alkaline solutions.The hydrochloride CI8Hl9NO3,HCl + 2H20 forms small colourlessneedles which in aqueous solutions give [a]= = +163*6' ( p = 2,t = 15").The pZatinochZoride is a yellow flocculent precipitate. Theniirnte and suZphate are both crystalline. When heated with potasharid a little water the base melts to a brown mass which floats onthe surface of the fused potash. This brown mass is the potassiumcompound of p-oxyacanthine. This conversion into a P-modificationalso takes place veiy readily even at ordinary temperatures when thealkaloid is acted on by alkalis o r barium hydroxide in the presence ofalcohol. Ether now no longer extracts the alkaloid froni the alkalinesolution. Hydrochloric acid precipitates P-oxyacanthine which issoluble both in alkalis and in excess of acid.If however the alkalinesolution of the @compound is supersaturated with hydrochloric acid,a-oxyacanthine hydrochloride crystallises out. The author believesthe &modification is due to the alkaloid taking up an additionalmolecule of water. Oxyacanthine very closely resembles narcotine inproperties284 ABSTRACTS OF CHEMICAL PAPERS.Berbamine crystallises in small scales of the composition C,,H,,NO,When anhydrous it melts a tThe hydrochzoride crystallises in scales the nitrate in needles ;+ 2H,O.156".the pZatinochZoride forms a yellow crystalline precipitate.It is easily soluble in ether.L. T. T.Colchicine. By S. ZEISEL (Monatsh. Chem. 7 557-597).-Previous observations on the composition and properties of colchicine]lave for the most part been very discordant; in this paper a longsummary is given.The principal results obtained by the author are asfollows the composition of colchicine is expressed by the formulaC2?H2,NOfi ; i t combines with chloroform to form A crystalline com-pound C22H25NOfi,2CH CI3 readily decomposed by water into itscomponents. Colchicine is slightly basic but its salts with theexception of an aurochloride C?zH25N06,HAuCld cannot be obtainedfrom their aqueous solutions. Colchiceine formed from colchicine,when heated with a trace of hydrochloric or sulphuric acid has thecomposition 2C21H27NOfi,H?0. As the difference between the twocompounds is one CH or methylene group and as methyl alcohol isproduced in the decomposition it follows that colchiceine is a de-methyla ted colchicine.Colchiceine possesses at once the properties of a base as evidencedby the formation of an aurochloride Cz~H2~NO6,HAuCl4 and also thoseof a monobasic acid or more probably of a phenol as shown by theformation of a copper derivative ( C21H~~NOc)2Cu and by the readinesswith which i.t dissolves in alkalis.As colchicine has no acidicproperties i t is probably a methoxy-derivative of a compound ofwhich colcbiceine is the corresponding hydroxy-derivative.It is suggclsted that the molecular formula of each of the abovesubstances is the double of that given ; owing to the complex compo-sition of the substances the number of hydrogen-atoms is given witha certain reserve. V. H. V.Ecgonine. By C. E. MERCR ( B e y . 19 3002-3003).-The authorhas repeated an experiment made by Calmels and Gossin (Abstr.,1885 912) and finds that ecgonine when distilled with almost drybarium hydroxide yields methylamine and not ethylamine as one ofthe products ; this corresponds with the behaviour of tropine underlike conditions. When ecgonine hjdrochloride is heated with anc qua1 weight of phosphorus pentachloride and 10 parts of chloroforma t 100" for 10 hours a base is obtained which yields a well crystalliseda urochloride C9H13N@2,HAuC14 corresponding with ecgonine less theelements of 1 mol. HzO. The base has not yet been obtained in thepure state. M. P. w.A New PtomaYne producing Tetanus. By L. BRIEGER (Bey.,19 3119-321) .-The author has already described an alkalo'id,tetanine obtained in the cultivation of Rosen bach's microbe. Thebeef extract in which the microbe had been cultivated for four to sixweeks was acidified with hydrochloric acid boiled and filtered ; thefiltratp evaporated and treated with lead acetate and alcohol filtered,and the lead removed as far as possible a s chloride and finally aORGANIC CEUZMISTRT. 285sulphide. The strongly alkaline filtrate was distilled with steam,acidified with hydrochloric acid evaporated to dryness and treatedwith alcohol t o remove ammonium chloride. After removing thealcohol the new base was separated as its aurochloride.The free base C5H,,N is volatile boils about loo" but was notobtained free from water. The hydrochloride is crystalline melts at205" and is very readily soluble in water and absolute alcohol. Theaurochloride C,H,,N,HAnC& crystallises in plates and melts at 130".The pZatinochZoride ( C5E:,,N),,H2PtC1 crystallises in plates is decom-posed at 240° and is sparingly soluble in water. The picrate crystal-lises in readily soluble needles. The base gives a yellow precipitatewith phosphomolybdic acid a white precipitate with phosphotungsticacid and a red crystalline precipitate wifh potassium bismuth iodide.Injected hypodermically in a comparatively large dose it produces thesymptoms of tetanus.By R. NEUNEISTER (Zed. B i d 23,381-401).-Thequestion investigated in this research was whether or not eachalbumose was converted into isomerides belonging to the anti- andhemi-groups of digestion products.The method previously described by Riihne and Chittenden ofseparating proto- from deutero-albumose is not a satisfactory one.Hetero-albumose is easily separated by its being precipitated when thesalts are dialysed out from a mixture of the albumoses. It can alsobe separated from the mixture by saturating it with sodium chloride;part of the proto-albumose and the whole of the deutero-albumoseremain in solution. In the precipitate hetero-albumose can be sepa-rated by dialysis as before. By acidifying the filtrate which containsthe deutero-albumose and part of the proto-albumose the proto-albumose and about half the deutero-albumose are precipitated ; thisis filtered off ; the deutero-albumose remaining in solution is not mixedwith any other albumose; the sodium chloride is dialysed off thefluid is saturated with ammonium sulphate and thus the peptonealone is left in solution the precipitate of deutero-albumose isredissolved and obtained free from ammonium sulphate by dialysis,and finally precipitated by alcohol. It gives no precipitate withcopper sulphate ; previous statements that such a precipitat'e occurswere due to its admixture with proto-albumose.On prolonged heating of proto-albumose with 5 per cent. sulphuricacid deutero- albumose is formed. Hetero-albumose yields the samesubstance and also anti-slbumid. The same result is obtained onpeptic digestion and also on tryptic digest'ion more rapidly in thelatter case than the former. The formation of the so-called globulin-like substance does not occur in tryptic digestion.No deutero-albumose is formed directly from fibrin; but proto-and hetero-albumose are intermediate products in its formation bothby acids and by ferments.Anti-albumid yields dentero-albumose also and seems to be largelya bye-product of the formation of hetero-albumose. The deutero-albumose obtained is an anti-product yielding only anti-peptone ; muchinsoluble anti-albnmid is left after prolonged digestion which willA. J. G.Albumoses.VOL. LII. '1286 ABSTRACTS OF GEEMICAL PAPERS.yield no more albumose. This insoluble substance swells with sodiumhydroxide; it is turned yellow by nitric acid and orange on thesubsequent addition of ammonia ; in its solubilities it much resembleskeratin.The deutero-albumose formed from proto- and he tero-albumose iscalled ampho-deutero-albumose as it is subsequently converted intoamphopeptone (that is hemi- and anti-peptone) ; the anti-productsfrom proto-albumose are however exceedingly small in quantity mdthe author suspects that his method of preparing proto-albumose doesnot give him that substance quite free from traces of hetero-albumose ;and that perfectly pure proto-albumose will be found to be a purehemi-albumose. The changes in the digestion of albumin are repre-sented in the following schemes.Albumin. -- Hemi-albumin. Anti-albumin.Proto-slbumoee. Hetero- (dys) -albumose. Anti-albumid.Amphodeutero-albumose. Amphodeutero-albumose. Antideutero-albumose.Amphopeptone. Amphopeptone. Antipep tone.W. D. H.Vitelloses. By R. NEUMEISTER (Zeit. Biol. 23 402411).