摘要:

J O U R N A L c. P’. BAKEE, €’h.D., B.SC. C. H. BOTHAYLEY. W. A. DAVIS. T. EWAN, B.Sc., Ph.D. M. 0. FOBSTEB, Ph.D., D.Sc. E. COOLDING, B.Sc. W. D. HALLIBURTON, M.D., B.Sc., A. HARDEN, M.So., Ph,D. L. M. JONES, B.Sc. L. DE KONINGH. A. LAPWORTH, D.Sc. N. LEONARD, B.Sc. H. R. LE SUEUR, B.So. F. R. S. THE CHEMICAL SOCIETY. D, A. Louis. 1’. M. LOWRY, D.Sc. J. MCCUE, Ph.D. N. H. J. MILLER, Ph.D. G. T. MORGAN, D.Sc. K. J. P. ORTON, M.A., Ph.D. J. 0, PHILIP, M.A., Ph.D. R. H. PICKABD, D.Sc., Ph.D. T. H. POPE. E. C. ROSSITER.. M. J. SALTER. L. J. SPENCER, M.A. J. J. SODBOROUGH, Ph.D., DSc. E. W. WHEELWRIGHT, B.A., Ph.D. ABSTRACTS OF PAPERS ON ORGANIC CHEMISTRY. H. E. AEbISTBOSG, Ph.D., F.R.S. J. DEWAR, LL.D., F.R.S. E. DIVERS, M.D., F.R!S. WYNDHAM R. DUNSTAN, M. A., F. R.S. H. J. H. FENTON, M.A., F.R.S. C. E. Gaov~s, F.R.S. R. MELDOLA, F.R.S. J. EMERSON REYNOLDS, D.Sc., F.R.6. A. SCOTT, D.Sc., F.R.S. T. E. THORPE, LL.D., F.R.S. W. A. TILDEN, D.Sc., F.R.8. Cbitar : W. P. WYNNE, D.Sc., F.R.S. Sub- bbifm : A. J. GREENAWAY. 1901. Vol. LXXX. Part I. LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW, 1901.RICHARD ULAY & SONS, LIMITED, Lomox bc BUKGAY.

ISSN:0368-1769    

DOI:10.1039/CA90180FP001

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

J O U R N A L C. F. BAKEE, Ph.D., KSc. C. €1. BOTHAMLEI-. W. A. DAVIS. T. EWAN, B.Sc., P1i.D. &I. 0. FOI~S'I'ER, Ph.D., D.Sc. E. GOULDIKG, E.Sc. W. D. HALLIBURTOX, R'I.D., E.Sc., A. HARDEN, M.Sc., P1i.D. L. M. JONES, B.Sc. L. DE KONINGH. A. LAPWORTH, DSc. N. LEONARD, R.Sc. H. R. J,E S v ~ u n , R.Sc. F.R.S. OF D. A. LOUIS. T. M. LOWRY, D.Sc. J. MCCRAE, P1i.D. N. €I. J. MILLER, Ph.D. G. T. MORGAN, D.Sc. K. J. P. ORTON, M.A., Ph.D. J. C. PHILIP, M.A., Ph.D. R. H. PICKAILD, D.Sc., P1i.D. T. H. POPE. E. C. ROSSITEB. RI. J. SALTER. L. J. SPENCER, M.A. J. J. SUDBOROUGH, Ph.D., D.Sc. E. TV. WHEELWRIGHT, E.A., P1i.n. THE CHEMICAL SOCIETY, ABSTRACTS O F PAPERS ON PHYSICAL, INORGANIC, MINERALOGICAL, PHYSIOLOGICAL, AGRICULTURAL, ANALYTICAL CHEMISTRY. H. E. ARIISTI:ONG, Ph.D., F.R.S. J. DEWAR, LT,.D., F.R.S. E. DIVERS, M.D., P.R.S. WYNDHAM R. DUXSTAN, RI. A., F. R. S. H. J. H. FEKTON, M.A., F.R.S. C. E. GJ:OTES, F. R.S. R. MELDOLA, F.R.S. J. Emrmx REYNOLDS, D.Sc., F.R.S A. SCOTT, D.Sc., F.R.S. T. E. TiIoRrE, LL.D., F.R.S. TV. A. TILDES, D.Sc., F.R.S. @ bifm : W. P. WYNNE, D.Sc., F.R.S. Sltb- mifar : A. J. GREESAWAS. 1901. Vol. LXXX. Part 11. LONDON: GURNEY & JACKSON, I, PATERNOSTER ROW. 1901.R~CHARD CLAY & SONS, ~~IMlTEFJ LONDOK Q BUNOAY.