-Following on the lines of Kuhne and Chittenden the products of thedigestion of vitellin have been subjected to analysis. The variety ofthe proteid employed was plant vitellin (phytovitellin) preparedfrom pumpkin seed.Coagulated vitellin was found to be the best to employ ; ill pepticdigestion syntonin WCLS formed a8 one product. This resembledordinary acid albumin except that it was insoluble in strong nitricacid and gave the biuret reaction not the ordinary purple colour. Asubstance antivitellid corresponding with anti-albumid was alsoformed but no coagulable substance like that obtained in the pepticdigestion of globulin.The ultimate products of digestion are peptones ; vitellose is thename given to the intermediate products proto- hetero- deutero-and dysvitellose which correspond with the albumoses with siinilarprefixes. These may be separated from one another and from pep-tones as the albumoses are.Protovitellose becomes deuterovitellose on further peptic digestion :when subjected to the action of the tryptic ferment a trace of antivitelliPHYSIOLOGICAL CHEMISTRY. 287is formed; the end products are antipeptone tyrosine leucine andthe substance which becomes violet with bromine.Heterovitellose and dysvitellose derived from it do not differ intheir properties from the analogous albumoses ; under tryptic diges-tion much antivitellid is formed the end product being antideutero-vitellose. Under prolonged peptic digestioli amphodeuterovitelloseis formed.The anti- and ampho-varieties of deuterovitellose correspond withthe similarly named albumoses. W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8875200225

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a l C h e m i s t r y . 287 Gases of Parotid Saliva. By R. KULZ (Zeit. Bid, 23, 321- 328).-Observations on the gases of human saliva have not been prz- viously made. The saliva was obtained by means of a gum elastic mnula (which was found to be better than the metal one at first used) inserted into Stenson’s duct; the saliva was collectell over mercury to obviate the danger of absorption of atmospheric air. As the mean of 11 analyses, the total quantity in volume from 100 C.C. of saliva, was 7 C.C. of gas, of which 1 G.C. was oxygen, 2.5 nitrogen, and 3.5 C.C. carbonic anhydride. By the addition of phos- phoric acid, a large amount (40-60 per cent.) of carbonic acid con- tained in the saliva as carbonates was obtained. The amount of oxygen and nitrogen i n the saliva exceeds that in the blood-serum. With regard to the carbonic anhydride present, and the alkalinity of the secretion which is due to the carbonates, it, is found that food in the stomach does not alter the reaction of the saliva as it does that of the urine.After an abundant secretion of gastric juice, many observers have noted, and these experiments confirm their results, that the urine becomes less acid or even alkaline. That there is no such effect on the saliva is shown both by the estimation of the carbonic acid and by titration. W. D. H, Free Hydrochloric Acid of the Gastric Juice. By H. A. LANDWEHR (Chem. Centr., 1886, 484J.-The author has previously shown, in conjunction with Fick, that the action of this acid on diastase is inverted in the presence of peptoues, in the sense that ita activity is increased rather than suspended ; the cause probably lying in its combination with amido-acid groups of the peptones.Calm has recently shown (Deut. Arch. f. Zzliw. Med., 23) that in certain pathological conditions the gastric juice has the reactions rather of an organic acid than of dilute hydrochloric acid. It is well known that lactic acid decomposes sodium chloride. That this thken place in cold dilute solution is readily seen by comparative observations of the acidity (methyl-violet being used as indicator) of a, lactic acid solution before and after addition of sodium chloride. u 2288 ABSTRACTS OF CHEMICAL PAPERS. The author applies these observations to a discussion of the origin and nature of the acidity of gastric juice, arriving at the following hypothesis :-Lactic acid is formed by fermentation from the mucus of the stomach, and, acting on alkaline chlorides, liberates hydro- chloric acid, which is forthwith taken up i n combination by the albumino’ids of the food.The sodium lactate is simultaneously assi- milated. With the gradual peptonising of the albuminoyds, the hydrochloric acid is liberated. c. I?. c. Ferment Organisms of the Alimentary Canal. By N. MILLER (Ohem. Centr., 1886, 580) .-Of the 25 micro-organisms identified by the author in the mouth, 12 were also found in the intestines, and 8 in the stomach. Although normal gastric juice is antiseptic, the conditions in the stomach are often such as to prevent contact of the organisms therewith, which then continue active.These organisms are also carried forward into the intestines by liquids which remain only a short time in the stomach. In most cases, these organisms exert a peptonising but only seldom a diastatic action. I n some cases, they induce lactic fermentation of carbohydrate solutions ; in ot,hers acetic and butyric. In some instances the fermentation was attended with the evolution of carbonic anhy- dride and hydrogen. C. F. C. Formation of Fat in the Dog from Carbohydrates. By J. MUNK (Bied. Centr., 1886, 748-750).--8 bitch was allowed to fast for 31 days, this being the period stated by Hofmann to be necessary for the removal of all fat from the system-31 per cent. of the weight was lost. The animal was then fed with 200 grams of flesh, 100 grams of gelatin, and an increasing ration of starch and sugar in equal parts (300 to 500 grams).After 25 days the animal was killed and examined, when it was found to have increased in weight at a rate of 36 grams daily, and, taking the lowest valuation, nine-tenths (960 grams) of the whole fat found in it had been pn t on during the 25 days. The sources from which the fat could have been formed were three: namely, fat in the flesh given, decomposed albumin, and carbohydrates. Of the fat produced by the decomposition of albumin, there would be according to Voit and Pettenkofer 12 per cent., according to Henne- berg 51 per cent.-415 grams should be formed ; but this quantit,y must be reduced to 42 to 45 per cent. if Zuntz’s method of calculating Henneberg’s results is to be followed ; the author therefore considers t h a t 343 to 364 grains fat must be attributed to albumin; the fat from the meat amounted to 75 grams.However, whatever may be the quantity of actual fat from albumin, there appears to be no doubt that 788 grams (max.) 470 grams or 542 to 521 grams of fat (accord- ing to the method of calculation used), had to be sought for from other sources, namely, the gelatin and starch. The author allows for argument’s sake that 338 grams might come from the gelatin (this, however, according to Voit and Pettenkofer, is inadmissible), even then 162 grams of fat must have come from the carbohydrates. E. w. P.PHYSIOLOGICAL CHEXISTRT. 289 Relation between the Destruction of Glucose and the Pro- duction of Animal Heat and Work.By A. CHAUVEAU and KAUF- MANN (Compt. rend., 103, 974-975, 1057-1064, 1153--1159).-0n comparing two organs which, under ordinary physiological conditions, have very unequal thermogenic activities, it is always found that the destruction of glucose is much greater in the organ in which combus- tion is most active, or, in other words, the heat developed in animal tissues, which is proportional to the amount of internal combustion, is also proportional to the quantity of glucose removed from the blood in the capillaries. Analyses of the blood of the masseter muscle and parotid gland of the horse during a etate of repose, showed that the activity of combus- tion in the muscle as measured by the amount of oxygen absorbed and of carbonic anhydride produced is to that in the gland as 4.57 : 1, whilst the destruction of glucose is as 5.68 : I.During the process of mastication and insalivation, the activity of combustion in the muscle is iocreased by 3.5 times, whilst the consumption of glucose in the blood traversing the muscle is in- creased to almost the same extent. In the gland, the ratio between the activity of combustion at rest and in action is 60 : 87, whilst the consumption of glucose is as i 0 : 90. In experiments of this kind, i t is important to take into account not only the composition of the blood, but also the volume which traverses the orgau in unit time. Details of the method of experiment and of the analyses are given in the original papers. Glucose is always found in the nutritive secretions, but never in any tissues except the live]..Glycogen, on the other hand, does not occur in the blood, but only in the hepatic and muscular tissues. Analyses of muscle in repose and in action confirm the statement that glycogen accumulates while the muscle is a t rest, but disappears during activity. The glucose which disappears from the capisllrtries leaves them in company with oxygen, and is more or less compktely con- verted into water and ca.rbonic anhydride in the organs andl tissues. The glycogen which bas acciimulated in the muscles provides the materials for combustion during periods of great activity when the supply of glucose is not equal to the demand. Only a portion of the glucose which disappears from the capillaries is consumed ; the remainder becomes converted ixI to muscular glycogen by dehydration, and then forms a reserve.During excessive work, the glycogen becomes hydrated and reconverted into glucose, which is consumed. The liver is the indirect collaborator of the muscles during activity. In fact the hepatic gland performs its functions as a glycogenic organ the more actively each time that any work is done by any part of the animal economy. This is established by the fact that the blood never becomes appreciably poorer in glucose even during activity. On the contrary, there is often an excessive production of glucose, especially if the activity is localised as in mastication. So long as the liver furnishes glucose to the blood in sufficient quantity, SO long does the animal continue to develop the quantity of heat necessary for the activity of the other organs and the maiEte- nance of the bodily temperature.When the glycogenic function of290 ABSTRACTS OF CHEMICAL PAPERS. the liver becomes enfeebled, glucose disappears from the blood-vessels, org,inic combustion rapidly diminishes, and death supervenes a s a, result of arrested calorification. C. H. B. Origin of the Bile Colouring Matters. By H. STERN (Chem. Centr., 1886, 481) .-The author’s experiments were performed on pigeons. The bile-ducts being: ligatured and provision being made for collecting the urine separately, by ligaturing the rectum above the entrance of the urethra, it, was found that within 14 hours the urine was highly charged with these colouring matters. After death, the tissues were found to be similarly charged.I n a second series of experiments, the liver was thrown entirely out of the circula- tion. I n this case neither in the blood, urine, nor tissues were any traces of these colouring matters found. The author concludes from his experiments that these substances originate entirely in the liver ~u bstance. c. I?. c. Active p-Hydroxybutyric Acid. By E. KUTA (Zeit. BioZ., 23, 323-339) .-The author has previously described tbe occurrence of this substance in diabetic urine. It may be prepared as follows :- Diabetic urine which gives the ferric chloride reaction and is strongly lmorotatory is (after the removal of the sugar by fermeutation) concen- trated to a thin syrup, and neutralised with sodium hydroxide. three times as much 95 per cent.alcohol is added, which produces an abundant precipitate ; from the alcoholic filtrate, the alcohol is evaporated, and more alcohol added ; thiR is repeated until alcohol gives no further precipitate ; the last traces of alcohol are removed by shaking with ether. To the residue, sulphuric acid is added, and the mixture shaken with an eqnal volume of etber. The ether is driven off by heat, and the remaining brown syrup gives a precipitate with lead acetate, which is filtered off. From the filtrate, excess of lead is removed by sulphuretted hydrogen ; bnrytn- water is added, and the barium salt of the acid is obtained in solution. Urea is then precipitated by means of mercuric nitrate, excess of mercury being removed by treatment with sulphuretted hydrogen.From the solution of the barium salt, the silver salt is obtained by adding a solution of silver sulphate ; the barium sulphnte is removed, and on concentration crystals of the silver salt are obhained and purified bF recrystallisation. The free acid is obtained by decompos- ing the solution of the silver salt with sulphuretted hydrogen. The specific rotatory power of this acid is [aID = -23.4. Theamnionium salt has the specific rotation denoted by [a]= = -16.3. Minkowski’s test for this acid in urine (Arch. exp. Path. u. Phwwnk., 18, 41) is not regarded as trustworthy ; and the obtaining of crystals of a-crotonic acid, on adding sulphuric acid, is preferred. The presence of a substance which rotates polarised light Go the left, which gives the ferric chloridp reaction, and which is not precipitable by lead acetate, may be taken as strong presumptive evidence of the presence of p-hgdroxybutyric acid.Bmzoic acid (from the decomposition of hippuric acid), salicylic acid, and phenol, might possibly be con- founded w i t h it; methods of avoiding such a mistake are given. TheVEGETABLE PETYSIOLOCfY AND AGRICULTURE. 291 acid does not appear to be present in the urine of healthy men or animals; but it occurs in unhealthy urines not only in cases of diabetes, but also in cases of scarlet fever, measles, diphtheria, scurvy, and in certain mental affections. W. D. H. Physiological Action of Convolvulin and Jalapin. By G. DRAGENDORFF (Chem. Gentr., 1886, 589).