ISSN:0368-1769    

DOI:10.1039/CA90180FP003

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

14 ABSTRACTS OF CHEMICAL PAPERS, Inorganic Chemistry. Origin of A€mospheric Hydrogen. By ARMAND GAUTIER (Compt. rend., 1900, 131, 647-652).-The hydrogen in the atmo- sphere may be derived, not only from volcanic action and other well known sources, but also from the action of water on ancient granitic rocks a t 4emperatures considerably below a red heat. Granite from the interior of a fairly large block, powdered in an atmosphere of carbon dioxide and afterwards heated with dilute acids at 100’ or with water alone a t 280°, yields a considerable quantity of gas, consisting mainly of hydrogen, together with hydrogen sulphide, ammonia, carbon dioxide, nitrogen, and traces of unsaturated hydro- carbons, and sometimes traces of methane. A granite from Vire when heated with phosphoric acid diluted with its own volume of water, gave 1400 C.C.of gas per kilogram and 916 C.C. of this was hydrogen. With water only a t 280-300°, the proportion of gas liberated is smaller. The hydrogen and the ammonia that accom- panies it are probably due to the action of the water on nitrides and chiefly on iron nitrides, although possibly some of the hydrogen may be derived from its action on carbides. Higher Hydrogen Peroxides. By A. BACH (Bey., 1900, 33, 3111--3118).-This paper is largely a reply to criticisms by Arm- strong (Proc., 1900, 16, 134) and Baeyer and Villiger (Abstr., 1900, ii, 719) of a previous paper (Abstr., 1900, ii, 470). Although Caro’s acid when diluted does not reduce potassium permanganate, yet, undiluted, it rapidly decolorises a solution of the latter in concen- trated sulphuric acid (permanganic oxide) ; the titration is sharply defined, and the whole of the oxygen of the persulphate is evolved together with that due to the permanganate.The view that a catalytic decomposition of the Caro’s acid here occurs, appears to be excluded by the fact that the latter yields no oxygen either with manganous sulphate or with the liquid obtained after titrating Caro’s acid with permanganic anhydride. The existence in Caro’s reagent of a ‘‘ higher persulphuric acid,” (S0,H*O*O*S03H),, is therefore assumed, which on dilution yields the acid, SO,H*O*OH, incapable of reducing potassium permanganste. In the higher acid an ozonoid grouping is probable, since Cnro’s acid is formed on dissolving sodium dioxide in C. H.B.INORGANIC CHEMISTRY. 15 well cooled sulphuric acid, although, on warming, ozone is evolved (compare Bamberger, Abstr., 1900, ii, 536). W. A. D. Action of the Silent Electric Discharge on Sulphur Per- fluoride. By MARCELLIN P. E. BERTHELOT (Ann. Chirn. Phys., 1900,[vii], 21,205).-Sulphur perfluoride when submitted to the silent electric dis- charge remains unaffected, its stability under these conditions being comparable with that of the fluorides of boron and silicon ; the gas is not absorbed by bromine, thiophen, or acid solutions of cuprous chloride. G. T. M. Distribution of Sulphuric Acid in the Atmosphere. By HERMANN OST (Chem. Centr., 1900, ii, 733; from Chern. Ind., 23, 292-296).-In order t o compare the quantity of sulphuric acid in the atmosphere at various places, rectangular pieces of cotton wool or floconn6, 20 x 30 em., saturated with barium hydroxide solution, were attached to the branches of trees in such a way that the material was kept taut and these were then left exposed for a considerable period.On the Suutel mountains, far from any commercial industry and where scarcely any coal is burnt, only 0*0555-0*180 gram of sul- phur trioxide was found to have been absorbed in 153 days, whilst on the plain north of Hanover between Fuhrberg and Celle and 8 kilometres from the latter, 0*118-0.323 gram was absorbed in 193 days ; the maximum amount was obtained by exposing the material in an open position unprotected on every side and away from trees, and the minimum in forests. I n the neighbourhood of Hanover, 0*534-0.790 gram was absorbed in 175 days.Any sulphur pre- sent in mineral dust was excluded from the tests. E. W. W. Persulphates. By RODOLFO NAMIAS (L’Orosi, 1900,23,218-223). -Persulphates rapidly absorb moisture from the air with the forma- tion of the corresponding sulphate and sulphuric acid accompanied by the evolution of oxygen. Solutions of the persulphates are, however, very stable and may be employed in volumetric analysis for the estimation of substances having a reducing action. The best method of estimating the persulphates is to add excess of potassium iodide to a cold solution of the persulphate having a concentration not greater than 0.5 per cent. and after the liquid has remained for 10-12 hours, to estimate the free iodine by means of standard sodium thiosulphate solution.In neutral solution, the persulphates have the power of dissolving many metals such as zinc, iron, and aluminium, the two normal sulphates being formed; copper is not attacked by neutral or acid solutions of the persulphates but is rapidly dissolved in presence of ammonia, under which conditions zinc and iron are slowly acted on. Silver undergoes gradual solution by either the acid or ammoniacal solution. Chromium salts, in solutions either neutral or faintly acid with sulphuric acid, are quantitatively converted into chromic acid by excess of persulphate, a reaction useful in the estimation of chromium in steels, the chromium being first converted into chromate by means16 ABSTRACTS OF CHEMICAL PAPERS. of persulphate, the iron then separated by the addition of ammonia, and the chromate finally determined volumetrically. By mixing ammonium persulphate and ammonium hydroxide with the solution of a manganese salt, complete precipitation of a hydrated manganese dioxide takes place, the oxidation being much easier and more convenient than when bromine is employed, The oxidising action of persulphates in either acid or neutral solu- tion can be made use of in the bleaching of such materials as textile fabrics, wood, and ivory, whilst when mixed with sulphuric acid they bave the function of energetic depolarisers and may replace the nitric acid of the Bunsen cell. When heated with a persulphate at 70--80°, ethyl alcohol is rapidly converted into aldehyde, whilst many organic compounds capable of oxidation, especially closed chain compounds, give up hydrogen and yields sulphonic derivatives.Thus quinol reacts with the persulphates, forming an insoluble sulpho-compound, and diaminophenol, pphenylene- diamine, p-aminophenol, &a, give characteristic colour reactions. On adding a persulphate to a cold solution of aniline hydrochloride, R dark green precipitate is formed, which is insoluble in water or alcohol and when treated with sodium hydroxide or carbonate solution turns dark green but remains insoluble. T. H. P. Action of Hydrogen Peroxide on Thiosulphates. By ARNOLD NABL (Bey., 1900,33,3093-3095).- When hydrogen peroxide is added to a solution of sodium thiosulphate, a marked rise of temperature occurs and the solution becomes alkaline to litmus.This reaction is not due to liberation of sodium hydroxide, but to the formation of a new sulphur base, possibly in accordance with the equation 2Na,S,03 + H,O, = Na,SO, + Na,S03 + S,H*OH. The new base is not volatile with steam, is insoluble in alcohol, and its aqueous solution has n strongly alkaline reaction and a green fluorescence. It precipitates the hydroxides of silver, copper, iron, and uranium from their salts, reduces hot Fehling’s solution, and pre- cipitates the sulphide from stannic chloride. It yields a platinichloride which is quickly reduced, especially on heating. The base probably possesses analogies with trimethylsulphine hydroxide afid with hydroxy 1- amine. A. L. Nitrogen Iodide. By OTTO RUFF (Bey., 1900, 33, 3025-3029).-When iodine is added to liquid ammonia cooled to -SO0, a black powder (possibly N13:N13) is first formed, but eventually brownish-red plates with a greenish shimmer are obtained, which have the com position N13,12NH,. At - 35O t o - 40°, olive-green needles with the composition NI,,3NH3 are obtained ; under diminished pressure, these lose ammonia and yield ordinary nitrogen iodide, N13,NH, (compare Hugot, Abstr., 1900, ii, 274). When one atom of iodine is added to a mixture of 1 mol. of sodamide and liquid ammonia, cooled with liquid air, a violent reaction takes place; the product is a black compound, apparently of the com- position Na,N13, in which the nitrogen is quinquevalent. On further addition of a second atom of iodine, or of 1 mol. of ammonium iodide,INORGANIC CHEMISTRY.17 one or other of the compounds NI3,12NH, and N13,3NH, is formed, according to the temperature. The cooling mixtures required were obtained by adding alcohol slowly to liquid air contained in a Dewar’s beaker or in a beaker jacketed with cotton-wool, until the solidified alcohol redissolved to a syrupy liquid ; when the temperature had risen to - TOo, more liquid air and then alcohol were added as before, and the operation was repeated until enough of the mixture had been prepared. The sub- stances prepared were filtered through glass wool and asbestos in a filter tube surrounded with the cooling mixture, which was contained in a Dewar’s vessel. The washing was performed in the same tube, first with cooled liquid ammonia, then with cooled absolute ether, C.F. B. Formation of Nitric Acid during Combustions. By MARCELLIN P. E. BERTHELOT (Ann. Chirn. Phys., 1900, [ vii], 21, 145-201).- The experimental results embodied in these five memoirs have already been published (compare Abstr., 1899, ii, 648; 1900, ii, 475, 476, 538). G. T. M. By R. DUPOUY (Chem. Centr., 1900, ii, 8 3 6 ; from Bull. Trav. Soc. Pharrn. Bordeaux).-A sample of officinal arsenic triiodide, consisting of a crystalline powder, when treated with water left a yellow, insoluble residue of antimony oxyiodide, SbOI, this compound being formed by the action of water on antimony triiodide contained in the drug. The insoluble residue from a second sample consisted of antimony oxyiodide and free arsenic, whilst a third samplg left a residue of free arsenic alone.Another preparation containea an excess of free iodine and formed a clear brown solution which gradually became colourless. Arsenic triiodide should be tested by titrating with mercuric chloride, silver nitrate, or iodine solution ; in the first case, the compound Hg12,2HI is formed, whilst in the last two silver iodide and hydriodic acid are formed respectively. Arsenic Triiodide. E. W. W. Constitution of the Perborates. By EMIL J. CONSTAM and J. CORA BENNETT (Zed. anorg. Chem., 1900, 25, 265--269).-The mode of preparation of the perborates and the fact that the ammonium salt contains +H,O appear to indicate a doubled formula for these com- pounds. The authors, however, find that the difference between the electrical conductivities a t v = 1024 and B = 32 is 9 4 units, indicating a monobasic acid, so that the simple formula must be assumed.At- tempts to produce a perborate by the electrolysis of orthoborates were unsuccessful, and hence did not confirm Tanatar’s observations (Abstr., 1898, ii, 427). Reactions of Oxygen and Carbon Monoxide in the Presence of Alkalis. By MARCELLIN P. E. BERTHELOT (Arm. Chim. Phys., 1900, 1 vii], 21, 205-206).-After leaving a mixture of equal volumes of carbon monoxide and oxygen at the ordinary temperature for three months over a concentrated solution of potassium hydroxide, it was found that the former gas was absorbed by the alkali to form potass- ium formate, whilst the whole of the latter remained unchanged ; a L. M. J. VOL. LXXX. ii. 218 ABSTRACTS OF CHEMICAL PAPERS, similar result was attained in 14 hours by conducting the experiment at looo. When ammonia is substituted for potassium hydroxide either at the ordinary temperature or at looo, there is no formation of am- monium carbonate, and the absorption of carbon monoxide is very slight.G. T. M. Aotion of Sodammonium and Potassammonium on certain Metalloids. By CHARLES HUGIOT (Ann. China. Phys., 1900, [ vii 3, 21, 5-87).-This memoir contains an extensive bibliography and a detailed account of the preparation of compounds previously described (compare Abstr., 1896, ii, 20 ; 1898, ii, 573 ; 1899, ii, 151, 650, 747 ; 1900, ii, 14, 274). Hydration Processes. By PAUL ROHLAND (Ber., 1900, 33, 2831-2833. Compare Abstr., 1899, ii, 590).-It has been found that certain substances exert an influence on the hydration of Portland cement exactly similar to that which they have on the hydration of calcium oxide, Thus calcium chloride, aluminium chloride, and sodium carbonate accelerate, potassium dic hromat e, calcium chromate, boric acid, borax and potassium sulphate retard hydration, and sodium or lithium chloride has no action.The same generalisations do not hold good for the hydration of calcium sulphate ; in this process, sodium chloride, aluminium chloride, potassium dichromate, calcium chromate, and potassium sulphate accelerate, boric acid, bomx and sodium carbonate retard hydration, and calcium chloride is indifferent. The acceleration or retardation is roughly proportional to the con- centration of the solution of substance employed.If the velocity of hydration is great, then the added substance has a greater influence, either accelerating or retarding, than when the velocity is small. G. T. M. J. J. S. Constitution of Hydraulic Cements. By ORAZIO REBUFFAT (Gaxxetta, 1900, 30, ii, 177-182).-A correction of misquotations of the author’s views on this question. Action of Sea-Water on Pozzuolana Mortar. By ORAZIO REBUFFAT (Gaxzelta, 1900, 30, ii, 157--164).-The author’s experi- ments lead to the following conclusions. 1. Sea-water transforms the cement of mortar made from pozzuolana into a hydrated aluminium sili- cate whichcontainssrnall quantities of lime, magnesia, and the alkalis, and is perfectly stable towards the salts of sea-water. 2. Since pozzuolana mortar immersed in sea-water ultimately loses the whole of its lime, the employment of mixed mortars of cement and pozzuolana recom- mended by Michaelis cannot result in the fixation of the free lime of the cement.T. H. P. Artificial Pozzuolana. By ORAZIO REBUFFAT (Gaxxetta, 1900, 30, ii, 182-1 90). -Experiments on artificial pozzuolana lead to the following conclusions. 1. Aluminium silicate of the composition 2SiO,,A1,0,,2H,O, when heated a t 700--800°, loses water and assumes the nature of pozzuolana ; the residue has not the power to take up again the moisture given off. It is to the presence of this silicate that T. H. P.INORGANIC CHEMISTRY. 19 clay owes the pozzuolana properties it acquires on heating. 2. The silicate is not more easy of attack by hydrochloric acid after heating, although it becomes readily soluble in dilute alkali hydroxide solutions.3. The compound 2Si0,A120, combines with lime in the presence of water, giving a substance of the composition 2Si02,A103,3Ca0, 1 OH2?, the formation of which determines the setting of pozzuolana made from kaolin or from clay heated a t '700-800°. 4. This double silicate is readily decomposed by acids or by solutions of ammonium or mag- nesium salts, these salts removing the lime and leaving a hydrated aluminium silicate, 2Si0,,AI2O3,4H20, which in its chemical characters closely resembles certain varieties of the mineral halloysite. T. H. P. Slow Action of Hydrogen Bromide on Glass. By MARCELLIN P. E. BERTHELOT (Ann. Chim. Phys., 1900, [vii], 21, 206).-When glass tubes containing gaseous hydrogen bromide are examined after two years, a portion of the gas is found to have disappeared and drops of its aqueous solution are formed, the water being probably derived from the slow action of the gas on the alkaline silicates and sulphates which enter into the composition of the glass.Radio-active Lead and Radio-active Rare Earths. By KARL A. HOFMANN and EDUARD STRAUSS (Ber., 1900, 33, 3126-3131).- Pure lead sulphate was isolated from pitchblende, the uranium micas, broggerite, cleveite, and samarskite, which was radio-active although containing no trace of bismuth (polonium), barium (radium), titanium, thorium or uranium ; the sulphate was insoluble in dilute sulphuric acid, but easily soluble in basic ammonium tartrate. The derived lead chloride crystallised from hot water, and then showed diminished radio-activity, whilst the crystals from the mother liquors showed in- creased activity.Only traces of radio-active bismuth could be iso- lated from pitchblende, the uranium micas and samarskite. A mixture of cerium and yttrium oxalates, isolated from braggerite, cleveite and samarskite, and freed from thorium and uranium, was found to be radio-active, the oxides derived therefrom being especially so. Uranosouranic oxide,U308, from all the minerals already named, and also from euxenite, is always radio-active, and the same is true of the derived uranium oxalate, although on recrystallising the latter, the most solu- ble fractions are found to be inactive. Thoria from broggerite, cleve- ite, and samarskite is active, although from euxenite, which is closely allied to samarskite in composition it is obtained inactive.W. A. D. Formation of Mixed Crystals of Thallium Nitrate and Thallium Iodide. By C. VAN EYK (Proc. R. Akad. Wetensch. Amsterdam, 1900, 3, 98--101).-The relation between the composition of mixtures of the fused salts and that of the mixed crystals deposited on cooling has been examined. The melting point line is of Roozeboom's type I V (compare Abstr.: 1900, ii, 132), and rises immediately from the solidi- fying point of the nitrate, showing that mixed crystals are deposited from the melt. The mixed crystals deposited on solidification of mixtures with 0-9.9 molecular per cent. of the iodide are white ; those from mixtures with more iodide are red.The white mixed crystals contain GI. T. M. 2-220 ABSTRACTS OF CHEMICAL PAPERS. from 0-8 molecular per cent. of the iodide, and the red from 65-100 per cent. Mixtures containing from 18-65 molecular per cent. of the iodide solidify at 215.5" to a, conglomerate of the limiting mixed crystals, Thallium nitrate, which is rhombic a t the ordinary tempera- ture, is rhombohedra1 above l42', but this transition temperature is lowered by admixture with the iodide ; similarly, the transition point ( 1 6 9 O ) of the iodide is lowered by addition of nitrate. Alterations in the Chemical Properties of Elements Pro- duced by the Addition of Traces of Foreign Substances. By GUSTAVE LE BON (Compt. rend., 1900, 131, 706--708).-When mercury is alloyed with traces of magnesium, it acquires the property of decomposing water, and becomes rapidly oxidised by exposure to the air at the ordinary temperature, a perceptible alteration being caused by the addition of only 1/14,00Oth part of magnesium.Mag- nesium contaminated with mercury rapidly decomposes water in the cold. Aluminium foil, coated with a thin film of mercury, is quickly oxidised on exposure to air, and a strip of the metal placed verti- cally in a vessel containing water and mercury is continuously cor- roded at its lower end until completely disintegrated (compare Hunt and Steele, Abstr., 1899, ii, 33). Behamiour of Mixtures of Mercuric Iodide and Silver Iodide. By H. W. BAKHUIS ROOZEBOC~M (?roc. K. Akad. Wetensch. Amsterdam, 1900, 3, 84--86).-1nvestigation of fused mixtures of these salts shows that the melting point of mercuric iodide is lowered from 257' to 242' by an admixture of 14 molecular per cent.of silver iodide, whilst the melting point of silver iodide is lowered from 526' to'242' by an admixture of 86 molecular per cent. of mercuric iodide. The course of solidification shows that two kinds of mixed crystals are formed; on the mercuric iodide side, crystals of the rhombic mercuric iodide type with 0-4 molecular per cent. of silver iodide, on the other side crystals of the regular silver iodide type with 18-100 molecular per cent. of silver iodide. After solidification, mixtures containing from 4-18 molecular per cent. of silver iodide consist of a conglomerate of the two limiting mixed crystals. Those with 4 per cent.of silver iodide undergo a change at about 127', because the mercuric iodide is transformed from the rhombic into the tetra- gonal form, When the mixtures with 18-100 molecular per cent. of silver iodide are cooled below 157q the mixed crystals of the composition HgIq2AgI are suddenly transformed into a compound of the same composition, the colour changing at the same time from pink to red. This temperature (157') is comparable with the solidi- fying point of a chemical compound deposited from a liquid mixture. From mixed crystals containing less silver iodide than corresponds with the formula Hg12,2AgI, the formation of the latter compound occurs at temperatures from 157-118'; from mixed crystals con- taining more, at temperatures from 157-1 35'. The temperatures, 1 1 8 O and 135O, are analogous to eutectic points, the conglomerates formed consisting of Hg12,2AgI with either HgI, or AgI.The temperature of transformation of regular silver iodide into the hexa- J. C. P. G. T. M.INORGANIC CHEMISTRY. 21 gonal form is lowered by admixture of mercuric iodide from 157' to 135' ; the temperature of transformation of rhombic mercuric iodide into the tetragonal form is lowered by admixture of silver iodide from 127' to 118'. When the conglomerates of double salt with mercuric or silver iodide are further cooled to 45', the double salt changes from red to yellow, whether it is pure or mixed with mercuric or silver iodide. J. C. P. Separation of Cerite Earths from Monazite Sand. By RICHABD Jos. MEYER and E. MARCKWALD (Ber., 1900,33,3003-3013).-The crude material is the commercial #cerium oxalicum oxydul pur,' which is obtained as a residue after the extraction of thorium from monazite sand; it contains 25 per cent. of water and gave 32.5 per cent. of cerium oxalate, 21.5 per cent. of didymium oxalate, and 14 per cent. of lanthanum oxalate. The oxalates are dissolved in nitric acid and separated as ammonium double nitrates. The cerium is pre- cipitated as basic ceric sulphate from a solution of the mixed nitrates by adding ammonium persulphate and chalk (Witt and Theel, Abstr., 1900, ii, 403), and is purified by dissolving in boiled nitric acid (nitric oxide reduces the ceric salt), separating as ammonium double nitrate, and recrystallising from nitric acid. The didymium and lanthanum salts in the filtrate from the cerium precipitation are separated (from ytterbium salts, &c.) by adding potassium sulphate to the boiling solution until it no longer shows the didymium absorp- tion-spectrum ; the double sulphlttes which separate can be dissolved by boiling with nitric acid and pouring into boiling water, and are purified by precipitating as oxalates ; these are then dissolved in nitric acid, and the solution is boiled until free from acid.The separation of didymium from lanthanum is effected by adding mag- nesia until the solution no longer shows the didymium spectrum (Muthmann and Rolig, Abstr., 1898, ii, 518); by repeating this operation twice and precipitating twice with oxnlic acid and ammonia, the didymium is obtained nearly pure and free from all but a mere trace of lanthanum. The lanthanum is finally precipitated with ammonium oxalate in presence of ammonium chloride.Molecular Weight of Aluminium Compounds. By ELMER P. KOHLER (Amer. Chem. J., 1900, 24, 385--397).-The molecular weights of the aluminium derivatives of acetylacetone and ethyl acetoacetate were determined by the boiling point method, carbon disulphide being used as the solvent, and found to accord respectively with the formulae Al(C,H702)3 and Al(C6H,0,),. Determinations of the molecular weights of aluminium bromide and iodide in the same solvent agree with the formulze and A1216. The molecular weights of the compounds of aluminium bromide with benzenesulphonic chloride and nitrobenzene, and of the compound of aluminium chloride with nitrobenzene, are shown by the same method tocorrespond with theformulzeA12Br6,2CGH,=S02C1; A1,Br6,2C6H,*N02, and AI,C16,2C6H,*N02 J in each case, it appears that 1 mol.of the aluminium haloid com bines with 2 mols. of benzenesulphonic chloride or nitrobenzene to form 1 mol. of the product. It follows that the T. M. L.22 ABSTRACTS OF CHEMICAL PAPERS. addition of benzenesulphonic chloride or nitrobenzene to a solution of aluminium bromide of known boiling point should not affect the boiling point so long as the bromide is in excess; on the other hand, the addition of the bromide to a solution of benzenesulphonic chloride or nitrobenzene rJhould immediately lower the boiling point, and the depression should be proportional to the quantity of bromide added ; these conclusions were verified by experiment. A method is thus obtained for determining the changes which occur when an aluminium haloid is brought into contact with a given substance in an indifferent medium.The substance under investigation is added in successive portions to a solution of aluminium bromide of known con- centration and boiling point until it is present in excess, and a further quantity of aluminium bromide is then added ; the readings of the thermometer after each addition of material give an accurate account of what is taking place in the solution. By this means, it was found that the compounds of aluminium bromide with benzoyl chloride, benzo- phenone, and phosphorus oxychloride have respectively the composi- Acetophenone, benzenesulphonacetone, and ethyl benzoate form similar additive products with aluminium haloids ; benzene and naphthalene, however, slowly react to form insoluble compounds, whilst pyridine and quinoline yield crystalline additive compounds also insoluble in carbon disulphide.An experiment with aluminium bromide and p-dibromobenzene showed that the non-applicability of Friedel and Crafts' reaction to dihalogen compounds is not due to a combination of the dihalogen compound with the aluminium haloid. If one of the components of the additive compounds is present in large excess, dissociation occurs ; thus, cryoscopic determinations of the molecular weights of aluminium bromide and chloride in nitro- benzene solution point to the formuls AlBr, and AlC1,. Benzoyl chloride combines with aluminium bromide, in the absence of a sol- vent, to form a compound the molecular weight of which i8 shown by determination in carbon disulphide to correspond with that required for the formula A12Br6,2C6H,*COC1, whereas the determination in nitrobenzene gives an impossible value.The conclusion of Werner and Schmujlow (Abstr., 1898, ii, 214), that AlCl, is the only formula admissible for aluminium chloride is not justified, since they determined the molecular weight in pyridine, which combines with aluminium chloride to form a well crystallised compound. E. G. tion A1,Br6,2C6H,* coc1, AI2Br6,2COPh2, and AI,Br6,2POCl,. Cobalt Selenide. By HENRI FONZES-DIACON (Compt. Fend., 1900, 131,'704--705).-The selenide, CoSe, is obtained in an amorphous form by the action of selenium vapour on cobalt, and also by that of hydrogen selenide on heated cobalt oxide or chlorate.The sespuiselenide, Co,Se,, is produced by passing hydrogen selenide over cobalt chloride at moderately high temperatures ; at lower tem- peratures, these substances react with the formation of friable grey diselenide, corresponding with the formula CoSe, ; this substance roadily evolves selenium when heated. The selenide, Co,Se,, prepared by the interaction of hydrogenINORGANIC CHEMISTRY. 23 selenide, hydrogen chloride, and cobalt chloride at a dull red heat, forms violet-grey, regular octahedra, the specific gravity at 15' being 6.54. A subselenide, Co2Se, is obtained as a fused mass with a silvery lustre by reducing the preceding compounds in a current of hydrogen at a bright red heat; when this action is continued for some con- siderable time, the substance undergoes further reduction, but without yielding cobalt.These selenides are only slowly decomposed by hydrochloric acid and by hydrogen chloride at high temperatures. Chlorine and oxygen displace selenium from the heated selenides, the action in the latter case giving rise to the formation of selenium dioxide and cobalt oxide. The selenides readily dissolve in bromine water con- taining excess of bromine. Cobalt selenate, when reduced by hydrogen, yields either oxyselen- ides or a mixture of selenides and cobalt, according to the temperature employed. G. T. M. Ammoniacal Cobalt Arsenates. By 0. DUCRU (Compt. rend., 1900, 131,675-678).-The action of arsenic acid or an arsenate on solutions of cobalt salts containing ammonium rsalts and ammonia yields three insoluble ammoniacal cobaltous arsenates, Co3(As0,),,2NH,,6H,0, and Co3(As0,),,3NH,,5H,0, formed from the hydrated arsenate, Co3(As0,),,8H,0, by the partial displacement of water by an equal number of ammonia molecules.The composition of the product depends on the proportion of ammonia present, and is not affected by the proportion of ammonium salts. By 0. DUCRU (Compt. rend., 1900, 131, 702-704. Compare preceding abstract).-A solution containing a mixture of nickel and ammonium salts and free ammonia when treated with arsenic acid or a soluble arsenate, produces in the cold or on gently warming a gelatinous greenish-white precipitate which deepens in colour and becomes crystalline when the mixture is heated on the water-bath.The crystals are anisotropic and belong to the monoclinic system; they vary in composition according to the amount of ammonia present. The octahydrated nickel arsenate,. produced in the absence of am- monia, crystallises in needles and is identical in composition and crys- talline form with the mineral annabergite. When the solution contains 1 *38 per cent. of ammonia, a monoammonionickel ccrsenate is obtained ; with 6.9 per cent, of this reagent, a diccrnmonnio-salt is formed, the corresponding triammonio-compound being precipitated in more concentrated ammoniacal solutions, These salts behave in a char- acteristic manner when heated at 1 5 5 O , the composition of the com- pounds before and after heating being indicated in the following table : Co3(As04)2,NH3,7H,O, C.H. B. Ammoniacal Nickel Arsenates. Ni3( As0,),,8H20. Ni3( AsO4),1$R,O. Ni,(As0,),,7H20,NH3. Ni,(AsO,),lH,O,$NH,, Ni,( A s0,)2,6H,0,2NH3. Ni,( AsO,)~,~H,O, 3NHr N13( ASO,) ,&H,O,$NH,. Ni,(AsO,), $HI,O,$NH,24 ABSTRACTS OF CHEMICAL PAPERS. The anhydrous arsenate, Ni3(As0J2, is obtained in each case on heating the salt at dull red haat. Periodic Phenomena in the Dissolution of Chromium in Acids. By WILHELM OSTWALD (Zeit. physikal. Chem., 1900, 35, 204-256).-A continuation of the author's earlier paper (Abstr., 1900, ii, 730), in which the previous observations of periodicity by the dissolution of metals are fully discussed, and improvements on the apparatus employed by the author are described, An alloy of chrom- ium and aluminium was employed and the effect of various compounds in bringing about regular periodicity investigated.It was found that dextrin has a remarkably powerful effect in this direction, other colloidal carbohydrates being active to a smaller extent. The periodic time increases as the action progresses and a number of experi- ments testing the regularity of this increase are recorded. Various curves obtained are given in the paper and further investigations are promised. L. M. J. By JACOBUS M. VAN BEMMELEN [and G. M. RUTTEN] (Proc. K. Akad. Wetensch. Amsterdam, 3, 196--203).-The various solid phases of this system have been ex- amined. The normal salt, Bi20,,3N206,10H20, has not a true melting point, but decomposes at 75.5" into a liquid and the basic salt Bi,O,,N,O,,H,O.Two other normal salts with 4H20 and 3H20 respectively, have been discovered but not isolated ; their composition has been deduced by means of Schreinemakers' graphical method. The basic salt, Bi203,N20,,2H,0, is the first product of the action of cold water or dilute nitric acid (with less than 6 per cent. of N20,) on the decahydrate, or of cold water on n not too acid solution of his- muth nitrate. It forms very thin, crystalline plates, without definite shape and showing double refraction; these cannot be dried over sulphuric acid without decomposition, and in contact with the mother liquor they are converted into another basic salt. The basic salt, Bi20,,N,05,H20, is formed from Bj203,N205, 2H20 when the latter remains in contact with a solution containing more than 1 per cent.of N,O,; the time required for its formation diminishes as the percentage of N20, rises. The crystals are monoclinic, but when the same salt is formed by the decomposition of the decahydrate a t 75*5O, it has the form of thin, hexagonal prisms. The basic salt, 6Bi,0,,5N20,,9(8)H20, is formed at the ordinary temperature from Bi203,N20,,2H20, when the latter remains for some months in contact with a very dilute solution (less than 1 per cent. of N205 and less than 0.33 per cent. of Bi203) ; it is obtained also when the decahydrate is decomposed with water, and the solid salt which is formed is dissolved in much water. The crystals belong to the rhombic system; over sulphuric acid, they lose neither nitric acid nor water.The salt 2Bi203,N,0,,H20 is the final product of the action of boiling water on the normal salt. The compounds Bi203,2N20,,2H,0 and 10Bi,0,,9N20,,7H20 are also described. The basic salts, 5Bi20,, 4N20,, 9H,O, 4Bi203, 3N20,,9H,0, ~Bi,0,,3N,0,,8H20, and 5Bi,0,,3N,05,6H20, described by other lnvestigatoi s, are declared not to exist. Isotherms, giving the composition of the liquid phases which are in G. T. M, The System Bi203-N~05-H20.MINERALOGICAL CHEMISTRY, 25 equilibrium with the different solid phases have been totally or partially determined for the temperatures 20°, 30°, and 65'. The isotherms have been graphically represented in equilateral triangles, and from these tl figure in space has been drawn showing the con- ditions of equilibrium.The form of the triple lines in this system agrees with the form of those for the system HgO-SO,-HH,O (Hoit- sema, Abstr., 1896, ii, 15). By MARCELLIN P. E. BERTHELOT (Ann. Chim. Phys., 1900, [ vii], 21, 202-204).-Analyses of Egyptian gold coins of the earliest epochs indicate that the material employed in their pre- paration consisted of argentiferous alluvial gold ; only in later periods, from the time of Crcesus onwards, does it appear that the metal was refined, the desilverisation process being that described by Pliny. Owing to the rarity of minerals yielding gold free from silver, it is possible, by analyses of the golden articles found in Egyptian tombs, to state approximately the epoch of their manufacture. The gold leaf coverings of the mummies of the 6th and 12th dynasties contain 90-92 per cent. of gold, about 4 per cent. of silver, and 4-5 per cent. of organic matter, whereas those of the Persian epoch, ten centuries later, consist of nearly pure gold. Certain Properties of Alloys of the Gold-Copper Series. By SIR W. C. ROBERTS-AUSTEN and T. KIRKE ROSE (Proc. Roy. Xoc., 1900, 67, 105-1 12).-The authors have investigated the freez- i n g point curve for gold-copper mixtures. The freezing points of the pure metals are respectively, gold, 1063' ; copper, 1083O, and a mini- mum of 905' corresponding with an eutectic mixture was found for the alloy containing about 82 per cent. of gold, or 60 per cent. in atomic proportions. The atomic proportionsof the eutectic mixture agree closely with those for the eutectic mixture of silver-copper,&he freezing point curves also resembling one another closely, Microscopic examination was made of the various alloys, and these confirmed the existence of the eutectic alloy which makes its appearance even in the solidification of alloys containing only 27 per cent. of gold, as gold is com- paratively slightly soluble in copper, Copper is, however, more easily soluble in gold than in silver, so that the character of rich gold-copper alloys is not very marked, the crystals closely resembling those of J. C. P. Egyptian Gold. G. T. M. pure gold. L. 31, *J.