-The question of the excre- tion of these glucosides after beiiig taken into the human stomach has been investigated by Bernatzik (Wiener med.Jb., 1862-63) ; traces only were found in the fseces, none in the urine. This result was confirmed by Kohler and Zincke (W. Jb. f i r Pkarm., 32, 1) ; who, however, succeeded in isolating these purgatives from the stomach and intestines. The author has repeated these investigations, adopt- ing a simpliged method of examination of the parts for the glucosides and products of decomposition (convolrulic and jttlapic acids), based on extraction with chloroform. 0.8 gram of the glucosides was the quantity given, cats being taken as the subject of the experiments. The author confirmed the previous results in regard to the non- excretion of the drugs in the faeces and urine.The animals were killed after the lapse of four hours, and the orgams examined ; appreci- able quantities of the drugs were found in the stomach and small intestines, less in the duodenum, traces only in the lungs and pancreas. No evidence was obtained that the glucosides are converted into the derived acids. c. F. c.PHYSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a l C h e m i s t r y .287Gases of Parotid Saliva. By R. KULZ (Zeit. Bid, 23, 321-328).-Observations on the gases of human saliva have not been prz-viously made. The saliva was obtained by means of a gum elasticmnula (which was found to be better than the metal one at firstused) inserted into Stenson’s duct; the saliva was collectell overmercury to obviate the danger of absorption of atmospheric air.As the mean of 11 analyses, the total quantity in volume from100 C.C.of saliva, was 7 C.C. of gas, of which 1 G.C. was oxygen, 2.5nitrogen, and 3.5 C.C. carbonic anhydride. By the addition of phos-phoric acid, a large amount (40-60 per cent.) of carbonic acid con-tained in the saliva as carbonates was obtained. The amount of oxygenand nitrogen i n the saliva exceeds that in the blood-serum.With regard to the carbonic anhydride present, and the alkalinityof the secretion which is due to the carbonates, it, is found that foodin the stomach does not alter the reaction of the saliva as it does thatof the urine. After an abundant secretion of gastric juice, manyobservers have noted, and these experiments confirm their results,that the urine becomes less acid or even alkaline.That there is nosuch effect on the saliva is shown both by the estimation of thecarbonic acid and by titration. W. D. H,Free Hydrochloric Acid of the Gastric Juice. By H. A.LANDWEHR (Chem. Centr., 1886, 484J.-The author has previouslyshown, in conjunction with Fick, that the action of this acid ondiastase is inverted in the presence of peptoues, in the sense that itaactivity is increased rather than suspended ; the cause probably lyingin its combination with amido-acid groups of the peptones. Calm hasrecently shown (Deut. Arch. f. Zzliw. Med., 23) that in certainpathological conditions the gastric juice has the reactions rather ofan organic acid than of dilute hydrochloric acid.It is well known that lactic acid decomposes sodium chloride.Thatthis thken place in cold dilute solution is readily seen by comparativeobservations of the acidity (methyl-violet being used as indicator)of a, lactic acid solution before and after addition of sodium chloride.u 288 ABSTRACTS OF CHEMICAL PAPERS.The author applies these observations to a discussion of the originand nature of the acidity of gastric juice, arriving at the followinghypothesis :-Lactic acid is formed by fermentation from the mucusof the stomach, and, acting on alkaline chlorides, liberates hydro-chloric acid, which is forthwith taken up i n combination by thealbumino’ids of the food. The sodium lactate is simultaneously assi-milated. With the gradual peptonising of the albuminoyds, thehydrochloric acid is liberated.c. I?. c.Ferment Organisms of the Alimentary Canal. By N. MILLER(Ohem. Centr., 1886, 580) .-Of the 25 micro-organisms identified bythe author in the mouth, 12 were also found in the intestines, and8 in the stomach. Although normal gastric juice is antiseptic, theconditions in the stomach are often such as to prevent contact of theorganisms therewith, which then continue active. These organismsare also carried forward into the intestines by liquids which remainonly a short time in the stomach.In most cases, these organisms exert a peptonising but only seldoma diastatic action. I n some cases, they induce lactic fermentation ofcarbohydrate solutions ; in ot,hers acetic and butyric. In some instancesthe fermentation was attended with the evolution of carbonic anhy-dride and hydrogen.C. F. C.Formation of Fat in the Dog from Carbohydrates. ByJ. MUNK (Bied. Centr., 1886, 748-750).--8 bitch was allowed to fastfor 31 days, this being the period stated by Hofmann to be necessaryfor the removal of all fat from the system-31 per cent. of the weightwas lost. The animal was then fed with 200 grams of flesh, 100 gramsof gelatin, and an increasing ration of starch and sugar in equal parts(300 to 500 grams). After 25 days the animal was killed andexamined, when it was found to have increased in weight at a rate of36 grams daily, and, taking the lowest valuation, nine-tenths (960grams) of the whole fat found in it had been pn t on during the 25 days.The sources from which the fat could have been formed were three:namely, fat in the flesh given, decomposed albumin, and carbohydrates.Of the fat produced by the decomposition of albumin, there would beaccording to Voit and Pettenkofer 12 per cent., according to Henne-berg 51 per cent.-415 grams should be formed ; but this quantit,ymust be reduced to 42 to 45 per cent.if Zuntz’s method of calculatingHenneberg’s results is to be followed ; the author therefore considerst h a t 343 to 364 grains fat must be attributed to albumin; the fatfrom the meat amounted to 75 grams. However, whatever may bethe quantity of actual fat from albumin, there appears to be no doubtthat 788 grams (max.) 470 grams or 542 to 521 grams of fat (accord-ing to the method of calculation used), had to be sought for fromother sources, namely, the gelatin and starch.The author allows forargument’s sake that 338 grams might come from the gelatin (this,however, according to Voit and Pettenkofer, is inadmissible), eventhen 162 grams of fat must have come from the carbohydrates.E. w. PPHYSIOLOGICAL CHEXISTRT. 289Relation between the Destruction of Glucose and the Pro-duction of Animal Heat and Work. By A. CHAUVEAU and KAUF-MANN (Compt. rend., 103, 974-975, 1057-1064, 1153--1159).