ISSN:0368-1769    

DOI:10.1039/CA9018005014

出版商:RSC    

年代:1901

数据来源: RSC

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MINERALOGICAL CHEMISTRY, Mineralogical Chemistry. 25 Minerals of Roumania. By PETRU PONI (Ann. 8ci. Univ. Jassy, 1900, 1, 15--148).-A complete and systematic description is given of Roumanian minerals, with notes on their occurrence at various localities, The paper is in French, and quotes much information and many analyses (some of which are given below) from the somewhat inaccessible Roumanian journals. Structural formulae are discussed,26 ABSTRACTS OF CHEMICAL PAPERS. and several new analyses are given. Two new minerals are described under the names badenite and brostenite. Pyrrhotite : an analysis (I) by Saligny, published in 1883, gives the formula Fel,S,?. Bccdelzite.-This IS a massive mineral with a granular structure and steel-grey colour ; sp. gr. 7.104. It occurs with chalybite, erythrite, and annabergite at Badeni, district of Muscel. From the analysis (11) it appears t o be related to smaltite (or safflorite), but with part of the arsenic replaced by bismuth ; formula (Co,Ni,Fe),(As,Bi),. Smaltite, also from Badeni, gave Saligny in 1883 the results under 111 (also CaCO,, 5.1 9 ; MgCO,, 1 *46 j insoluble, 4-99 ; manganese, trace).S. Cu. Fe. Co. Ni. As. Bi. Gangue. Total. I. 30.29 0.22 50.20 - - - - 19-18 99*89 Ia. 33.96 33-57 32.02 - - - - 0.20 99.75 11. 0.27 - 5.98 20.56 7.39 61.54 4-76 A 100.50 111. - 0.33 12.26 21-93 - 52.43 0.67 - 100.30 Twenty-severn analyses are given of salt ; besides sodium chloride, there are small amounts of magnesium chloride, sodium sulphate, calcium sulphate, water and insoluble matter. Analyses are also given of haematite, magnetite and limonite.Brostenite.-This occurs abundantly as compact, friable, black masses in crystalline schists near Brosteni, district of Sucdva. It sometimes surrounds rhodochrosite, of which mineral it is evidently an alteration product. The three recalculated analyses (IV-VI) give the formuls, 2Mn0,,R0,2H20, 3MnO,,RO,l +H,O, and 1 3Mn02,5R0, 12H,O respec- tively. The mineral is therefore a manganite of iron and manganese, and is perhaps related to chalcophanite, 2Mn02,(Mn,Zn)0,2H20. IV. 52.40 6.16 11.47 3.05 - 11-97 - 14-75 99.80 V. 68.06 8.96 4.08 3-82 0.61 7.17 1.97 5.51 100°18 VI. 61.95 3.11 12.02 2.70 0.72 10.90 - 8-20 99.60 A white, saccharoidal, dolomitic limestone from Sucdva gave analysis VII ; greyish-yellow crystalline chalybite associated with badenite gave VIII ; yellowish, amorphous rhodochrosite associated with bro- stenite gave IX.CaO. MgO. Feu. MnO. CO,. Insol. Total. Sp. gr. Copper-pyrites gave the results under Ia. MnO, MnO. FeO. CaO. MgO. H20. CaCO,. Gangue. Total. VII. 34.30 18.43 - - 47.36 0.30 100.39 - VIII. 4-46 7.21 40.72 6.12 39.49 2.21 100-21 3-455 IX. 4.07 2.30 3.17 50.29 39.02 1-42 100.27 3.193 Large crystals of augite gave anal, X by Murgoci (1895). Acicular crystals of tremolite from the dolomitic limestone of Sucbva (anal. VII) gave XI. Zoisite gave XI1 by Murgoci (1894). Analyses of ser- pentine, by Murgoci (1895), and of riebeckite (Abstr., 1899, ii, 768), are quoted. SiOP A1203. Fe,O,. CaO. MgO. H,O. Total. Sp. gr. X. 45.82 37.46 14.20 4.16 - 101.66 3.232 XI.58.22 0.92 - 13.37 25.33 1.76 99-60 2.937 - - - XII. 36.49 34.19 24.81 3.67 2.91 102.07PHYSIOLOGICAL CHEMISTRY. 27 New analyses of roumanite (Abstr., 1897, ii, 502 ; 1898, ii, 523) are given under XI11 and XIV; the first is of yellowish-brown material, and the second of material showing golden and greenish flashes. Seven analyses are also given of ozocerite (Abstr., 1897, ii, 502). Succinic Melting C. H. 0. S. Ash. Total. acid. point. XIII. 80.04 9.76 9.13 0.83 0.24 100*00 3.2 310-312' XIV. 80.32 10.02 8-17 1.06 0.43 100*00 2.1 318-330 Numerous analyses are also given of mineral waters and of various naturally occurring saline substances, as well as of anthracite and lignite. L. J. S. By SAMUEL L. PENFIELD (Amer. J. Xci., 1900, [iv], 10, 346-350).-The formula of turquoise is usually given as 2A1,O,,P,0,,5H2O, the copper, which is always present, being considered to be an accidental impurity (2Cu0,P205,4H,0 accord- ing to Clarke, 1886) to which the colour of the mineral is due.A new analysis is given of pure material from the Crescent Mining District, Lincoln Co., Nevada ; this is of a beautiful robin's-egg blue colour, and breaks with a smooth fracture; under the microscope, it appears to be homogeneous, and there is no evidence of the presence of two substances. P,O,. A120,. Fe20s. CuO. H20. Jnsol. Total. Sp. gr. 34.18 35.03 1.44 8.57 19.38 0.93 99.53 2,791 A consideration of this and other trustworthy analyses suggests that the copper is present as an essential constituent of the mineral; and this is also supported by the fact that finely powdered turquoise dis- solves in hydrochloric acid as a whole without discoloration. The new formula, (Al(OH),,Fe(OH),,Cu(OH),H],PO,, represents the mineral as a derivative of orthophosphoric acid with the hydrogen atoms largely replaced by the univalent radicles Al(OH),, &c. In some analyses, ap- proximately two-thirds of the hydrogen atoms are so replaced, and the formula becomes [A~(OH),,F~(OH),,CU(OH)]~,HPO,. By Prraux (J. PIkxrm., 1900, [vi], 12, 261-262).-These waters are very similar to those of Hamman-Lif and Bourbonne-18s-Bains, and have an average temperature of about 44'. The greater portion of the salts present in the waters consists of sodium chloride, the rest consisting of calcium, magnesium and potassium sulphates, calcium chloride, and calcium carbonate. H. R. LE S. Chemical Composition of Turquoise, L. J. 8. Analysis of the Thermal Waters of Achkel.

ISSN:0368-1769    

DOI:10.1039/CA9018005025

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 27 Effect of Gestation on the Amount of Mineral Matter, especially Phosphoric Acid and Calcium, in Cow’s Milk. By A. KORT (Bied. Centr., 1900, 29, 667-668 ; from Ing. Agr. Gemblom, 1899, 453--475).-The percentage amounts of mineral matter, and especially of phosphoric acid and calcium, diminish more or less regu-28 ABSTRACTS OF CHEMICAL PAPERS. lady as the time of calving approaches, notwithstanding the decrease in lactation. During the period of the greatest flow of milk, the percentage amounts of phosphoric acid and calcium are lowest, whilst the total amounts are greatest. The amounts of mineral constituents gradually became normal as the production of milk diminishes, but again de- crease towards the middle of the period of gestation.Normal feeding has practically no effect on the amount of mineral matter in milk. I n the case of herbivorous animals, gestation has no effect on the amounts of phosphoric acid and calcium in the urine; feeding has the predominating effect. As regards carnivoroua animals, however, the amount of phosphoric acid in the urine decreases during gestation. Division of Unfertilised Eggs. By ALBERT P. MATHEWEI (Amr. J. Physiol., 1900, 4, 343-347).--The experiments mere made on the eggs of Arhacia, and show that lack of oxygen, heat (32-33'), and exposure t o ether, chloroform, or alcohol for a short time are all followed by karyokinetic nuclear division. The essential basis in all casesappears to be the production of localised areas of liquefaction in the protoplasm, and it is suggested that the centrosome normally plays the part of a liquefying enzyme.Influence of Digestion on Animal Heat. By EDWARD T. REICHERT (Arne?*. J. Physiol., 1900, 4, 397-404).-Experiments on dogs show that the rise of temperature during digestion is due to increase of heat production. The maximum rise is during the fourth hour after a meal or later, but the changes in heat production (deter- mined calorimetrically) and temperature are not proportional, for the greatest increase in heat production occurs during the first hour after feeding. The most marked effects are observed when the diet consists of proteid and fat, next with proteid, and least with fat. Colostrum is rich in ash constituents. N. H. J. M. W. D. H. W. D. H. Gmeous Metabolism of the Submaxillary Gland.11. Ab- sorption of Water. By JOSEPH BARCROFT (J. Physiol., 1900, 25, 479--486).-The ' chorda blood ' contains less water than the arterial blood. After the first minute of stimulation, the water lost from the blood exceeds in volume the saliva secreted, and may be measured by multiplying the volume of saliva by a factor the mean value of which is 1.12. In the first half minute of secretion, there is a large flow of saliva, followed in the second half minute by a relatively small flow. I n the first half minute theabsorption of water from the blood is large ; this is diminished in the second half minute. Metabolism in Forced Feeding. By W. HALE WHITE and E. I. SPRIGGS (Proc. Physiol. Xoc., 1900, xxvii-xxviii).-Okser- vations were carefully made on a woman for 56 days.If all the gain of weight had been proteid, the nitrogen corresponding to it would have been 441.8 grams. But as the nitrogen not accounted for in urine and faxes was 661.04 grams, 219 grams of nitrogen have to be accounted for in some other, at present unexplained, way. W. D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY. 29 Metabolism in the Dog before and after removal of the Spleen. By DIASMID NOEL PATON (J. Physiol., 1900, 25,443-461). -After removal of tb spleen there is a more rapid excretion of water after a meal, which probably indicates more rapid absorption. Otherwise there is no essential difference in the course or nature of the metabolism either during fasting or after feeding with the ordin- ary proteids of flesh, with vegetable food such as oatmeal, or with food rich in nucleins, such as thymus gland.By EDUARD PFLUGER (Pfliiger’s Archiv, 1900, 82, 303-380).-Largely polemical. The main conclusion is that fat, like proteid and carbohydrate, undergoes hydrolytic decomposition before absorption, and is never absorbed as emulsified neutral fat. W. D. H. Absorption of Fat. W. D. H. Nutrition in Summer and Winter in Moderate Climates. By KARL ERKST RANICE (Zeit. Biol., 1900, 40, 288-323).-Experi- ments on man show that within ordinary ranges of temperature there is no correspondence between a warm temperature and a necessarily more limited supply of food. In summer temperatures of over ZOO, the instinctive lessening of appetite is related to pathological con- ditions induced by the excessive heat.Properties and Origin of Lymph. By LEON ASHER and FREDERIC W. BUSCH (Zeit. Biol., 1900,40, 333-373. Compare Abstr,, 1899, ii, 165).-The formation of urea from ammonium salts in the liver is accompanied by increased lymph formation : the lymph produced is more concentrated owing to increase of proteid. The formation of glycogen produced by injection of sugar into the portal system is ac- companied by increase in lymph formation, but the concentration of the lymph remains constant. The intravenous injection of an assimil- able proteid, such as casein, produces also a more abundant lymph which is richer in proteid. Heidenhain’s lymphagogues of the first class cause increased liver activity and so lead to increased lymph formation ; after intense activity of the liver, the coagulability of the lymph from the thoracic duct lessens.Activity of the pancreas similarly causes increase in lymph formation. These facts are all considered to support the view that lymph formation resembles the physiological process of secretion. Formation of Glycogen after Feeding on Galactose. By ERNST WEINLAND (Zeit. Biol., 1900, 40, 374-385).-1n the rabbit, the administration of galactose leads to the formation of glycogen in the liver. W. D. H. Urea Formation in the Body. I. Introduction. By WLADIMIR VON GULEWITSCH (Zed. physiol. Chm., 1900, 30, 523-532). 11. The Occurrence of Arginine in the Spleen. By WLAUIMIR VON GULEWITSCH and A. JOCHELSOHN (dbid., 533-538).-A discussion on the relative importance of the processes of hydrolytic decomposition of nitrogenous matter in the body, and of oxidation in intra vitam urea formation introduces a series of papers.However important oxidation may be, there can be little doubt that hydrolysis occurs also in nitro W. D. H. W. D. H.30 ABSTRACTS OF CHEMICAL PAPERS. genous katabolism. Drechsel’s well known work on the formation of urea from arginine in vitro renders it extremely probable that part, at any rat?, of the urea formed in the body may pass through the arginine stage. Hitherto, although arginine has been found in plants, its existence has never been shown in the animal body, and the first step in the series of investigations shows it to be present in the spleen of the ox, Future papers will deal with its fate in the body.W. D, H. Lactase of the Pancreas. By ERNST WEINLAND (Zeit. Biol., 1900, 40, 386-391).-The administration of milk increases the pro- duction of pancreatic lactase. Feeding on milk-sugar alone does the same thing. This is not due to the milk-sugar or any of its decom- position products passing into the pancreas; but the sugar acts as a stimulus, possibly to the secretory nerves of the organ. W. D. H. [Lecithin in Brain and Milk.] By ROB. BUROW (Zeit. physiol. Chem., 1900, 30, 495--507).-The lecithin was extracted by means of an ether-alcohol mixture, and estimated from the amount of phos- phorus in the extract. I n different animals, it was found that the amount of lecithin in the milk varies, its proportion becoming greater as the relative brain weight of the animal increases.The following table gives the principal results : Calf. Dog. Man. Relative brain weight .. . . .. ..*.. ... 1 : 370 1 : 30 1 : 7 } 1-40 2.11 3.05 Lecithin of milk in percentage of . . . . . . . . . . , . , . . . . . . . . . . . . . . pro t eid W. D. H. Relationship of Iron in the Urine and in the Blood. By ADOLF JOLLES and FERDINAND WINKLER (Chem. Centr. 1900, ii, 687-688 ; from Arch. exp. Path. Pharrn., 44, 464-476).-The daily excretion of iron in the urine averages 8 milligrams. The iron coefficient, that is, the proportion between the iron in the blood and urine, is 104.6 in health, but sinks in disease, and in anaemia gravis is only 7.2; here the excretion of iron is increased six-fold. I n chlorosis, the excretion is normal, but the iron-coefficient falls.W. D. H. Diuretic Effects of Sodium Chloride. By WILLIAM H. THOMPSON (J. Physiol., 1900, 25, 487-51 8).-The intravenous injection of small amounts of an isotonic solution of sodium chloride is followed usually by diuresis which is out of proportion to the volume of fluid injected, This is completed three or four hours after the injection.. The excre- tion of urea and nitrogen is augmented, but the maximum occurs earlier than the maximum excretion of water. The diuresis is not caused by elevation of blood-pressure. A hydramic condition of the blood is produced, but this is not the sole factor in producing the increased flow of urine. A diminution in the urinary clrlorides is probably produced by the anssthetic. The kidney volume corresponds i n a general way to urinary outflow ; but there are eXCeptiObS to thisVEGETABLE PHYSIOLOGY AND AGIRICULTURE.31 rule. Bowman's theory explains urinary secretion better than Ludwig's. This is to be explained by the amount of lymph present. W. D. H. By NARZISS ACE (Chem. Centr., 1900, ii, 688; from Arch. exp. Path. Plzarm., 44, 31 9-348).-Dimethylxanthine acts on rabbits very markedly as a diuretic, and theophylline and paraxanthine are much more effective than theobromine. Of the monomethylxanthines, 4-methylxanthine acts as a diuretic, whilst heteroxanthine hardly acts in this way at all. Xanthine, isocaff eine, deoxycaff eine, and deoxytheobromine- are not diuretics. The presence of methyl groups in the 4 : 6 and 1 : 6 positions appears to, be of greater importance for diuretic action than in the 1 : 4 position.Action of Phloridzin on the Kidneys. By JULIUS YON K~SSA (Zeit. Biol., 1900, 40, 324-332).-1n spite of what some observers have stated to the contrary, phloridzin does produce a nephritic condition. It also produces fatty infiltration of the liver and muscles. The nearly related pentoside, hesperidin, produces nephritis and albuminuria but not glycosuria. Physiological Action of certain Isomeric Hydroxyquinolines. By BELA VON FENYVESSY (Zeit. physiol. Chem., 1900, 30, 552-564),- The two hydroxyquinolines, carbostyril and kynurin, were investigated in rabbits and frogs. Administered by the mouth, the former causes paralysis by a curare-like action on the nerve-endings. The urine con- tains sugar, and after the removal of this by fermentation, is strongly laevorotatory ; the substance to which this was due was crystallised out, and analysis of its potassium salt showed it to be carbostyril- glycuronic acid. A part (about 25 per cent.) of the drug leaves the body as an ethereal sulphate. Two experiments were made in which the drug was given subcutaneously. One rabbit died; the urine of the other did not contain the optically active material. Kynurin given by the mouth has no ill-effects on rabbits, but in- jected under the skin of frogs it produces much the same paralytic effects and heart-weakening as carbostyril, although less marked in degree. The urine of the rabbits in this case also contains a Iaevo- rotatory material, which yields kynurin on decomposition. Elementary analvsis of the crvstalline material obtained from the urine shows Diuretic Action of certain Purine Derivatives. W. D. H, W. D. H. that"it is not a co&pound of glycuronic acid as anticipated. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9018005027

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGIRICULTURE. 31 Chemistry of Vegetable Physiology and Agriculture, Gaseous Exchanges between Plants and the Atmosphere. By TH. SCHLOESINQ, jun. (Compt. rend., 1900, 131, 716-719. Com- pare Abstr., 1893, ii, 137, 180; 1894, ii, llO).-Comparative experi- ments, made on buckwheat and dwarf nasturtiums cultivated in media32 ABSTRACTS OF CHEMICAL PAPERS. freed from nitrifying organisms show that the plants, under these conditions, readily accommodate themselves to the substitution of ammonium salts for nitrates ; buckwheat thrives slightly better on nitrates, whilst ammonium salts seem more favourable to the growth of nasturtiums. During the entire period of development, the plants evolve a volume of oxygen which is greater than that of the carbon dioxide absorbed.This excess of oxygen is derived principally from the reduction of the mineral salts extracted from the soil, and is very appreciably diminished when the nitrates are replaced by ammonium salts. The quantitative results obtained in these experiments are exhibited in tabular form, Assimilation of Free Atmospheric Nitrogen by Mycelia in the above-ground portions of Plants. By LORENZ HILTNER (Bied. Centr., 1900, 29, 705-706 ; from Centr. Bakt. Par., 5, ii, 831-832).--In 1897, A. E. Vogl discovered a fungus in the so-called hyalinic layer of seeds of Lolium temulentum. The results of experi- ments made by the author in which Lolium italicum and 1;. ternulenturn were grown together in sand, with and without addition of potassium nitrate, indicate that in the case of L.temulentum, free nitrogen is assimilated. It was not possible t o separate completely the roots of the two varieties of Lolium. The resiilts for the above-ground growth (in the pots without nitrate) are as follows (grams) : G. T. M. Dry matter. N. Lolium temulentum ............... 5.173 0.0304 ,, italicum ................ 0.974 0.0067 The amount of combined nitrogen in the seed and in the water given to the plants did not exceed 8 milligrams, whilst the roots of the two varieties together contained 7.8 milligrams of nitrogen, In the nitrate pots, there was a gain of 0.068 gram of nitrogen. N. H. J. M. R61e of Oxygen in Germination. By PIERRE MAZB ( A m . Inst. Pasteur, 1900, 14, 350-368).-The failure of seeds to germinate under water is due to deficiency of oxygen.Whilst the seeds appear to be unchanged, they are in reality undergoing various changes ; the hydrolysing diastases, and particularly zymase, are as active as in seeds germinating normally. On the other hand, the oxidations necessary for the elaboration of reserve foods being impossible under these conditions, the embryos remain inert. Small seeds (cruciferous, for instance) may develop slowly a t the expense of their internal atmosphere. Starchy seeds rapidly lose their germinating power, whilst oily seeds are more resisting. There is, however, no reason to suppose that any seeds are capable of resisting prolonged immersion in water. The weakening of the vitality of submerged seeds is due to the production of toxic compounds, especially aldehyde.The development of the plant a t the expense of the reserve substances of the seed seems to depend on a certain number of diastasic actions,VEGETABLE PHYSIOLOGY AND AQRICULTURE. 33 the equilibrium of which cannot be disturbed without sooner or later causing death. Diffusion of Enzymes in the Seeds, with Special Reference to the Fat-decomposing Enzymes. By C. LUMIA (Bied. Centr., 1900, 29, 669-673 ; from Xtax. sper. agnw. ital., 1898, 31, 353).- When the endosperm of growing plants was extracted successively with water and ether, the ethereal residue was found to be acid. Seeds similarly treated gave neutral residues. Eat is therefore decomposed in the endosperm during germination. The results of experiments with Ricinuo communis show that an aqueous extract of the germinating seeds libefated a considerable amount of acid from ricinus oil, which was added.When the extract was first boiled, the production of acid was comparatively small. Thymol was added in each case. N. H. J. M. By ALEX- ANDER TSCHIRCH and H. KRITZLER (Chem. Centr., 1900, ii, 585-586 ; from Ber. deut. phann. Ges., 10, 214--222).-The aleurone-grains of the seeds of a variety of plants were found to consist mainly of glob- ulins, similar to the globulins of animal proteids. The crystalloids contain at least two globulins of different solubility in 1 to 10 per cent, solutions of salts ; they are insoluble in concentrated solutions of ammonium sulphate, sodium chloride (with a trace of acetic acid), and potassium dihydrogen phosphate, and either insoluble or sparingly soluble in concentrated magnesium sulphate solution.Aleurone- grains contain also, possibly, small amounts of albumosee. The globoids contain protein (globulin), calcium, magnesium, and phosphoric acid ; they dissolve in concentrated solutions of ammonium sulphate, acidified sodium chloride, and potassium dihydrogen phos- phate, and are sometimes sparingly s o h ble and sometimes insoluble in concentrated magnesium sulphate solution. The germinating power of seeds probably depends directly on the solubility of the crystalloids in dilute sodium chloride solution. The proteids in old seeds which are insoluble in 10 per cent. sodium chlor- ide solution, but soluble in 1 per cent. sodium carbonate solution, correspond with Weyl’s albuminates, and are not identical with Osborne’s insoluble modification of globulin.The oil of the seeds is not present as drops, but is mixed with the cell plasma; the gluten grains are free from oil. Dependence of the Production of Transitory Starch on Temperature and on the Action of Oxydases. By J. G~riras (Bied. Centr., 1900, 29, 685-687; from Woch. Brauerei, 1899, 16, 519, and Centr. Bakt. Par., 1899, 5, 7’75).-Sucrose is the first carbo- hydrate utilised in the germination of barley, the starch not being used until the embryo reaches a certain stage and is able to furnish the enzymes necessary for rendering the starch available. The rootlet is encldsed in a gum which probably consists of galactans; this con- tains a liquefying enzyme. When a hole is bored through a potato the exposed surface soon becomes covered with cork.The latter contains two oxydases, an N. H. J. M. Microchemical Examination of Aleurone-grains. N. H. J. M. VOL LXXX. ii. 334 ABSTRACTS OF CHEMICAL PAPERS, a-oxydase and a P-oxydase. The a-oxydase is a carrier of free at- mospheric oxygen and is destroyed by prolonged con tact with alcohol, or by heating with alcohol for 15 minutes at 50 -53' ; it dissolves readily in glycerol, and is precipitated with only partial destruction by lead acetate. The P-oxydase liberates loosely combined oxygen. Neither the Q- nor the P-oxydase is hydrolytic. For detecting oxydases, paper soaked in an alcoholic solution of tetramethyl-p-phenylenediamine is employed ; the dried paper, when moistened and placed on vegetable tissues containing oxydases, causes them to become coloured violet when exposed to air.Barley contains a substance, sperntase, which resembles oxydases, except in its extremely slight action on guaiacol; it is destroyed by heating with alcohol at 55-57O. As germination proceeds, the action of the spermase a t first increases, then diminishes until it ceases. Probably the cessation is only apparent, the action being masked by reducing substances. Saps. 111. By ALEXANDER H~BERT (Bull. 8oc. China., 1900, [iii], 23, 839-842). Compare Abstr., 1896, ii, 494, and 1898, ii, 446).-A specimen of the sap or juice of the vanilla plant from the Congo was found to contain about 4 per cent. of crystallised calcium oxalate, to w,hich the known irritant action of the juice is possibly due.Proteids and reducing substances are also present, but neither alkaloids nor fats could be detected. By ERNST FRICKE (Chem. Centr., 1900, ii, 769 ; from Zeit. oflentl. Chem., 6, 292).-On a meadow near Rams- beck, Westphalia, which is occasionally flooded by waste liquors containing zinc, and on soil near Bockwiese and Lautenthal which is known to contain zinc, a cruciferous plant very similar to Arubis HaZZeri has been found to flourish. In both cases, the plant contained zinc, and in the latter case the plant substance free from water and sand yielded 1.3 per cent, of ash which contained 0.94 per cent. of zinc. E. w. w. Oil and Fat of Stillingia Sebifera. By MASSIMO TOHTELLI and R. RUGUERI (Annali del Lab. Centr. delle Gabelk, 1900, 4, 205-215 ; and L'Orosi, 1900, 23, 389-297).-The seeds of Stillingia sebiJera contain 20.0 per cent.of fat and 19.2 per cent. of a very mobile, pale yellow oil, having the sp. gr. 0.9438 a t 15'/15O and [a], -3.41" at 16'; the other chemical and physical constants have also been determined. T. H. P. Genesis of Terpenoid Compounds in Plants. By EUQSNE CHARABOT (Ann. Chim. Phys., 1900, [ vi], 207-288). -A detailed account of work already published (compare Abstr., 1900, i, 363; ii, 101, 241, 361, 362; this vol., i, 38). G. T. M. Simultaneous Presence of Sucrose and Gentianose in Fresh Gentian Root. By EMILE BOURQUELOT and HENRI HEBISSEY (Compt. rend., 1000, 131, '750-752. Compare Abstr., 1898, i, 349 ; Abstr., 1900, i, 511).-Fresh gentian root is shown to contain both sucrose and gentianose, the Former being, perhaps, produced by the decompo- N. H.J M. N. L. Plants Containing Zinc.VEGETABLE PHYSIOLOGY AND AGRICULTURE, 35 sition of the latter sugar. Full details are given in the paper of the Presence of Invertin or Sucrase in Grapes. By V. MARTINAND (Compt. rend., 1900, 131, 808-810).-Invertin was found to be pre- sent in crushed grapes which, before maceration, had been carefully sterilised to destroy any enzyme which might be present on the outer surface of the skin. The amount of invertin present is sufficient to invert the whole of the sucrose present in the grapes. The invertin which is found in wine comes from the grape itself, and not from the enzyme which has produced fermentation in the wine. The invertin present in grapes is not so readily oxidisable as that obtained from other sources.It is absent from diseased wines, and from wines which have undergone strong oxidation. Colouring Matter of Beetroot and its Absorption Bpectrum. By JULIUS FORMLNEK (J. pr. Chem., 1900, [ii], 62, 310-314).-Beet- root contains an unstable colouring matter, which shows a yellow absorption band and, when warmed or kept, soon changes into the substance which exhibits the well-known blue and violet absorption bands. R. H. P. By WILHELM JOHANNSEN (Bied. Centr., 1900, 29, 717 ; from Tidsskr. Landbr. Pkunt., 1899, 5, loo).-Nitrogen was determined in ten large and in ten small seeds. The following are the average results. Large seeds (450 mg.), N= 3.35 ; small seeds (226 mg.),N = 3.1'7. The average for all the seeds (338mg.) was N = 3-26 per cent.There were only relatively few cases in which the small seeds had a lower, and the large seeds a higher percentage of nitrogen than the average of all the seeds. By THEODOR REMY (Bied. Centr,, 1900, ZS, 664-665 ; from El. Gersten-, Hopfen- u. Kartofelbuu, 1899).-Experiments with hops in which farmyard manure was applied t o soil not particularly deficient in humus-nitrogen decidedly increased the yield without having any marked effect on the quality of the hops. I n the case of peat land (a typical East Prussian hop soil) containing 1-97 per cent. of nitrogen, the results showed that dung should only be employed in moderation, being injurious, rather than beneficial, as a source of nitrogen. By FLAMINIO BRACCI (Bied.C'entr., 1900, 29, 673-675 ; from Stax. sper. agrar. ital., 1899, 32, 161)-The dif- ferent parts of the olive have the following percentage composition : separation and identification of the sucrose. N. L. H. R. LE S. Nitrogen in Peas. N. H. J. M. Manurial Experiments with Hops. N. H. J, M. Cultivation of Olives. Organic Per cent. in Ash. Water. matter. N. Ash. K,O. Na,O. CaO. P,O,. Branches ... 32 5 65.6 1.9 0.75 20.56 11 38 30.94 15'39 Leaves ..,... 53.6 43.4 3.0 1.01 18.68 8.51 35.64 7.68 Fruit ..,...... 52.7 45'5 1'8 0'45 66-30 4-82 5.71 6.65 It is estimated that the following amounts of manurial constituents are lost per hectare per annum (in wood, leaves, and fruit) : N, 27.9 ; K,O, 37.2 ; CaO, 13.9 ; and P,O,, 8.8 kilos. N. H. J. M. 3-236 ABSTRACTS OF CHEMICAL PAPERS.80-called Invisible Injury [to Trees] by Smoke. By PAUL SORAUER and EMIL RAMANN (Bied. Certtr., 1900, 29, 678-685 ; from Bot. Centr., 1899, 90, 50-56, 106-116, 156-168, 205-216, and 251-262).-Pine trees, 8-9 years old, in pots were subjected for an hour, in one case every day, and in others every second, third, or fourth day respectively, to the action of sulphur dioxide (0.0022 volume per cent. of the air) obtained by burning a mixture of carbon disulphide and alcohol. According to the frequency of the treatment, the amount of sulphuric acid in the needles was increased by 0.189, 0.112, 0,079, and 0.072 per cent. There was no visible change in the appearance of the needles either in the first or the second year ; microscopical examination showed, however, that i u many of the needles the chlorophyll substance had undergone changes or was completely destroyed.Similar experiments were made in which the trees were subjected to the action of hydrogen chloride (0.00386 volume per ceiit.), ob- tained by burning a mixture of amyl chloride and alcohol. The amount of chlorine in the needles was appreciably increased, but the increase had no relation, as in the case of sulphur dioxide, to the frequency of the treatment. Less acid was, however, on the whole, absorbed by those plants which were rendered damp by spraying than by the others. Microscopic examination revealed no alteration in the chlorophyll substance. The stronger trees absorbed less acid than the weaker ones. The results show that hydrogen chloride is less dangerous to pines than sulphur dioxide.N. H. J. M. Butter Fat. By ALPH. VAN ENCIELER and P. WAUTERS (Bied. Centr., 1900, 29, 666-667; from Contrib. 2tude de la graisse du beurre, Brussels, 1899, pp. 14).-Butter Gbtained a t different periods was examined, as well as the butter from single cows. The rations of the cows included cotton seed meal or sesame cake. The conclusion is drawn that abnormal butter fat may be pro- duced at all times of the year, and that its formation does not depend on the feeding or on the period of lactation, but on physi- ological conditions not yet understood. I n the authors' experi- ments, the Reichert-Meissl number varied from 23.3 to 38.5. N. H. J: M. Peat. By ARTHUR PETERMANN (Bied. Centr., 1900, 29, 714-716 ; from Bul.stat. ngron. Gembloux, 1899, No. 66, 11).-Peat from Herzo- genwald was air dried, well mixed, and heated in an iron retort at about 450'. The following amounts of products were obtained from 1000 kilos. of air-dried peat: Coke, 3375 grams ; methyl alcohol, 600 c.c.; acetic acid, 3.058 grams; and tar, 57.6'75 grams. The tar yielded oil boiling at 0-loo", 100-200°, and 200-300'; 2.5, 12-75', and 17.00 grams respectively ; paraffin, 14.425 ; and coke, 11 grams. The yield of ammonia was 921 grams, and there was sufficient illuminating gas (from 2 kilos.) to burn with a good flame for 6 hours. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 37 Estimation and Composition of Humus and its Nitriflca- tion. BY CRARLES RIMBACH (J Arner. c'hem. SOC., 1900, 22, 695-703).-Humus, extracted in the usual manner, was precipi- tated with a mixture of calcium and magnesium sulphates.The humate (28 grams) was mixed with ignited sand (2 kilos.), which was then inoculated with soil extract and kept at about 25' for two months, water being added when necessary. It was then found that 5.94 per cent. of the humus nitrogen had become nitrified. When soils are extracted with dilute hydrochloric acid, a certain variable amount of humus is dissolved. The amount of nitrogen in the sodium hydroxide extract differs from that in the ammonia extract, and cannot be directly referred to the amount of organic matter in the latter. I n the usual process for determining humus, a certain amount of ammonia (about 5 per cent.) is included in the organic matter, making the results too high.Sodium hydroxide solutions extract more nitrogen than ammonia, and the question still remains, which of the two solvents is preferable. Composition of the Coprogenic Mud of Ranger Lake in Livonia. By MAXIMILIAN GLASENAPP (Bied. Centr., 1900, 29, 665-666; from Baltische Woch., 1899, 40)-The mud is a light grey substance of the following composition (air dried) : Water, 7-60; nitrogenous organic matter, 11 -75 ; non-nitrogenous organic matter, 26.34 ; potassium, sodium, and calcium sulphates, 0.61, 0.66, and 2.67 ; calcium phosphate and carbonate, 0.37 and 15.86 ; magnesium carbonate, 5.33; ferric oxide and alumina, 2.88 ; silica and sili- cates, 25.93 per cent. The mud can be obtained in large amounts in dry summers, and is locally useful astt manure.Denitriflcation and the Action of Farm-yard Manure. By THEODOR PFEIFFER and OTTO LEMMERMANN (Landw. Vewuchs-$tcct., 1900, 54, 386--462).-The utilisation of the nitrogen in the soil is hindered by an increase in the amount of organic matter as well as by denitrifying bacteria. Manuring with farmyard manure, dung, &c., not only increases the amount of organic matter but, acts as a carrier of bacteria. I n pot experiments, the injurious effect of organic matter and denitri- fying bacteria was only observed in the case of the first crop, but not after wards. When the amount of organic matter in the soil was increased by adding potassium citrate, or when pure cultures of denitrifying bacteria were added, there was a loss of nitrogen in the free state.I n the case of farm-yard manure, the production of elementary nitro- gen is quite unimportant as compared with other factors which give rise to incomplete utilisation of the nitrogen; this holds good even in pot experiments. On light sandy soil the utilisation of nitrates is not affected by an application of 800 cwt. of old bullock or horse manure or fresh horse dung. I n pot experiments, the same manure gave quite different results, but these have no direct. bearing on practical agriculture. The varying results obtained with di$erent kinds of stable-manure N. H. J. M. N. H. J. M.38 ABSTRACTS OF CHEMICAL PAPERS. cannot be attributed either to the differences in the amounts of the different forms of nitrogen, and cannot be explained by denitrification and liberation of free nitrogen. The amounts of non-nitrogenous organic substances, especially xylan, had in these experiments no relation to the nitrogen assimilated. The differences observed would seem to be due to the various degrees of stability of the nitrogen compounds. When farm-yard manure is improperly kept, the production of available forms of .nitrogen may be entirely suppressed, even under conditions most favourable to the decomposition of the non-nitrogenous constituents. This is attributed mainly to the proteolytic ferments being injured, but requires further investigation. The above conclusions are drawn from the results of a number of pot and plot experiments, which are fully described. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9018005031