-0ncomparing two organs which, under ordinary physiological conditions,have very unequal thermogenic activities, it is always found that thedestruction of glucose is much greater in the organ in which combus-tion is most active, or, in other words, the heat developed in animaltissues, which is proportional to the amount of internal combustion, isalso proportional to the quantity of glucose removed from the bloodin the capillaries.Analyses of the blood of the masseter muscle and parotid gland ofthe horse during a etate of repose, showed that the activity of combus-tion in the muscle as measured by the amount of oxygen absorbedand of carbonic anhydride produced is to that in the gland as 4.57 : 1,whilst the destruction of glucose is as 5.68 : I.During the process of mastication and insalivation, the activityof combustion in the muscle is iocreased by 3.5 times, whilst theconsumption of glucose in the blood traversing the muscle is in-creased to almost the same extent. In the gland, the ratio betweenthe activity of combustion at rest and in action is 60 : 87, whilst theconsumption of glucose is as i 0 : 90.In experiments of this kind, i tis important to take into account not only the composition of theblood, but also the volume which traverses the orgau in unit time.Details of the method of experiment and of the analyses are givenin the original papers.Glucose is always found in the nutritive secretions, but never in anytissues except the live].. Glycogen, on the other hand, does not occurin the blood, but only in the hepatic and muscular tissues. Analysesof muscle in repose and in action confirm the statement that glycogenaccumulates while the muscle is a t rest, but disappears duringactivity.The glucose which disappears from the capisllrtries leavesthem in company with oxygen, and is more or less compktely con-verted into water and ca.rbonic anhydride in the organs andl tissues.The glycogen which bas acciimulated in the muscles provides thematerials for combustion during periods of great activity when thesupply of glucose is not equal to the demand. Only a portion of theglucose which disappears from the capillaries is consumed ; theremainder becomes converted ixI to muscular glycogen by dehydration,and then forms a reserve. During excessive work, the glycogenbecomes hydrated and reconverted into glucose, which is consumed.The liver is the indirect collaborator of the muscles during activity.In fact the hepatic gland performs its functions as a glycogenic organthe more actively each time that any work is done by any part of theanimal economy.This is established by the fact that the blood neverbecomes appreciably poorer in glucose even during activity. On thecontrary, there is often an excessive production of glucose, especiallyif the activity is localised as in mastication.So long as the liver furnishes glucose to the blood in sufficientquantity, SO long does the animal continue to develop the quantity ofheat necessary for the activity of the other organs and the maiEte-nance of the bodily temperature. When the glycogenic function o290 ABSTRACTS OF CHEMICAL PAPERS.the liver becomes enfeebled, glucose disappears from the blood-vessels,org,inic combustion rapidly diminishes, and death supervenes a s a,result of arrested calorification.C. H. B.Origin of the Bile Colouring Matters. By H. STERN (Chem.Centr., 1886, 481) .-The author’s experiments were performed onpigeons. The bile-ducts being: ligatured and provision being madefor collecting the urine separately, by ligaturing the rectum abovethe entrance of the urethra, it, was found that within 14 hoursthe urine was highly charged with these colouring matters. Afterdeath, the tissues were found to be similarly charged. I n a secondseries of experiments, the liver was thrown entirely out of the circula-tion. I n this case neither in the blood, urine, nor tissues were anytraces of these colouring matters found. The author concludes fromhis experiments that these substances originate entirely in the liver~u bstance.c. I?. c.Active p-Hydroxybutyric Acid. By E. KUTA (Zeit. BioZ., 23,323-339) .-The author has previously described tbe occurrence ofthis substance in diabetic urine. It may be prepared as follows :-Diabetic urine which gives the ferric chloride reaction and is stronglylmorotatory is (after the removal of the sugar by fermeutation) concen-trated to a thin syrup, and neutralised with sodium hydroxide. threetimes as much 95 per cent. alcohol is added, which produces an abundantprecipitate ; from the alcoholic filtrate, the alcohol is evaporated, andmore alcohol added ; thiR is repeated until alcohol gives no furtherprecipitate ; the last traces of alcohol are removed by shaking withether.To the residue, sulphuric acid is added, and the mixtureshaken with an eqnal volume of etber.The ether is driven off by heat, and the remaining brown syrupgives a precipitate with lead acetate, which is filtered off. From thefiltrate, excess of lead is removed by sulphuretted hydrogen ; bnrytn-water is added, and the barium salt of the acid is obtained in solution.Urea is then precipitated by means of mercuric nitrate, excess ofmercury being removed by treatment with sulphuretted hydrogen.From the solution of the barium salt, the silver salt is obtained byadding a solution of silver sulphate ; the barium sulphnte is removed,and on concentration crystals of the silver salt are obhained andpurified bF recrystallisation. The free acid is obtained by decompos-ing the solution of the silver salt with sulphuretted hydrogen.Thespecific rotatory power of this acid is [aID = -23.4. Theamnioniumsalt has the specific rotation denoted by [a]= = -16.3.Minkowski’s test for this acid in urine (Arch. exp. Path. u. Phwwnk.,18, 41) is not regarded as trustworthy ; and the obtaining of crystalsof a-crotonic acid, on adding sulphuric acid, is preferred. The presenceof a substance which rotates polarised light Go the left, which givesthe ferric chloridp reaction, and which is not precipitable by leadacetate, may be taken as strong presumptive evidence of the presenceof p-hgdroxybutyric acid. Bmzoic acid (from the decompositionof hippuric acid), salicylic acid, and phenol, might possibly be con-founded w i t h it; methods of avoiding such a mistake are given. ThVEGETABLE PETYSIOLOCfY AND AGRICULTURE. 291acid does not appear to be present in the urine of healthy men oranimals; but it occurs in unhealthy urines not only in cases ofdiabetes, but also in cases of scarlet fever, measles, diphtheria, scurvy,and in certain mental affections. W. D. H.Physiological Action of Convolvulin and Jalapin. By G.DRAGENDORFF (Chem. Gentr., 1886, 589).-The question of the excre-tion of these glucosides after beiiig taken into the human stomachhas been investigated by Bernatzik (Wiener med. Jb., 1862-63) ;traces only were found in the fseces, none in the urine. This resultwas confirmed by Kohler and Zincke (W. Jb. f i r Pkarm., 32, 1) ;who, however, succeeded in isolating these purgatives from the stomachand intestines. The author has repeated these investigations, adopt-ing a simpliged method of examination of the parts for the glucosidesand products of decomposition (convolrulic and jttlapic acids), basedon extraction with chloroform. 0.8 gram of the glucosides was thequantity given, cats being taken as the subject of the experiments.The author confirmed the previous results in regard to the non-excretion of the drugs in the faeces and urine. The animals werekilled after the lapse of four hours, and the orgams examined ; appreci-able quantities of the drugs were found in the stomach and smallintestines, less in the duodenum, traces only in the lungs and pancreas.No evidence was obtained that the glucosides are converted into thederived acids. c. F. c

ISSN:0368-1769    

DOI:10.1039/CA8875200287

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 291 Chemistry of Vegetable Physiology and Agriculture. Bacterial Life in Relation to Oxygen. By P. LIBORIUS (Chem. Centr., 1886, 579). - The author classifies these organisms as follows :- (1 .) Exclusively anaerobic : amongst these there are manx which multiply without attendant fermentation. (2.) Exclusively aerobic : reduced to inactivity by deprivation of oxygen. This class includes :-B.Jlvorscens liquifaciens, B. aerophilzcs, B. cyonogenus, B. fmcus, B. aquatilis fuscus, B. subtilis. With excep- tion of tbe first .named, which appears to determine a special fermenta- tion of albuminoids with formation of volatile fatty acids, the bacteria of th-is group have not been closely studied in relation t o fermentation. (3.) Optionally anaerobic : activity lowered, but not suspended, by deprivation of oxygen.This class includes d l fhe pathogenic organisms : B. anthracis, B. typhi abdorn. From this general view of the conditions of bacterial life, and from his own epecial investigations, the author concludes that an attendant fermentation is not an essential condition of anaerobic activity in the sense in which it has been so stated by Pasteur and Nageli. C. F. C.292 ABSTRACTS OF CHEMICAL PAPERS. Wine and Brandy from Raspberries and Strawberries. By A. ROMMIER (Compt. rend., 103, 1266--1268).-The ferment of the raspberry, which has been described by lie Be1 as Levure wurtzii, is not able to convert the whole of the sugar of the raspberry into alcohol. In order to ascertain if this is due to want of activity in the ferment, or to the action of some constituent of the fruit, energetic el1ipso:dal wine yeast was mixed with the liquid.Fermentation then proceeded rapidly, and not only the sugar existing in the fruit, but two or three times the quantity of added sugar, was converted into alcohol. Raspberry brandy, obtained by distilling the wine, is very aromatic, and has the odour of raspberries, then becomes slightly smoky, but finally acquire8 a very fine bouquet. The ferment of strawberries is more active, but fermentation is accelerated by the addition of ellipsoydal wine yeast.. Strawberry wine from French strawberries is less acid than that from raspberries, and keeps well, provided that it contains 16 per cent. of alcohol. The brandy has a strawberry bouquet, which becomes stronger after some time, but does not alter in character. The flavour of the brandy from English strawberries, although made with a double quantity of added sugar, is still so strong as to be unpleasant, but if diluted with water the strawberry bouquet develops in perfection, h fact which indicates that more sugar might he added with considerable advantage.Levure wurtzii and others, such as L. apiculatus, have no inversive properties, and can therefore act only on invert sugar, and are unable to alter the sacchnrose which also exists in the juices of many fruits. A higher yield of alcohol can be readily obtained by adding an inver- sive ferment like the ellipsoidal yeast of wine. Zymotic Virus and Fermentation. By S. ARLOING (00mpt.rend., 103, 1268--1270).-The virus of gangrenous septicsemia and of symptomatic anthrax have the power of fermenting nitrogenous substances such as peptone, albumin, and yolk of egg. The products are ammouiacal compounds, with possibly indole and skntole. Hy- drogen, nitrogen and carbonic anhydride are evolved, the hydrogen being present in much greater relative proportion in the gases from albumin and yolk of egg than in those from peptone. These facts confirm the analogy between zymotic virus and ferments. The gaseous infiltration which characterises gangrenous septicsemia and symptomatic anthirtx is in all probability due to the fermentation of the carbohydrates and nitrogenous compounds in the tissues. Loss of Nitrogen by Plants during Germination and Growth.By W. 0. ATWATER and E. W. ROCKWOOD (Arner. Chem. J., 8,3'L7--343).-During the germination of seeds, and the early growth of plants, may there be a material loss of nitrogen ? (compare Abstr., 1885, 1005). Yeas were allowed to germimte and grow for A certain length of time in moist sand, and the nitrogen contained in them and also in the sand and moistlire estimated. The sum of these two quantities was always less than the computed nitrogen in the original seeds, the loss varying from 6 to 16 per cent., according to the time C. H. B. C. H. B.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 293 of the experiment and the locality. Only in cases where a quantity of the rootlets had been torn off in removing the plants from the sand did the nitrogen in the moist sand exceed 3 per cent.of the whole. Bearing in mind the work of other experimenters, the authors believe that this loss of nitrogen, which is not observed in the germination of all seeds, is not a normal process of the growth of the plant, but is caused by processes of decomposition that depend on the presence of microbes . H. B. Variations in the Chemical Composition and Physical Pro- perties of American Oats. By C. RICHARDSON (Amer. Chem. J., 8, 364-374 ; compare Abstr., 1885, 585).-The grains vary consider- ably in weight, size, weight of husk, and in the way in which the husk encloses the grain, according to the environmeut,s of the plants. The chemical composition! however. is far more constant, and the propor- tion of husk aud kernel and the compactness of the grain prove to be the all-important factors, and the weight per bushel the best means of judging of the value of the grain.No differences can be shown to exist such as might be expected between the largest and smallest oats, those having the lowest and highest proportion of kernel, &c. The detailed results are embodied in ti series of tables. H. B. Loss occasioned by Improper Methods of Pickling Wheat. By P. GRASSMAN (Bied. Centr., 1886, 766--774).-1t is customary to treat wheat before sowing with solution of copper sulphate, which destroys the spores of bunt (Tilletia caries), but generally no special attention is paid to the quantity of sulphate employed; consequently much loss ensues, owing to the destruetive action of the sulphate on the germinative power of the grain.Kuhn recommends that for every 5 bushels of wheat 1 lb. of siilphnte be dissolved in 50 parts of water. In this solution, the wheat is to be soaked for 12 to 16 hours, after which, the liquid being first removed from above, the grain is to be dried for 24 hours. The liquid is to be removed from above, because the diseased grains and the fungus float to the top, so that if the liquid is drawn OW from below, or if the grain is lifted out through the liquid, the damaged grain and spores will be mixed again with the healthy material. Grossman has examined the effect of prolonged drying and increased streugth of s'olution on the vitality of the seed, and finds that both of these conditions are highly detri- mental to the germinative power, and that where germination is not actually destroyed, the sprout will be unhealthy and weak, and germi- nation will be delayed.Tables are given showing in detail the results of various mixtures and times of drying on the germination. Nitrogen Compounds in Vegetable Soils. By BERTHELOT and ANDRB ( C m p t . rend., 103, 1101-1104) .