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

38 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Estimation of Ozone. By OTTO BRUNCK (Ber., 1900, 33, 2999--3000).-A reply to Ladenburg (Abstr,, 1900, ii, 721). T. M. L. [Estimation of Persulphates and Chromium.] By RODOLFO NAMIAS (L’Orosi, 1900, 23, 218--223).-See this vol., ii, 15. Estimation of Nitric Acid in Water. By N. N. KOSTJAMIN (Chem. Centr., 1900, ii, 878-8‘79; from Pharm. Zeit., 45, 646)- Five C.C. of the sample are slowly mixed with a freshly prepared solu- tion of 1 part of brucine in 3000 parts of sulphuric acid of sp. gr. 1.84 until a permanent rose coloration is formed. The greater the amount of nitrate the less of the reagent will be required. If nitrites should be present, these must be expelled by boiling with dilute sul- phuric acid, A table is given showing the number of C.C.of the reagent required for samples containing from one to twenty milligrams of nitric Volumetric Estimation of Phosphorous Acid. By OTTO KURLINU (Bey., 1900, 33, 2914--2918).-Phosphorous acid may be estimated volumetrically by the aid of potassium permanganate solution but the reaction takes some time for completion. Zinc sulphate is added to the solution of the acid and the liquid is then heated on the water-bath and treated with permanganate solution. The zinc sulphate reacts with the alkali produced from the permanganate, yielding zinc hydroxide which carries down the manganese dioxide rapidly and com- pletely. The titration is eithm carried out until the liquid remains permanently coloured for 10-15 minutes, or an excess of perrnangan, pentoxide per litre.L. DE I(.ANALYTICAL CHEMISTRY. 39 ate is added, the liquid heated for 1--1*5 hours, and filtered, the precipitated manganese dioxide being then treated with potassium iodide and sulphuric acid and the liberated iodine estimated with thio sulphate. The excess of permanganate may also be estimated in the filtrate. A. H. Destruction of Organic Substances by means of Chromyl Chloride in Toxicological Analysis. By C. PAGEL (Chem. Centr., 1900, ii, 784; from Pharm. Post, 33, 489--490).-The apparatus con- sists of a tubulated retort fitted with a separating funnel and connected with a balloon which is in turn connected with two wash-bottles, of which the first is half filled with water and the second with a 1 per cent. solution of potassium hydroxide The balloon is cooled by a thin stream of water.The finely divided, dried substance is put into the retort, 30-40 grams of a mixture of two parts of sodiumchloride and one part of potassium dichromate are added for every hundred grams of material, and sulphuric acid is gradually introduced through the funnel. On heating, yellow fumes of chromyl chloride are evolved which carry over all the arsenic and most of the antimony and mer- cury. Altogether 40-50 C.C. of sulphuric acid are used and the heating is continued until the charred mass has become quite clear again. The residue in the retort may contain non-volatile metallic chlorides. The process seems a particularly delicate one for arsenic, and the author has found this to be a normal constituent of some parts of the animal body (spleen, brain, testicles, ovaries, &c.).By HEINRICH GOCKEL (Zeit. angew. Chem., 1900, 1034).-Koch (Abstr., 1895, ii, 86) has described an apparatus which, with slight modification by Ledebur, has become the recognised apparatus of the Society of German Iron Smelters. The author has made another slight modi- fication to render it still more convenient. In its new form, the apparatus differs from the previous one by having a wider ground neck into which fits the condenser through which passes a thistle funnel tube reaching to the bottom of the flask ; the top of the neck of the flask is expanded, so that it can be filled with water to seal the apparatus after introducing the condenser. The side tube of the flask is placed somewhat higher than before. The acid mixture is poured through the funnel tube which is theu sealed by means of a glass rod.At the lower end of the condenser is fitted a small slightly bent hook supporting a little glass bucket con- taining the sample; by a slight jerk this is made to drop into the acid. Recognition of Barium Compounds as the Cause of Poisoning. By DIOSCORIDE VITALI (L'Orosi, 1900, 23, 260--263).-The detection of barium in the stomach contents or in the matter ejected by vomit- ing and the determination of the form in which it was administered may be carried out as follows. The material is first examined to see whether it gives a marked alkaline reaction, after which it is filtered and the residue extracted with boiling water so long as the latter becomes alkaline.If now the filtrate has an alkaline reaction and barium L. DE K. Flask for the Estimation of Carbon in Iron and Steel. L. DE K.40 ABSTRACTS OF CHEMICAL PAPERS. carbonate is precipitated on passing carbon dioxide through it, the poisoning was brought about by barium oxide or hydroxide. If the addition of dilute sulphuric acid to the filtrate from the barium carbonate causes evolution of hydrogen sulphide and precipitation of barium sulphate, barium sulphide must have been taken. To detect barium chloride, nitrate, or acetate, the filtrate from the carbonate is evaporated to small volume and finely divided, pure lithium carbonate added until the liquid gives a persistent alkaline reaction, when it is boiled and filtered and the precipitate washed; the filtrate is eva- porated to dryness on the water-bath, the residue extracted with a mixture of equal volumes of strong alcohol and ether, and the alcohol- ethereal solution evaporated to dryness.The presence in the solid residue thus obtained, of lithium chloride, nitrate, or acetate shows that the corresponding barium salt was the cause of poisoning. In the event of barium carbonate having been employed, tliis will have been converted to a small extent into the chloride in the stomach, but as vomiting in general occurs soon after the administration of the barium salt, it will mostly remain as carbonate in the insoluble portion of the stomach contents, and may be detected by treating the latter with hydrochloric acid, which will cause evolution of carbon dioxide and the formation of soluble barium chloride.By THOMAS ROMAN and G. DELLUC (J. €'harm., 1900, [vi], 12, 265-267).-When alcohol is stored in galvanised iron vessels, a small quantity of the zinc is dissolved. A chloroform solution of urobilin serves as a very delicate test for zinc, with which it gives a green fluorescence, even when the merest trace of the metal is present. I n making the test, it is necessary to mix the chloroform solution with 24 times its volume of absolute alcohol, in order to prevent the formation of an emulsion. T. H. P. Presence of Zinc in Alcohol. H. R. LE S. Volumetric Estimation of Copper as Oxalate, with Separation from Cadmium, Arsenic, Tin, and Zinc. BY CHARLES A. PETERS (Arner. J. Sci., 1900, [iv], 10, 359--367).-The process is based on the fact that under certain definite conditions copper may be completely precipitated as normal oxalate.After being thoroughly washed on an asbestos filter, the precipitate may be treated with 5-10 C.C. of dilute sulphuric acid (1 : I), diluted with a suitable quantity of water, heated to boiling and titrated with permanganate, or it may be dissolved in 10 C.C. of hydrochloric acid mixed with 0.5 gram of manganous sulphate and titrated with permanganate at I n order to ensure the complete precipitation of the copper, there should be present at least 0.0128 gram of its oxide in 50 C.C. of liquid, containing as nearly as possible 5 C.C. of strong nitric acid; two grams of oxalic acid will completely precipitate the copper after 12-16 hours.Ammonium nitrate interferes with the complete precipitation. The process is not suited for the separation of copper from bismuth and antimony ; cadmium, arsenic, iron, and small amounts of tin do not interfere. I n the presence of zinc, the precipitate is sligbtly con- 30-5 0'.ANALYTICAL CHEMISTRY. 41 taminated with zinc oxalate. Numerous test analyses are given in By FRIEDRICH BULLNHEIMER (Chem. Centr., 1900, ii, 991-992 ; from Chem. Zeit., 24,870-871).- The following process is recommended for poor ores. 1-2 grams of the finely powdered sample are fus6d in a nickel crucible with 4 grams of sodium peroxide and 3 grams oE sodium hydroxide, first over a very small and then over a full flame until the bottom of the crucible begins to glow. When the mass has solidified, the crucible is placed while hot in a beaker containing some water and the solution is then transferred to a 250 C.C.flask. If the liquid is coloured green by manganese, it is decolorised by means of hydrogen peroxide. When cold, the liquid is diluted to the mark, and half of the filtrate is mixed with 20 grams of ammonium nitrate. After any silica or stannic acid has deposited, magnesium nitrate is added to precipitate any phosphoric or arsenic acid. Afher 6 hours, the liquid is filtered, the precipitate washed with ammoniacal water and the filtrate made faintly acid with nitric acid. 20-30 C.C. of mercury solution (200 grams of mercurous nitrate heated with 20 C.C. of strong nitric acid and alittle water and then diluted to 1 litre) are added, and after a few hours the liquid is nearly neutralised with ammonia.The precipitate is washed with water containing a little mercurous nitrate and then ignited and weighed. In the presence of much molybdenum, the precipitate ahould be mixed with ammonium chloride and then be reignited. the paper. L. DE K. Estimation of Tungsten in Ores. L. DE K. AnaJysis of Tin and Tin-plated Wares. By V. MAINSBRECQ, (Chem. Centr., 1900, ii, 743-744; from Rev. intern. falsijc, 13, 113--115).-Ten grams of the finely cut up sample are treated in an Erlenmeyer flask with strong hydrochloric acid and left overnight. Any undissolved matter, which may contain arsenic, antimony, and the bulk of the copper, is filtered off and treated with nitric acid, which converts the antimony into trioxide and dissolves the arsenic, which may be precipitated as ammonium magnesium arsenate. The hydro- chloric acid solution is oxidised with nitric acid, neutralised with ammonia, again slightly acidified with hydrochloric acid, and pre- cipitated with a strong solution of ammonium nitrate; the filtrate from the stannic hydroxide contains the lead and the remainder of the copper, which are precipitated as sulphides and then separated by the thiocyanate method.The filtrate contains zinc and iron, which are separated by means of ammonia, the zinc being finally weighed as sulphide. Tin and copper are, however, best determined in a separate portion. One gram is dissolved in nitro-hydrochloric acid, the tin precipitated by means of ammonium nitrate as directed, and the copper estimated in the filtrate either by potassium thiocyanate or colori- metrically. Tin-plate is simply dissolved in hydrochloric acid ; copper Sources of Lo8a in the Estimation of Gold and Silver in Copper Bars, and a Method for its Avoidance. By RANDOLPH VAN LIEW (Chm.Ccntr., 1900, ii, 992; from Eng. and Min. J., 69, 469, 498).--In order t o minimise the loss of gold and silver in is not likely to be present, L. DE K.42 ABSTRACTS OF CHEMICAL PAPERS, the assay of copper bars, the following method is proposed. One or two assay tons of the turnings is dissolved in the cold in 350 C.C. of water and 100 C.C. of nitric acid of sp. gr. 1.42. After 18-20 hours, a further addition of a t most 30 C.C. of acid must be made, and within 24-26 hours the solution will be completed. Any nitrous fumes are expelled by means o f a current of compressed air in about 20-30 minutes; sodium chloride is then added.The silver chloride, mixed with the insoluble matter containing the gold, is collected on a filter, care being taken to wash i t all down to the bottom. The cone of silver chloride is covered with 4-5 grams of assay-lead and with the filter heated at a temperature low enough to cause reduction of the silver chloride without any volatilisation of the chloride ; cupellation &c., is then carried on as usual. L. DE K. Assay of Cupriferous Materials for Gold and Silver, By L. D. GODSHALL (Chem. Centr., 1900, ii, 992-993; from Trams. Amer. Inst. Mirn. Engin., Feb., 1900 ; Berg.-Huttenm. Zeit., 59, -454).-When applying the usual dry assay, care should be taken to examine the slags and the used cupel for traces of gold and silver.When the material is very rich in copper, it will be necessary to test for and estimate it in the weighed silver buttons. The sample is dissolved in nitric acid and after being diluted with water, lead acetate and a corresponding quantity of sulphuric acid are added ; the precipitated lead sulphate carries down any metallic gold, and after being dried, the precipitate is cupelled as usual. The filtrate is precipitated with a chloride or a bromide, and lead sulphate or bromide precipitated in the solution as before, and the resulting argentiferous deposit also cupelled in the usual manner. The material may also be dissolved in nitric acid, evaporated with addition of sulphuric acid, and the resulting solution treated for a very short time with hydrogen sulphide. The precipitated copper sulphide carries down any gold and this is then recovered like the The wet assay is best conducted as follows.silver. L. DE K. Waters Contaminated by Cystine. By MARCEL MOLINI~ (Compt. rend., 1900, 131, 720--721).-The development of a yellow coloration by the action of the mercurichloride of sodium p-diazobenzene- sulphonate which is not destroyed by sulphurous acid cannot be taken as an indication of the presence of cystine in natural waters, because the same result is obtained with slightly acidified distilled water ; on the other hand, the coloration is never produced in neutral solutions (com- pare Causse, Abstr., 1900, ii, 457, 458).G. T. M. Estimation of Iodoform in Dressing Materials, By G. FRERICHS (Chem. Centr., 1900, ii, 785; from Apoth. Zeit., 15, 544. Compare Lehmann, Abstr., 1900, ii, 372, 767).-0ne or two grams of the material are put into a 250 C.C. Erlenmeyer flask and 10-20 C.C. of alcohol or “spiritus aethereus” are added. Excess of N/10 silver nitrate and 10 C.C. of dilute nitric acid are then added, and after 15 minutes the egcess of silver is titrated with N/10 potassium thiocyanate. SeveralANALYTICAL CHEMISTRY. 43 determinations should be made to see whether the iodoforrn is eq.ually Estimation of Prussian Blue in Spent Gas Purifying Material. By A. 0. NAUSS (Chm. Centr., 1900, ii, 785-786; from J. Gasbel., 43, 696--697).-Ten grams of the sample are repeatedly shaken in a half-litre flask with 50 C.C.of 10 per cent. sodium hydr- oxide. Aftor 15 hours, the mixture is diluted to 605 C.C. and filtered. Fifty C.C. of the filtrate are added to 10 or 15 C.C. of a hot solution of iron alum (200 grams to 1 litre of water and 100 grams of sulphuric acid) and the whole is heated until the peculiar sweet odour has dis- appeared; the precipitate is filtered off and washed in a hot water funnel and then heated for a short time together with the filter with a definite volume of N/50 sodium hydroxide. The excess of alkali is then titrated with N/50 acid until a permanent pale greenish-yellow coloration is observed. To estimate cyanogen in gases, 100 litres of the gas are passed through an absorption Bask containing 20 C.C. of ferrous sulphate (1 : 10) and 20 C.C.of potassium hydroxide (1 :3) and then through a second flask containing 10 C.C. of the mixture. The contents of the flasks are emptied into a half-litre flask, a little more potassium hydroxide and ferrous sulphate, and 1 gram of lead carbonate, to remove hydrogen sulphide, are added, and the whole is boiled for a few minutes. When cold, it is made up to 505 C.C. and 50 C.C. are titrated as directed. One c.e. of N/50 alkali =0*0007794 gram of cyanogen. Detection of Methyl Alcohol in Mixtures. By S. P. MULLIKEN and HEYWARD SCUDDER (Amer. Chem. J., 1900, 24, 444-452. Compare Abstr., 1899, ii, 3S8).-Jandrier (Abstr., 1900, ii, 52) has recommended the use of gallic acid instead of resorcinol for the detec- tion of methyl alcohol, since he found that the colour reaction of the former reagent with formaldehyde is much more delicate than that of the latter, and is less likely to be obscured by coloration occasioned by the simultaneous presence of other aldehydes.The authors find that this modification of their test for methyl alcohol is inadmissible, since many other organic substances yield traces of formaldehyde on oxidation, which would not be detected by resorcinol but give the colour reaction with gallic acid owing t o its greater delicacy. A number of precautions are mentioned which should be adopted before applying the resorcinol test, in order to remove substances from the solution which could prevent or obscure the appearance of the characteristic rose-red ring, and a method of applying the test in the presence of much ethyl alcohol is described in detail. E.G. By R. GRASSINI (L’Orosi, 1900, 23, 224-225 and 297-298).-1f a dilute solution of cobalt chloride, the concentration of which is not less than 0.5 per cent. and is best about 5 per cent., is mixed with potassium thiocyanate solution and a layer of alcohol is poured on to the liquid, which is then gently shaken so that the two strata do not mix, the alcohol assumes a beautiful agure-blue colour which i s most intense at the surface of separation. distributed over the whole of the material. L. DE E(. L. DE K. Colour Reaction of Alcohol.44 ABSTRACTS OF CHEMICAL PAPERS. This eeaction is not disturbed by the presence of nickel salts except when the ratio of cobalt to nickel is extremely small; the coloration, is, however, destroyed by hydrogen peroxide.If ether is used in place of alcohol, no coloration is obtained, so that the reaction may be used as a means of detecting the presence of alcohol in ether, which, if it contains 5 per cent. of added alcohol gives a marked coloration. T. H. P. Estimation of m-Cresol in Cresol Mixtures. By HUGO DITZ (Zeit. angew. Chem., 1900, 1050--1052).-Raschig’s process (Abstr., 1900, ii, 694) is not applicable when the mixture contains more than 10 per cent. of phenol. The sample should be suitably diluted with a mixture containing no phenol but a known quantity of m-cresol. In Rascbig’s process, the o-cresol and p-cresol are oxidised to oxalic acid ; should this reaction be quantitative, it might prove of great value.If, however, phenol is entirely absent, t,he author thinks that the assay may be more conveniently effected by the bromine process proposed by himself and Cedivoda (Abstr., 1900, ii, 54). L. DE I(. Detection of Starch-Sugar in Wine. By ED. DELLE (Chern. Centr., 1900, ii, 744; from Rev. imttwm. faZs$c., 13, 131-132).- Tony-Garcin’s process is recommended. One hundred C.C. of the sample are shaken with 30 grams of animal charcoal and, after 2 hours, fihered. Normally fermented wine then shows a rotation of about + 13’. If the decolorised wine contains less than 2 grams of reducing sugar per Iitre and has a rotation of more than + 13’ before and after in- version, the presence of starch-sugar is proved. I f more sugar is Estimation of the true percentage of Starch in Potatoes.By GEORG BAUMERT and H. BODE [with A. FEST] (Zeit. angeur. Chern., 1900, 1074-1078, 11 11-11 13).-After reviewing earlier processes, the authors have finally adopted the following method : 3 grams of the finely ground, air-dried potato are stirred at intervals in a porce- lain beaker with 50 C.C. of cold water for an hour, the liquid is poured off as completely as possible through a small asbestos filter, and the latter returned to the beaker. Fifty C.C. of water are added, the beaker is closed with a lid and heated for three hours and a half in a Soxhlet digester a t a pressure of 3 atmospheres. After cooling, the contents of the beaker are rinsed with 150-200 C.C. of boiling water into a 250 C.C. flask and boiled for 10 minutes ; when cold, the liquid is made up to the mark and filtered.100-200 C.C. of the filtrate are mixed with 10-20 C.C. of aqueous sodium hydroxide (100 grams per litre) and from the clear and stable solution, 25 C.C. are taken and mixed with 100 C.C. of commercial absolute alcohol, about 1 gram of fine asbestos being added in order to facilitate the separation of the starch. The precipitate is now collected on a Soxhlet asbestos filter- tube and washed by means of the suction-pump with 80 per cent. alcohol. The starch is then dissolved by means of about 3-5 C.C. of 5 per cent. hydrochloric acid, reprecipltated with 25-30 C.C. of com- mercial absolute alcohol and again collected on the filter ; it is then present, the test becomes uncertain. L. DE I(.ANALYTICAL CHEMISTRY.45 washed first with 80 per cent. alcohol, then with absolute alcohol, and finally with ether. After drying to constant weight a t 120-130’ in a current of air, the tube is weighed; it is then ignited in a current of air or oxygen and reweighed, when the loss represents the amount of starch. On account of the dilution caused by the alkali, it should be multiplied by 1.1. I n order t o obtain the percentage of starch in the raw potatoes, the following formula is applied, 8 = lOO(v x 1*1)/Om3 x Zp, in whichf repre- sents the weight of the raw potatoes, I the weight of the air-dried mass, and w the loss on ignition, Further experiments have con- clusively shown that the loss on ignition really represents pure starch. L. DE K. New Process for the Estimation of Glycogen.By GEORU LEBBIN (Chern. Centr., 1900, ii, 880-881 ; from Zeit. ofemtl. Chem., 6, 325--327).-Twenty grams of horse flesh or liver are treated in a porcelain dish with 90 C.C. of water and 10 C.C. of 15 per cent. potassium hydroxide and heated over wire gauze until completely dissolved, when the whole is evaporated down to 30-35 C.C. After diluting to exactly 50 or 100 C.C. and filtering through glass wool, 25 C.C. are mixed with 50 C.C. of a mixture of 90 parts of alcohol and 10 parts of 40 per cent. potassium hydroxide. The precipitated crude glycogen is left over- night, collected on a filter and washed with alkaline alcohol. The filter is perforated and the contents are washed into a 100 C.C. flask with 80 C.C. of boiling water. The flask is well shaken, and when cold the contents are neutralised with 10 per cent, hydrochloric acid using tincture of litmus as indicator. After adding 3-4 more drops of the acid, 5-10 C.C.of Briicke’s reagent are added, the liquid diluted to the mark and filtered. Fifty c.c.of the filtrate are mixed with 75 C.C. of 95 per cent. alcohol, the precipitate is collected the next morning on a tared filter, and washed first with alcohol and then with ether, After being dried and weighed, the filter is burnt and any ash allowed for. L. DE K. Estimation of Acetic Acid. By V. DELFINO and M. MIRANDA (Chem. Centr., 1900, ii, 1038; from Mon. Xci., [iv] 14, ii, 696).