-The nitrogen in vegetable soils exists mainly in the form of insoluble compounds with carbon, hydrogen, and oxygen. Sieved and air-dried soil was suspended in water, mixed with various proportions of hydrochloric acid, kept, at different tempera- tures for varying lengths of time, and then filtered. The filtrate was E. W. P.294 ABSTRAUTS OF CHEMICAL PAPERS. carefully neutralised with potasb, then slightly acidified, and after- wards mixed with excess of magnesia, and the ammonia estimated by Schloesing’s process.The ammonia was also determined in the soil which had been in contact with water only, and the difference between the two quantities gave the amount of ammonia formed by the action of the acid on the nitrogen compounds in the soil. The quantity of ammonia thus formed increases with the concentration of the acid, the time, and the temperahre. The action of the hydrochloric acid is in fact precisely similar to its action on urea, asparagine, oxamide, &c. (this vol., p. 235), and hence i t follows that the nitrogen in the soil exists in part at least in the form of amides. After estimation of the ammonia, the liquid was carefully neutra- lised with sulphuric acid, evaporated to dryness on the water-bath, and the nitrogen in the residue estimated by means of soda-lime.This determination gives the amount of uitrogen present in the form of soluble amido-compounds, and it was found that the proportion of these compounds increases with the time of action of the hydrochloric acid and with its concentration. The amido-compounds thus rendered eoluble by the action of the acid may be divided into two groups, one of which remains in solution when the liquid is neutralised with potash, whilst the other is precipitated with the ferric, aluminium and calcinm oxides. In one experiment, the ratio between the nitrogen in the two groups was 23 : 17. Alkalis act on the nitrogenous matter in much the same way as hydrochloric acid. C. H. B. Manuring Rye with Thomas Slag and other Phosphates.By M. SIEVERT (Bied. Cevttr., 1886, 744-745).-The land had been manured in the previous year with farmyard manure, and in this season it received 30 lbs. PzO, and 10.5 lbs. N as ammonium sulphate or bone-meal per morgen. The phosphates applied were Thomas slag, bone-meal superphosphate, and Curavoa phosphate. In all cases the slag brought the lowest, and the superphosphate the highest yield, and from a money point of view the super- and Curayoa phosphates were the most advantageous. E. W. P. Thomas Slag and other Phosphates as Manure for Moor- lands. By RIMPAU and others (Bied. Centr., 1886, 732--742).-1n the previous year, the phosphates failed to produce any definite result (Abstr., 1886, 1069). The experiments have been repeated in the succeeding year without added manures, so as to obtain information regarding the after-effect of the manures.It appears, then, that the after-action of Thomas slag and precipitated phosphate are alike. A set of experiments similar to those already described (Zoc. cit.) have been made by Wagenheim, from which it appears that as a manure for rye, slag is as good as precipitated phosphate ; moreover, P. Wag- ner’s law, that so long as an increase is obtained by the employment of increased quantities of phosphate, that increase will be in direct ratio with the increase of manure, was corroborated. Another corroboration of Wagner’s law was also obtained when rye was grown, and a, distinct advantage of slag over precipitated phos-ANALYTICAL CHEMISTRY. 295 phate was noticed, in that the expenses were less with the former than with the latter.E. W. P. Superphosphate Manuring for Sugar-beet. By A. NATJTIER (Bied. Centr., 1886, 742-744) .-It was found in the neiqhbourhood of Peronne, where the land was rich (P,O, 0.34 per cent, N. 0.17, K20 0*53), that the addition of manures (nitre, ammonia, oil-cake, and phosphate) was unnecessary, as instead of an increase in the crop which paid for the manure the case was exactly opposite ; there was a deficiency and loss. Neither was the percentage of sugar in the juice appreciably altered. But, on the other hand, in poor land deficient in phosphates, a gain was obtained by the use of superphos- phate and natural phosphates, yet the total yield was lower, although the quotient of purity was higher than on the richer soil.E. W. P.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 291Chemistry of Vegetable Physiology and Agriculture.Bacterial Life in Relation to Oxygen. By P. LIBORIUS (Chem.Centr., 1886, 579). - The author classifies these organisms asfollows :-(1 .) Exclusively anaerobic : amongst these there are manx whichmultiply without attendant fermentation.(2.) Exclusively aerobic : reduced to inactivity by deprivation ofoxygen. This class includes :-B.Jlvorscens liquifaciens, B. aerophilzcs,B. cyonogenus, B. fmcus, B. aquatilis fuscus, B. subtilis. With excep-tion of tbe first .named, which appears to determine a special fermenta-tion of albuminoids with formation of volatile fatty acids, the bacteriaof th-is group have not been closely studied in relation t o fermentation.(3.) Optionally anaerobic : activity lowered, but not suspended,by deprivation of oxygen.This class includes d l fhe pathogenicorganisms : B. anthracis, B. typhi abdorn. From this general view ofthe conditions of bacterial life, and from his own epecial investigations,the author concludes that an attendant fermentation is not an essentialcondition of anaerobic activity in the sense in which it has been sostated by Pasteur and Nageli. C. F. C292 ABSTRACTS OF CHEMICAL PAPERS.Wine and Brandy from Raspberries and Strawberries.By A. ROMMIER (Compt. rend., 103, 1266--1268).-The ferment ofthe raspberry, which has been described by lie Be1 as Levure wurtzii,is not able to convert the whole of the sugar of the raspberry intoalcohol.In order to ascertain if this is due to want of activity in theferment, or to the action of some constituent of the fruit, energeticel1ipso:dal wine yeast was mixed with the liquid. Fermentation thenproceeded rapidly, and not only the sugar existing in the fruit, but twoor three times the quantity of added sugar, was converted into alcohol.Raspberry brandy, obtained by distilling the wine, is very aromatic,and has the odour of raspberries, then becomes slightly smoky, butfinally acquire8 a very fine bouquet.The ferment of strawberries is more active, but fermentation isaccelerated by the addition of ellipsoydal wine yeast.. Strawberry winefrom French strawberries is less acid than that from raspberries, andkeeps well, provided that it contains 16 per cent.of alcohol. Thebrandy has a strawberry bouquet, which becomes stronger after sometime, but does not alter in character.The flavour of the brandy from English strawberries, althoughmade with a double quantity of added sugar, is still so strong as to beunpleasant, but if diluted with water the strawberry bouquet developsin perfection, h fact which indicates that more sugar might he addedwith considerable advantage.Levure wurtzii and others, such as L. apiculatus, have no inversiveproperties, and can therefore act only on invert sugar, and are unableto alter the sacchnrose which also exists in the juices of many fruits.A higher yield of alcohol can be readily obtained by adding an inver-sive ferment like the ellipsoidal yeast of wine.Zymotic Virus and Fermentation.By S. ARLOING (00mpt. rend.,103, 1268--1270).-The virus of gangrenous septicsemia and ofsymptomatic anthrax have the power of fermenting nitrogenoussubstances such as peptone, albumin, and yolk of egg. The productsare ammouiacal compounds, with possibly indole and skntole. Hy-drogen, nitrogen and carbonic anhydride are evolved, the hydrogenbeing present in much greater relative proportion in the gases fromalbumin and yolk of egg than in those from peptone. These factsconfirm the analogy between zymotic virus and ferments.The gaseous infiltration which characterises gangrenous septicsemiaand symptomatic anthirtx is in all probability due to the fermentationof the carbohydrates and nitrogenous compounds in the tissues.Loss of Nitrogen by Plants during Germination andGrowth.By W. 0. ATWATER and E. W. ROCKWOOD (Arner. Chem. J.,8,3'L7--343).-During the germination of seeds, and the early growthof plants, may there be a material loss of nitrogen ? (compare Abstr.,1885, 1005). Yeas were allowed to germimte and grow for A certainlength of time in moist sand, and the nitrogen contained in them andalso in the sand and moistlire estimated. The sum of these twoquantities was always less than the computed nitrogen in the originalseeds, the loss varying from 6 to 16 per cent., according to the timeC. H. B.C. H. BVEGETABLE PHYSIOLOGY AND AGRICULTURE. 293of the experiment and the locality. Only in cases where a quantity ofthe rootlets had been torn off in removing the plants from the sanddid the nitrogen in the moist sand exceed 3 per cent.of the whole.Bearing in mind the work of other experimenters, the authors believethat this loss of nitrogen, which is not observed in the germination ofall seeds, is not a normal process of the growth of the plant, but iscaused by processes of decomposition that depend on the presence ofmicrobes . H. B.Variations in the Chemical Composition and Physical Pro-perties of American Oats. By C. RICHARDSON (Amer. Chem. J.,8, 364-374 ; compare Abstr., 1885, 585).-The grains vary consider-ably in weight, size, weight of husk, and in the way in which the huskencloses the grain, according to the environmeut,s of the plants.Thechemical composition! however. is far more constant, and the propor-tion of husk aud kernel and the compactness of the grain prove to bethe all-important factors, and the weight per bushel the best means ofjudging of the value of the grain. No differences can be shown toexist such as might be expected between the largest and smallest oats,those having the lowest and highest proportion of kernel, &c. Thedetailed results are embodied in ti series of tables. H. B.Loss occasioned by Improper Methods of Pickling Wheat.By P. GRASSMAN (Bied. Centr., 1886, 766--774).-1t is customaryto treat wheat before sowing with solution of copper sulphate,which destroys the spores of bunt (Tilletia caries), but generallyno special attention is paid to the quantity of sulphate employed;consequently much loss ensues, owing to the destruetive action of thesulphate on the germinative power of the grain.Kuhn recommendsthat for every 5 bushels of wheat 1 lb. of siilphnte be dissolved in50 parts of water. In this solution, the wheat is to be soaked for 12 to16 hours, after which, the liquid being first removed from above, thegrain is to be dried for 24 hours. The liquid is to be removed fromabove, because the diseased grains and the fungus float to the top, sothat if the liquid is drawn OW from below, or if the grain is lifted outthrough the liquid, the damaged grain and spores will be mixedagain with the healthy material. Grossman has examined the effectof prolonged drying and increased streugth of s'olution on the vitalityof the seed, and finds that both of these conditions are highly detri-mental to the germinative power, and that where germination is notactually destroyed, the sprout will be unhealthy and weak, and germi-nation will be delayed.Tables are given showing in detail the resultsof various mixtures and times of drying on the germination.Nitrogen Compounds in Vegetable Soils. By BERTHELOT andANDRB ( C m p t . rend., 103, 1101-1104) .-The nitrogen in vegetablesoils exists mainly in the form of insoluble compounds with carbon,hydrogen, and oxygen.Sieved and air-dried soil was suspended in water, mixed withvarious proportions of hydrochloric acid, kept, at different tempera-tures for varying lengths of time, and then filtered.The filtrate wasE. W. P294 ABSTRAUTS OF CHEMICAL PAPERS.carefully neutralised with potasb, then slightly acidified, and after-wards mixed with excess of magnesia, and the ammonia estimated bySchloesing’s process. The ammonia was also determined in the soilwhich had been in contact with water only, and the difference betweenthe two quantities gave the amount of ammonia formed by the actionof the acid on the nitrogen compounds in the soil. The quantity ofammonia thus formed increases with the concentration of the acid,the time, and the temperahre. The action of the hydrochloric acidis in fact precisely similar to its action on urea, asparagine, oxamide,&c. (this vol., p. 235), and hence i t follows that the nitrogen in thesoil exists in part at least in the form of amides.After estimation of the ammonia, the liquid was carefully neutra-lised with sulphuric acid, evaporated to dryness on the water-bath,and the nitrogen in the residue estimated by means of soda-lime.This determination gives the amount of uitrogen present in the formof soluble amido-compounds, and it was found that the proportion ofthese compounds increases with the time of action of the hydrochloricacid and with its concentration.The amido-compounds thus renderedeoluble by the action of the acid may be divided into two groups, oneof which remains in solution when the liquid is neutralised withpotash, whilst the other is precipitated with the ferric, aluminium andcalcinm oxides. In one experiment, the ratio between the nitrogen inthe two groups was 23 : 17.Alkalis act on the nitrogenous matter in much the same way ashydrochloric acid.C. H. B.Manuring Rye with Thomas Slag and other Phosphates.By M. SIEVERT (Bied. Cevttr., 1886, 744-745).-The land had beenmanured in the previous year with farmyard manure, and in thisseason it received 30 lbs. PzO, and 10.5 lbs. N as ammonium sulphateor bone-meal per morgen. The phosphates applied were Thomasslag, bone-meal superphosphate, and Curavoa phosphate. In all casesthe slag brought the lowest, and the superphosphate the highest yield,and from a money point of view the super- and Curayoa phosphateswere the most advantageous. E. W. P.Thomas Slag and other Phosphates as Manure for Moor-lands.By RIMPAU and others (Bied. Centr., 1886, 732--742).-1nthe previous year, the phosphates failed to produce any definite result(Abstr., 1886, 1069). The experiments have been repeated in thesucceeding year without added manures, so as to obtain informationregarding the after-effect of the manures. It appears, then, that theafter-action of Thomas slag and precipitated phosphate are alike. Aset of experiments similar to those already described (Zoc. cit.) havebeen made by Wagenheim, from which it appears that as a manurefor rye, slag is as good as precipitated phosphate ; moreover, P. Wag-ner’s law, that so long as an increase is obtained by the employmentof increased quantities of phosphate, that increase will be in directratio with the increase of manure, was corroborated.Another corroboration of Wagner’s law was also obtained when ryewas grown, and a, distinct advantage of slag over precipitated phosANALYTICAL CHEMISTRY. 295phate was noticed, in that the expenses were less with the former thanwith the latter. E. W. P.Superphosphate Manuring for Sugar-beet. By A. NATJTIER(Bied. Centr., 1886, 742-744) .-It was found in the neiqhbourhoodof Peronne, where the land was rich (P,O, 0.34 per cent, N. 0.17,K20 0*53), that the addition of manures (nitre, ammonia, oil-cake,and phosphate) was unnecessary, as instead of an increase in thecrop which paid for the manure the case was exactly opposite ; therewas a deficiency and loss. Neither was the percentage of sugar inthe juice appreciably altered. But, on the other hand, in poor landdeficient in phosphates, a gain was obtained by the use of superphos-phate and natural phosphates, yet the total yield was lower, althoughthe quotient of purity was higher than on the richer soil.E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8875200291

出版商:RSC    

年代:1887

数据来源: RSC