- The solution of the acetic acid (? acetate) is boiled with an excess of ferric chloride, The resulting ferric acetate is decomposed into acetic acid and ferric hydroxide which then becomes anhydrous and ad- heres firmly to the sides of the beaker; it is dissolved in warin sul- phuric acid, and reduced by means of a strip of silver foil.After removing the silver from the solution by means of hydrochloric acid, the iron is titrated as usual. L. DE K. Acidimetric Estimation of Protocatechuic Acid. By HENRI IMBERT (Bull. Xoc. Chim., 1900, [iii], 23, 832--834).-According to Massol (Abstr., 1900, i, 600), protocatechuic acid crystallises in yellow needles melting at 199’ and is neutralised by 1.5 mols. of alkali when phenolphthalein is used as the indicator. The author now describes experiments to confirm his former statement (Abstr., 1900, i, 226), that protocatechuic acid is monobasic towards phenolphthalein, although46 ABSTRACTS OF CEEMICAL PAPERS.the end point is somewhat obscure. colourless, as it is usually stated to be, and melted at 194-195’. Moreover the acid employed was N. L. New Method for the Detection of ‘‘ Saccharin ” and Salicylic Acid alone or in presence of each other, By E. RIEGLER (Chem. Centr., 1900, ii, 880 ; from Pharm. Centr.-Halle, 41,563-564). -0-01-0°02 gram of “saccharin” is dissolved in 10 C.C. of water and 2 drops of 10 per cent. sodium hydroxide and put into a separ- ating funnel. Solution of p-diazonitroaniline is added drop by drop with constant shaking until the greenish-yellow colour of the liquid has disappeared. After shaking with 10 C.C. of ether, the aqueous layer is removed, and 20-30 drops of 10 per cent. sodium hydroxide are added.At the place of contact between the ether and the soda, a fine green ring is formed; on shaking, the ether turns green and the alkali yellowish-brown. On removing the aqueous layer and adding 5 C.C. of strong ammonia, this turns a beautiful green, whilst the ether is decolorised. Under the same circumstances, salicylic acid first shows an intensely red ring, then a red aqueous but colourless ethereal layer which remains colourless when treated with ammonia, the latter turning red. If 0*02-0.03 gram of a mixture of I‘ saccharin ” and salicylic acid is treated in the same manner, there is obtained first a red, somewhat brownish, ring, then a green ethereal, and a red aqueous solution; on addition OF ammonia, a colourless ethereal and a violet ammoniacal layer.The colour of the latter varies i n shade according to the re- spective amounts of the two substances. The reagent is prepared by dissolving 2.5 grams of p-nitroaniline in 25 C.C. of water and 5 C.C. of sulphuric acid. Twenty-five C.C. of water and a solution of 1.5 grams of sodium nitrite are added, and the Estimation of 6cSaccharin” in Beverages. By ED. DELLE (Chem. Centr., 1900, ii, 744-745; from Rev. intern. falsijic, 13, 121--122).-1n the absence of salicylic acid, 50-100 C.C. of tbe liquid free from alcohol are acidified with phosphoric acid and shaken with ether, or better with a mixture of ether and light petroleum. The ethereal liquid is evaporated, and the residue carefully fused with potassium hydroxide. The fused mass is dissolved in water, the liquid acidified with acetic acid, and the salicylic acid formed extracted with benzene.The weight of the salicylic acid multiplied by 0.77 equals the (‘ saccharin.’’ It may also be estimated colorimetrically by means By PAUL VIETH and M. SIEGFELD (Chem. Centr., 1900, ii, 922; from Milch Zeit., 29, 593--597).-As the result of a long series of experiments, the authors state that the natural acidity of milk as found by titration with barium or sodium hydroxide with phenolphthalein as indicator is subject to serious variation. Determination of the Specific Heat of Fats. By VANDEVYVER- GRAU (Chem. Centr., 1900, ii, 923-924 ; from Ann. Chim. anal. up#, 5, 321--323).-Pure tristearin has, a t - 6*, a fairly constant specific whole is diluted to the mark. L.DE K. of ferric chloride. L. DE K. Acidity of Milk. L. DE K.AN ALP TICAL CHEMISTRY. 47 heat of 0.336. This increases at lo", ZOO, 304 and 40' to 0.397, 0.409, 0,449, and 0.501, and is at 50' 0.510. A t 50" to 55', the edges of small particles of tristearin begin to soften, and the specific heat quickly rises t o 1.3-1.4. Palmitin shows a similar curve, the specific heat varying from 0.330 at - 7" to 0.478 at + 60°, and more than 1 at 3-4' below the melting point, 66.5'. Other fats behave in the same manner. The author considers the determination of the specific heat of fats, if not impossible, at least extraordinarily difficult, as the heat Estimation of Fat in Finely Powdered Substances, parti- cularly in Cocoa and Cocoa Mixtures. By P. WELMANS (Chem.Centr., 1900, ii, 786-787; from Zed. ofentl. Chem., 6, 304-314).- Five grams of the material are put into a separating funnel and shaken with 100 C.C. of ether saturated with water for a few minutes ; 100 C.C. of water saturated with ether are then added, and the whole is again vigorously shaken until a complete emulsion has formed. When ths ether has sufficiently separated, 50 or 25 C.C. are pipetted off, the ether is distilled off, and the residual fat weighed. I n calculating, it must be remembered that the total volume of the ethereal layer is not 100 c.c., but 100 C.C. plus the volume of the f a t ; the sp. gr. of cocoa fat may here be taken as 1. Bonnema's tragacanth method (Abstr., 1899, ii, 822) is also service- able if due correction is made for the volume occupied by the fat.of fusion causes an elevation of temperature. L. DE K. L. DE I(. Absolute Iodine Absorption Number of Fats. By MASSJMO TORTELLI and R. RUUGERI (Annali del Lab. Chim. Centr. delle Gabelle, 1900,4, 191-204; L'Orosi, 23, 109--122).-The authors ascribe the varying values obtained for the absolute iodine absorption number of one and the same fat by Wallenstein and Finck's method (Chem. Zeit., 1894, 18, 1188-1191), to (1) the use of too small a quantity of mate- rial, and (2) a slight oxidation of the liquid fatty acids. These dis- turbing influences are avoided in the following process. Twenty grams of the oil or fat are saponified with alcoholic potassium hydroxide and afterwards converted into the lead soap, which is washed with 200 C.C. of hot (not boiling) water three times in succession, allowed to cool, dried between filter paper and heated in a reflux apparatus on a water- bath with 220c.c.of ether for 20 minutes. The flask is then cooled in a mixture of ice and water, and maintained at a temperature of 8-10' for 2 hours, after which the liquid is filtered through a pleated filter into a 200 C.C. flask, made up to volume with pure ether, and the stoppered flask left all night in flowing water. The clear ethereal solution, filtered if necessary, is next removed t o a separating funnel in which the soluble lead salt is decomposed by 150 C.C. of 20 per cent. hydrochloric acid; after vigorous shaking, the two layers are allowed to separate, and the lower aqueous liquor, together with the lead chloride, run off from the funnel. This is repeated with another 100 C.C.of the acid, after which the ethereal solution is washed twice with 150 C.C. of distilled water, filtered, and distilled u r t i l 40-60 C.C. remain. The residue is then placed in a 100 C.C. flask immersed to its neck in a water bnth which is heated to boiling while48 ABSTRACTS OF CHENICAL PAPERS. n current of carbon dioxide is passed through a narrow tube bent at a right angle and drawn out nearly to a point, and reaching almost to the bottom of the flask. After an hour’s heating the flask is removed from the bath, and 8-15 drops (according as the oil contains more or less cotton seed oil or other drying oil), neglecting the first few, aspirated into a tared flask, and tho iodine number determined in the usual way.A large number of fats and oils have been examined by this method, the values obtained being greater, and nearer to the theoretical values, than those given by any process previously proposed. T. H. P. Solidiflcation Point of Fatty Acids. By R. MORESCHIN~ (Anmli delLa6. Centr. delle Gabelle, 1900,4,293-302. Compare Abstr., 1900, ii, 465).-The true solidifying point of a mixture of fatty acids obtained from soap may be found as follows. A test-tube 22-25 mm. wide is fixed by means of a stopper in a cylindrical glass vessel containing air having an initial temperature about 1 5 O lower than the required solidi- fying point, About 20 grams of the mixed acids are fused and poured into the test-tube, the change of temperature being noted. As soon as the rate of cooling shows signs of slackening, the mass is subjected to vigorous stirring, this being kept up as long as the temperature con- tinues to fall.After a time the mercury begins to rise and reaches a maximum a t which it remains motionless for some two minutes ; this maximum represents the true solidification point. By THEODOR GEUTHER (Chem. Centr., 1900, ii, 879-880; from Zeit. ofentl. Chem., 6, 328--329).-The author prepares the reagent by pouring 25 C.C. of water on to 5 grams of powdered sodium phosphotungstate and then adding a t once 30 C.C. of pure nitric acid of sp. gr. 1.39. This reagent keeps for about a year. To apply the test, 5 grams of the filtered lard are put into a tared test-tube, 3 grams of pure chloroform are introduced, and then 20 drops of the reagent.After thoroughly shaking, the tube is put aside and the coloration observed within two minutes ; colora- tions forming after two minutes should be ignored. The presence of only 5 per cent. of vegetable oil betrays itself by a plain, dark-green coloration. A yellowish-green coloration may be due to stale or rancid By ALB. J. J. VANDEVELDE (Chem. Centr., 1900, ii, 783 ; from Bull. Assoc. Belg. des Chimistes).-A criticism of Breinl’s process (Abstr., 1899, ii, 824). Light petroleum should on no account be used in this test as it also gives the reaction, particularly if it has a high boiling point. It follows that the reaction is not due to nitrogenous matters as suggested by Breinl. T. H. P. Modiflcation of Welman’s Reaction. lard.L. DE I(. Breinl’s Reaction for Sesame Oil. L. DE K. Modification of Hiibl’s Method of Estimating the Acid and Saponification Numbers of Wax, By OTTO EICHRORN (Zeit. anal. Chem., 1900, 39, 640--645).-The difficulty of saponifying wax, especially Russian wax, may be obviated by dissolving it in amyl alcohol. For estimating the free acids, 6 grams of wax are coveredANALYTICAL CHEMISTRY. 49 with 60 C.C. of pure amyl alcohol in a conical flask, and heated on an asbestos plate to boiling. Phenolphthalein is then added, and the titration made with N/10 alcoholic potash, which is added until the red colour disappears slowly. The liquid should be kept warmienough to prevent separation of the wax, and the titration should be finished at about 60°, higher temperatures being avoided near the end to prevent risk of saponification, The acid values so obtained are lower than those hitherto accepted.For the saponification, 5 grams are dis- solved in 60 c . ~ . of amyl alcohol, mixed with 25 C.C. of N alcoholic potash, the mixture gently boiled for half an hour, and titrated back with N/2 hydrochloric acid, after adding phenolphthalein. As soon as the solution has become colourless, the flask is heated until the liquid separates into two layers, and tbe addition of acid is continued until the lower, aqueous layer remains yellow even on long heating. A little water (10-25 c.c.) may be added to render the change more distinct. A blank experiment, conducted in the same manner, is indispensable. The presence of ceresin or paraffin does not interfere in any way.Analysis of Fruit Essences. By GUIDO FA~RIS (Anwli del Lab. Chirn. Centr. dells Gabelle, 1900, 4, 41--141).-A large number of experiments have beenmade on the methods of detecting the com- mon adulterants of oil of lemons. The results show that there is no absolutely certain way of determining the presence of extraneous sub- stances, although much can be learnt by the methods proposed by Schimmel & Co. and by Soldaini and Bert& which make use of frac- tional distillation and measurements of specific rotation. Other tests such as colour reactions and determination of physical constants, which are useful in some cases, are also considered. The addition of oils, resins, or balsams to oil of bergamot increases both its density and the residue left on evaporation, whilst oil of turpentine produces a diminution in the rotatory power and in the amount of esters.The admixture of lemon or orange oil with oil of bergamot increases its specific rotation and lowers its density, the amount of esters and the residue left on evaporation. Methods for examining sweet and bitter orange oils and oil of man- darins are also referred to. Valuation of Lemon Oil. By J. WALTHER (Chem. Centr., 1900, ii, 903; from Pharm. Centr.-H,, 41, 585-588. Compare Abstr., 1900, ii, 173, and Schimmel & Co.’s beschaytsber., April, 1900).- I n the author’s method of testing lemon oil, the sodium hydrogen carbonate should be added to the mixture of lemon oil and hydroxyl- amine hydrochloride in fine powder, so that it is gradually dissolved during the digestion and decomposes the hydrochloride; 80 parts of the carbonate are required for about 70 of hydroxylamine hydrochlor- ide. The end reaction with methyl-orange is described in the original By J.WALTHER (Chem. Centr., 1900, ii, 970 ; from Pharm. Centr.-H., 41, 613-616). -The quantity of carvone in ethereal oils is estimated by a method similar to that used for lemon oil (Abstr., 1900, ii, 173) 2-5 grams M. J. S. T. H. P. paper and numerous analyses are quoted. E. w. w. Estimation of Carvone in Ethereal Oils. VOL. LXXX. ii. e(50 ABSTRACTS OF CHEMICAL PAPERS. of the oil are mixed with 10 grams of a freshly-prepared solution of hydroxylamine hydrochloride (2 : 3), 25 C.C. of alcohol free from alde- hyde, and 2 grams of sodium hydrogen carbonate, and the mixture gently boiled for half an hour.To the cold solution, 6 C.C. of hydro- chloric acid of sp. gr. 1.12 are added, the volume made up to 500 c.c., and the unused hydroxylamine determined in 25-50 C.C. of the fil- tered liquid. The standard solution of alkali should be free from carbon dioxide. Three samples of caraway-seed oil of sp. gr. 0.913 a t 1S0, 0.907 a t 19O, and 0.893 at 15' were found to contain 52*5,48*5, and 10.0 per cent. of carvone respectively; a curled-mint oil of sp. gr. 0.932 at 18' contained 51 per cent. and another of sp. gr. 0.887 at 20°, 16 per cent. of carvone. Acid and Saponiflcation Numbers of some Copals. By WALTHER LIPPERT and H. REISSIGER (Zeit. angew. Chem., 1900, 1047--1050).-The following varieties of copal have been tested ; Angola copal, Angostura copal, Benguela copal, Brazil copal, Cameroon copal, Kauri gum, Dammara resin, and Madagascar, Zanzibar, Manilla, and Sierra Leone copals.The results have been duly tabulated. One gram of the finely powdered copal is treated for a few hours with 10 C.C. of chloro- form, 25 C.C. of alcohol are added, and the whole is gently warmed; if no solution takes place, a mixture of equal parts of ether and alcohol should be tried. Dichlorohydrin, which has been proposed as a universal solvent for resins, does not answer for copals. When cold, the acidity is taken with N/2 alcoholic potash using phenolphthalein as indicator. The saponification number was estimated in the usual manner by heat- ing with excess of standard alcoholic potash ; the use of chloroform is, of course, excluded here.Henriques' cold saponification process does Detection a n d Estimation of '' Dulcin " (Phenetolecarb- amide) in Articles of Food. By J. BELLIER(Chem. Centr., 1900, ii, 822; from Ann. Chim. anal. appl., 5, 333-337).-Lemonades or syrups, after dilution with water, are rendered alkaline with ammonia and shaken with ethyl acetate. In testing wine, 200 C.C. of the sample are treated with 2 grams of mercuric acetate and a little ammonia, and the filtrate is then shaken with 50 C.C. of ethyl acetate. When dealing with beer, 200 O.C. are mixed with 2-3 grams of sodium phosphotung- state and 10--201 drops of sulphuric acid, and the filtrate is shaken with 50 C.C. of ethyl acetate, after rendering alkaline with ammonia.I n either case, the solution in ethyl acetate is evaporated to dryness and the residue dissolved in a little sulphuric acid and mixed with a few drops of strong solution of formaldehyde. On adding water, a flocculent precipitate is formed which after 24 hours may be collected, washed, dried, and weighed ; its weight represents that of the '' dulcin." The Constituents of Digitalis and their Toxicological De- tection. By DIOSCORIDE VITALI (Chem. Centr., 1900, ii, 881 ; from Boll. Chim. Farm., 39, 597-602).-When testing meat which bad E. W. W. The acid number is estimated by direct titration. not work well with copals. L. DEK. It may be further identified by Jorissen's reaction. L. DE K.ANALYTICAL CHEMISTRY. 51 been purposely poisoned with digitalis, the author was only able to detect digitoxin.The meat is extracted with dilute alcohol, the alcohol evaporated, and the residual liquid treated first with lead acetste and then with sodium sulphate. The filtrate, after being ren- dered alkaline with ammonia, is shaken with chloroform, and from this the digitoxin is precipitated by adding 20 times its volume of a mixture of 1 part of ether and 7 parts of light petroleum. After a further purification with alcohol and ether, the digitoxin gives the re- action with Keller and Kiliani’s reagent very distinctly. L. DE K. Isolation and Estimation of Colchicine. By ALBERT B. PRES- COTT and HARRY M. GORDIN (Chem. Centr., 1900, ii, 784-785; from Apoth. Zeit., 15,521 -522).-Twenty-five grams of powdered colchicum corm or seeds are extracted in a Soxhlet apparatus for 2 hours with 35 per cent.alcohol ; the alcohol is distilled off, the oily residue rinsed with about 10 C.C. of hot water in a small separating funnel, and then shaken with 2-3 C.C. of light petroleum. After 15-20 minutes, the oily layer floats on the aqueous liquid. Without filtering, the latter is drawn off into a 100 C.C. flask, the stem of the funnel is rinsed with a little water, and the oily matter is again shaken with 10 C.C. of water. The whole is now put into a small dish, the light petroleum is removed by gently warming, and the contents are again transferred to the funnel and once more shaken with 2-3 C.C. of light petroleum ; by this repeated treatment, the whole of the alkaloid is removed from the oil.The turbid aqueous solution is diluted to 100 c.c., 1-2 grams of talc are added, and after shaking it is passed through a dry filter. The alkaloid may be estimated gravimetrically by first removing the water by means of a current of air, and finally drying the residue in a vacuum or over sulphuric acid. Volumetrically, it may be estimated by boiling it for 2 hours in a reflux apparatus with N/40 potassium hydroxide, and titrating the excess of the latter with N/40 hydro- chloric acid. L. DE K. Analysis of Quinine Glycerophosphate. By LEON PRUNER (J. I’harm., 1900, [vi], 12, 309-312).-The phosphoric acid in quinine glycerophosphate cannot be estimated by calcination and subsequent oxidation with nitric acid, as the carbon produced during calcination reduces the phosphoric acid and a loss of phosphorus occurs.Quinine is not completely precipitated from quinine glycerophosphate by alkalis in the cold. The following method of analysis gives accurate results :-the quinine glycerophosphate is dissolved in dilute nitric acid (1 : lo), a solution of sodium hydroxide added and the precipitated quinine filtered off. The filtrate is boiled for some time, when the re- mainder of the quinine is precipitated and may be removed by extraction with ether or chloroform. The mother liquor from the ethereal or chloro- form extraction is then mixed with a large excess of nitric acid together with 2-3 grams of potassium nitrate, evaporated t o dryness and calcined to a white ash, care being taken that sufficient nitric acid is present to avoid the presence of any free carbon during calcination.The phosphoric acid present in the residue may then be estimated by any of the usual methods. H. R. LE S. 4-252 ABSTBACTS OF CHEMICAL PAPERS, Analytical Chemistry of the Alkaloids. IV. Action of Bromine on Strychnine and Brucine. By EABL KIPPENBERGER (Zeit. and. Chem., 1900, 39, 609-627).-By acting on an acid solu- tion of a strychnine salt with an excess of bromine water, a gradual substitution of bromine for hydrogen takes place ; the monobromo- derivative is formed almost instantly, in the course of an hour di- and tri-bromostrychnine are formed, whilst the substitution of more hydrogen atoms only takes place after several hours, and in the course of 12 hours 16-17 atoms of bromine are taken up, with formation of strychnine perbromide. The presence of sodium chloride greatly ac- celerates the reaction. When moderate amounts of potassium bromide are present, yellow, nearly insoluble, monobromostrychnine hydrobromide perbromide, C,1H,20,N,Br,HBr,Brz, is rapidly formed together with a little of the dibromo-compound ; the presence of larger amounts of potassium bromide restricts the internal substitution. I n no case could more than 2 atoms of bromine be introduced into the molecule. Brucine forms a similar hydrobromide perbromide, but in conse- quence of its solubility in water, especially in the presence of acids, being greater than that of the strychnine compound, there is a greater tendency for the exterior atoms of bromine to effect substitution in the brucine molecule. The presence of both sodium chloride and potassium bromide favours the additive and hinders the substitutive reaction. The bromobrucine compounds exhi bit a rose-red colour. How- ever large the excem of bromine used, no perbromide containing more than two atoms of additive bromine could be obtained. Brucine salts behave in a similar manner. M. J. S. New Test for Gelatin and Isinglass. By OTTOMAR HENZOLD (Chem. Centrr., 1900, ii, 744, from Zeit. ofentl. Chem., 6, 292-293).- Fruit jellies in which gelatin is suspected are boiled with water, the hot liquid is filtered, and a portion of the filtrate is mixed in a test- tube with an excess of solution of potassium dichromate (1 : 10). The mixture is again heated to boiling, then rapidly cooled and mixed with 2-3 drops of sulphuric acid. Gelatin gives a white, finely divided precipitate which becomes sticky after some time ; vegetable jellies such as agar-agar, Iceland moss, and carrageen give no pre- Artiflcial Silk and its Distinction from the Natural Product. By A. SOLARO (Annali del Lab. China. Certtr. delle Gabelle, 1900, 4, 503--527).--Chemical and microscopical methods are given for dis- tinguishing natural silk from the artificial preparations having a basis of nitrocellulose or gelatin. cipitat e. L. DE K. T. H. P. Estimation of Humus. By CHARLES RIMBACH (J. A w . Chew, Soc,, 1900, 22, 695-703),-See this vol., ii, 37.

ISSN:0368-1769    

DOI:10.1039/CA9018005038

出版商:RSC    

年代:1901

数据来源: RSC

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53 General and Physical Chemistry. Lamps for Spectra. 11. By ERNST BECKMANN (.%it. physikcd. Chenz., 1900, 35, 443--458).-The paper contains a large number of practical details of the apparatus previously described (Abstr., 1900, ii, 701). For the appreciation of these, reference must be made to the original, with its numerous illustrations. Action of Heat on the Absorption Spectra and Chemical Constitution of Saline Solutions. By W. NOEL HARTLEY (Sci. Trans. Roy. DubZ. Xoc., 1900, 7, [ii], 253--312).-The author has examined the absorption spectra of nickel, copper, chromium, cobalt, uranium, and didymium salts, as well as that of potassium per- manganate. The changes in the spectra accompanying dilution and rise of temperature were specially noted. The author's conclusions are summarieed as follows.When a definite crystalline hydrate dissolves in a solvent which is not water, and is without chemical action on it, the molecule of the salt remains unchanged in chemical composition. I n any series of salts which are anhydrous, and do not form well-defined crystalline hydrates, the action of heat up to 100" does not cause alteration in their absorptiol; spectra, beyond that which is usual with substances which undergo no chemical change by such rise of temperature. The change is usually an increase in the intensity of the absorption, or a slight widening of the absorption bands. As a rule, crystalline metallic salts in which water is an integral part of the molecule dissolve in water at the ordinary tempera- ture without dissociation of the molecule.Crystallised hydrated salts, dissolved in a minimum of water a t 20°, undergo dissociation by rise of temperature. The extent of the dissociation may proceed as far as complete dehydration of the compound, so that more or less of the anhydrous salt may be formed in the solution. The most stable com- pound which can exist in a saturated solution at 16" or 20" is not always of the same composition as the molecule of the crystallised solid a t the same temperature, since the solid may undergo partial dissociation from its water of crystallisation when the molecule enters into solu- tion. Saturated solutions of deliquescent salts combine with water, when diluted, to constitute molecules of more complex hydrated com- pounds in such solutions. When a saturated solution of a coloured salt undergoes a great change of colour on dilution, or any remarkable change in its absorption spectrum due to the same cause, the dilution i s always accompanied by a considerable development of heat.J. C. P. J. C. P. Dielectric Constants of Pure Liquids. By B. BERNARD TURNER (Zeit. physikal. Chem., 1900, 35, 385--430).-The author has made an exhaustive study of Nernst's method of determining dielectric con- stants (Abstr., 1894, ii, 437), and introduced several alterations. The various means of eliminating the external capacity are compared, and the use of that method recommended in which the capacity of the VOL. LXXX. ii. 554 ABSTRACTS OF CHEMICAL PAPERS, trough employed is measured (1) with rod and condenser plate, (2) with rod alone. The ebonite lid of the trough is found to be a source of weakness, and is replaced by a glass lid of suitable construction.For exact measurements, the temperature coefficient of the apparatus must be taken into account. The standard condensers are enlarged and improved, whilst alterations in the compensation resistances are also described. With these improvements, it is possible to determine capacities five or ten times more accurately than with the older form of apparatus. The dielectric constants of the following pure liquids have been very accurately determined : benzene, 2.288 ; o-nitrotoluene, 27.7 ; water, 81.1, all at 18’; these liquids may suitably be employed as standards. The dielectric constants of the following have been accurately deter- mined, but either the liquids are more variable, or their purity has not been so thoroughly tested : ether, 4.368 ; aniline, 7.31 ; m-xylene, 2.3’76 ; nitrobenzene, 36.45, all at 18’.The dielectric constants of 16 other liquids and a number of temperature coefficients have also been determined. J. C. P. Influence of Non-electrolytes on the Conductivity of Elec- trolytes. By ARTHUR HANTZSCH (Zeit. anorg. Chem., 1900, 25, 332-34O).--The addition of carbamide, thiocarbamide, ethyl or methyl alcohol, ether, acetone? pyridine, urethane, or mannitol to aqueous solutions of the chlorides of the alkali or alkaline-earth metals diminishes the conductivity slightly, and to approximately the same extent. The addition of urethane or carbamide to solutions of silver ni- trate produces a small diminution of conductivity, alcohol and mannitol have a rather larger effect, whilst thiocarbamide and pyridine have a very large effect.The addition of 2 mols. of pyridine to 1 of silver nitrate, for example, reduces the conductivity by more than 30 per cent. The conductivity of ammoniacal solutions of ammonium chloride or calcium chloride is rather less than the sum of the conductivities of the solutions separately. The difference is somewhat greater in the case of ammoniacal solutions of silver nitrate. The latter contain the complex ionAg(NH3)2, so that tohe mobility of this ion must be about the same as that of the simple ion Ag. The author considers that the results are best interpreted by Werner’s theory (Zeit. anorg. Chem., 1889, 3, 267).T. E. Decomposition-potentials of Fused and Solid Electrolytes. By CHARLES CORNFIELD GARRARD (Zeit. aaorg. Chem., 1900, 25, 273-312).-The salts are fused in hard glass tubes with clectrodes of pure carbon. The currents produced by the application of a series of E.M.F.’s are observed and plotted in a curve. Each change of direc- tion of this curve indicates the beginning of some decomposition. From the decomposition-potential (E) of a salt at the temperature T, and the temperature coefficient dE/dT, the heat of formation, Q, of the salt can be calculated by means of Helmholtz’s equation, &= E - TdE/dT. Where two decomposition points (E, and 3,) exist, two heats of formation may be calculated (Q1 and &,). These are corn- pared with the heat of formation determined by the calorimeter (&). The following table contains the principal numerical results :GENERAL AND PHYSICAL CHEMISTRY.55 Substance. Temp. I- NaI ............... KI ................ PbI, ............. PbCI, ........... CdCl, ............ CdBr, ............ CdI, ............... AgCl .............. AgBr ............ AgI (solid) ..... ZnC1, ............ ZnBr, .......... AgI .............. 650" 674 470 669 563 591 468 536 566 564 465 467 504 -I- 1-1- 55000 92200 0.812 0'833 0'435 0.80 0.715 0.62 0.515 0.760 0.469 0.348 0-5 44900 75000 28100 25300 18300 - 7.7 - 8.9 - 6.5 - 7.3 -6.5 0 -728 1.238 1'225 0 '91 0.681 1'505 1'21 - 6.2 - 8'0 Heat of formation. 46500 75700 29800 25000 20600 Q2. 1 Q. Lead Chloride and Iodide.-These salts are probabIg ionised as follows : PbI, = PbI* +I' and PbI.= Pb** + I'. The separation of the ions Pb** and I' from their charges will require one potential, that of the ions PbI* and z' another. Since P b I decomposes spontaneously into PbI,, and P b when it is separated from its electric charge, it is obvious that this change is not reversible, and requires a higher poten- tial than the reversible discharge of Pb** and I' ions. I n accordance with this, the values of Q1 agree well with those of Q for these salts. The first decomposition point is indistinct and not readily observed, whereas the second is well marked; it follows from this that the salts are mainly dissociated into PbI* or PbCl* ions. The results are quite similar to those obtained with water. A saturated aqueous solution of lead chloride deposits P b and Pb0, at 1.568 - 0.002 t volts (with platinum point electrodes).A saturated aqueous solution of lead bromide gives P b and Br at 1.306 volts (16'). The decomposition is the irreversible one through PbBr* ions. With fused lead bromide, the results were untrustworthy owing to an increase of resistance at the anode; the curious behaviour of aqueous solutions of oxalic acid is shown to be due to a similar cause. The saturated aqueous solution of cadmium chloride gives two de- composition points, showing that the electrolytic dissociation takes place in two stages. Cuprous chloride, when fused, conducts the current in accordance with Ohm's law, and shows no polarisation. Model to Show Ionic Migration. By W. LASH MILLER and FRAKK B.KENBXCK (Zed. physikal. Chem., 1900, 35, 440-442).--Two horizontal cords, carrying cardboard riders at fixed distances to repre- sent the ions and stretched by weights at one end, are made to move in opposite directions and with different velocities by means of pulleys t o which the other ends of the cords are attached; the diameters of the pulleys are in the ratio I : 2 : 3. This model shows how the ions are separated at the electrodes, and how the concentration of the inter- T. E. 5-256 ABSTRACTS OF CHEMICAL PAPERS, mediate solution is affected by the migration of the ions. The poten- tial difference between the electrodes may be represented by the driving pressure on the pulleys, so that the apparatus serves to illus- trate Ohm's law (compare Miiller, Abstr., 1900, ii, 643 ; Kohlrausch, Abstr., 1900, ii, 712).By VANDEVYVER- GRAU (Chern. Centr., 1900, ii, 923-924; from Ann. Chim. anal. appl., 5, 321--323).-See this vol., ii, 46. Thermochemistry of the Hyperacids of Zirconium, Cerium, and Thorium. By L. PISSARJEWSKY (J. Russ. Phys. Chem. Xoc., 1900, 32, 609-637. Compare Abstr., 1900, ii, 466).-The following heats of reaction have been determined : J. C. P. Determination of the Specific Heat of Fats. ZrO, (hydrated) + mH,SO, = Zr(SO,), + H,O, + H,O + (n - 2)H,SO, +9*671 Gal. ZrO, (hydrated) = ZrO, +O + 21.786 Cal. 2 0 , (hydrated) + mH2S04 = Ce,(SO,), + H,O, + 0, + 2H,O + 2Ce(S0,J2 + H,O, = Ce,(SO,), + H,SO, +O, + 33.576 Cal. CeO, (hydrated) +mH,SO, = Ce(SO,), + 2H,O + (n - 2)H,SO, + CeO, (hydrated) = CeO, (hydrated) + 0 + 20-392 CaI.Tho, (hydrated) = Tho, (hydrated) + 0 + 14.290 Gal. The heats of sclution of hydrated thorium peroxide (Th,O,) and oxide in dilute nitric acid are 34.368 and 29.893 Cal. repectively. By dissolving zirconium peroxide in excess of hydrogen peroxide solution in presence of an alkali hydroxide, the sodium (with 9H,O) and potassium (with 9H,O) salts of perzirconic acid, H,Zr,O,,, were prepared but could not be obtained in a pure state. By M. 5. WREWSKY (2 Russ. Phys. Chem. Xoc., 1900,32,593-609).--The vapour pressure of a solution of potassium carbonate in a mixture of methyl alcohol and water is found to increase with the proportion of salt present. If P is the vapour pressure of the aqueous alcohol and P, that of the aqueous alcoholic potassium carbonate solution, the value of (P, - P)/P diminishes as the temperature rises.Experi- ments made with salts of the alkali and alkaline-earth metals show that the change produced in the value of the vapour pressure of aqueous methyl alcohol when equivalent quantities of salts of the same acid are dissolved in it, increases as the molecular weight of the base of the salt increases, whilst salts of the same base with different acids produce effects which decrease as the avidity of the acid increases. Further, the changes produced in the vapour pressure of such solutions at any temperature by replacing potassium chloride by sodium chloride or potassium carbonate by sodium carbonate are identical; a similar relation holds for the replacement of potassium carbonate by potassium chloride and of sodium carbonate by sodium chloride.The system methyl alcohol-water-potassium carbonate separates into two layers (one containing excess of water and the other excess of (n - 3)H,SO, + 29.954 Cal. 0.897 Cal. T. H. P. Vapour Pressures of Aqueous Alcoholic Salt Solutions.GENERAL AND PHYSICAL CHEMISTRY. 57 alcohol) which are found to have equal vapour pressures, that of the water being lowered and that of the alcohol raised by the presence of the salt. T. H. P. Vapour Pressure of a Series of Benzene Compounds. By ADOLF WINRELMANN (Zeit. physikal. Chem., 1900, 35, 480-482).- A criticism of certain statements made by Woringer (see Abstr., 1900, ii, 709). J, C. P. Vapour Pressures of Binary and Ternary Mixtures. By FUNS A.H. SCHREINEMAKERY (Zeit. physikal. Chem., 1909, 35, 459-479).-The greater part of this paper, dealing with the system water-phenol, has already been abstracted (this vol., ii, 9). The author has further investigated the three-phase system : water-aniline. The vapour in contact with the two conjugate liquids. aniline-water and water-aniline, has at temperatures from 41-90° a composition inter- mediate between those of the liquids. At 5 6 ~ 3 ~ and 7 5 O , the vapour from aqueous solutions of aniline contains more aniline than the liquid. The experimental results for the system water-aniline are shown to agree with van der Waals’ formula (Zoc. cit.). The compo- sition of the vapour phase of the system water-phenol-aniline, the liquid and solid phases of which have been previously investigated (Abstr., 1899, ii, 739 ; 1900, ii, 135), has been determined at 5 6 * 3 O , in contact with two conjugate liquid phases.By HANS EULER (Bey., 1900, 33, 3202-3206. Compare Abstr., 1900, ii, 532).--The author holds that a catalytic agent affects the dissociation of the substances primarily concerned in a reaction, and applies this to the hydrolysis of ethyl acetate, When R’is the equilibrium constant of the reaction, and k and k’ the velocity constants of the two opposite component re- actions, then K=k/k’. The catalytic agent has no effect on the ratio I%/#, but alters the absolute value both of k and k’ in the proportion 1 : 1 + kH, where H is the concentration of the hydrogen ions yielded by the catalytic agent, Since the ratio k/k’ is unaltered by the cata- lytic agent, the free energy of the reaction (= RTlog,k/k’) is also un altered.J. C. P. Most General Form of the Laws of Chemical Kinetics for Homogeneous Systems. By RUDOLF WEGSCHEIDER (Jfonatsh., 1900, 21, 693-786. Compare Abstr., 1900, ii, 199).-A theoretical paper, much of which is not suitable for abstraction. The author de- duces general equations for the velocity of all kinds of reactions at constant volume in homogeneous systems. He discusses the form which the equation expressing the reaction must have, and the conditions which must be fulfilled in order (1) that the ratio of the velocities of two reactions which take place simultaneously is independent of the time ; (2) that the concentration of a substance which is produced and de- composed in parallel reactions remains unchanged ; (3) that the con- centration changes of two substances are in a ratio to one another which is independent of the time.The form of the equation for reac tion velocities with varying volume and (in the case of gases) with constant pressure is deduced, and the formulse obtained are applied to J. C. P. Theory of Chemical Catalytic Action.58 ABSTRACTS OF CHEMICAL PAPERS, Bodenstein’s experiments on the formation of water from hydrogen and oxygen (Abstr., 1899, ii, 733). J. C. P. Sensitiveness to Light of Hydrogen Peroxide in Aqueous Solution on Addition of Ferro- and Ferri-cyanide. By WLADIM IR A. KISTIAHOWBKY (Zeit. physikal. Chem., 1900, 35, 431--439).-When a few drops of potassium ferrocyanide are added to a 1 per cent.solution of hydrogen peroxide kept in the dark, the decomposition of the peroxide is very slow ; if, however, the liquid is placed in direct sunlight, a brisk effervescence is observed in a few minutes, especially on shaking. It is shown that the liberation of oxygen from hydrogen peroxide under these conditions is in accordance with the equation : k.t =loga/(a- x), where k is a constant, a the initial concentration, and x the quantity of the hydrogen peroxide de- composed. The value of k when the reaction takes place in sunlight is 10-20 times greater than the value obtained when i t takes place in the dark. It is not necessary that the liquid be illuminated the whole time; a minute’s illumination is sufficient to accelerate the de- composition to the extent mentioned.It is shown that this accelern- tion is not due to a rise of temperature, but probably to a catalytic agent formed in the light from ferrocyanide and ferricyanide, an agent which is permanent even when illumination is discontinued. J, C. P. Absorption of Water Vapour by Chemical Compounds. By W. I. BUSNIKOFF (J. Russ. Phys. Chem. SOC., 1900, 32, 551-593. Compare Abstr., 1899, ii, 360 and 409)-9.7340 grams of aqueous sulphuric acid of the composition H2S04 + 2*285H20, and 42.9056 grams of acid corresponding with the hydrate H2S04 + 0*338H20 were placed under the same desiccator and the concentrations of the two determined from time to time. A t the end of 787 days the respective compositions were H2S04+ 0.8’77K20 and H2S04 + 0.648H20 ; so that if interchange of water between two masses of aqueous sulphuric acid takes place in such a manner that one of them forms a hydrate containing less than 1H20, the other will also give a hydrate with less than 1H20. Next two masses of 043054 and 51.0118 grams respect- ively of the same acid of the composition H,SO4+@285H2O were placed under a bell jar in vessels of the same sectional area so that equal surfaces were exposed to the air ; it was found that the weights of water absorbed in the two cases were almost identical, the rate of absorption being independent of the composition of the acid between the limits H,SO, + 0*285H20 and H,SO, + 2.038H20.It was previously shown (Zoc. cit.) that the hydrate H2S04 + 4H20 possesses a greater power of absorbing water than the hydrates immediately weaker and stronger than it ; further experiments show that in this hydrate the affinity with which the water is held also has a maximum value.On exposing approximately equal quantities of phosphoric oxide and the hydrate H2S0, + 0*887H20 togetherunderadesiccator, it is found that the former absorbs more water than the latter. Other experi- ments with aqueous sulphuric acids show that hydrates containing between 12 and 12.5 or between 18 and 19 mols. of water per H2S04INORGANIC CHEMISTRY. 69 have greater powers of absorbing water than the adjacent lower and higher hydrates. The absorption of water vapour by sodium sulphate has also been studied, as well as the interchange of water between the hydrated salt and aqueous sulphuric acid, when placed under the same desiccator.In the latter case, 3.7280 grams of Na,SO,+ 11*654H20 and 1.1742 grams of H,SO, + 0*274H20 were employed, the composition of the hydrated sodium sulphate being, after successive periods of 24 hours : Na2S0,+ (1) 1 1-654H20 (initial value), (2) 7.80H20, (3) 5*704H20, (4) 4*345H28, &c. The affinities of these hydrates for water are (1) 0*047,(2), 0.074 and, (3) 0.110, and (4) 0.162 respectively, these numbers increasing in a geometrical progression with constant ratio about 1.50. I n the same way, the sulphuric acid absorbs water, forming a t the end of each 24 hours hydrates which have affinities for water increasing in geometrical progression with a constant ratio about 1.50. I n the case of anhydrous potassium carbonate, the affinities of the various hydrates for water increase geometrically with a ratio of about 1-40. Experiments mere also made on the removal of water from aqueous potassium carhonate by means of sulphuric acid placed in the same desiccator. Anhydrous sodium nitrate absorbs water vapour, yielding after successive intervals of 24 hours hydrates which have affinities f o r water nearly equal in value. When the water is removed from the hydrated nitrate by placing it together with sulphuric acid under a desiccator, the hydrates obtained at the end of each day's exposure have aanities for water of the values 0,077, 0.112, and 0.349 respect- ively, there being in this case no constant ratio. Similar experiments were made with potassium nitrate, the affinities of the various hydrates for water being 1 *74, 1 *48, 1-48, 1 *72 and 1.76 respectively. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9018005053

出版商:RSC    

年代:1901

数据来源: RSC

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INORGANIC CHEMISTRY. 69 Inorganic Chemistry. Alleged Conversion of Phosphorus into Arsenic. By ANASTASIOS K. CHRISTOMANOS (Chem. Zeit., 1900, 24, 943-944).- Arsenic trisulphide, prepared from commercial phosphorus by Fittica's method, was tested for phosphorus and nitrogen, but without success. FRIEDRICH FITTICA replies that it is not surprising that the ordinary methods for the estimation of phosphorus and nitrogen should fail with arsenic, since the methods used for determining nitrogen in inor- ganic amino- or nitro-compounds are known to fail where t h e nitrogen isTmore firmly united, as in the case of many amino- and nitro-organic derivatives. T. H. P. By FRIEDRICH FITTICA (Chem, Zeit., 1900, 24, 991--992).-'l!he exact conditions are given under which, according to the author, phosphorus is oxidised to Conversion of Phosphorus into Antimony.60 ABSTRACTS OF CHEMICAL PAPERS.arsenic and antimony by means of ammonium nitrate and carbonate, and potassium nitrite. The composition PN20 is assigned to arsenic and P2N,0, to antimony. Crystalline Form of Calcium, Barium, and Strontium Sul- phides. By WILHELM MULLER (Cent?. &fin,, 1900, 178-179. Com- pare Abstr., 1898, ii, 376; 1899, ii, 97).-The material examined was prepared by E. Kunheim by heating in an electric furnace the sulphates of the alkaline earths with carbon : carbides are formed to- gether with the sulphides. Cavities are lined with small cubes which are optically isotropic and have a perfect cubic cleavage. Sp. gr. (Kunheim) : calcium sulphide, 2.4-2-5 ; strontium sulphide, 3.336.Mixed crystals of calcium and barium sulphide were also prepared. These sulphides are isomorphous with galena. Cadmium Selenide. By HENRI FONZES-DIACON (Conzpt. rend., 1900, 131, 895-8997).-When cadmium chloride is heated just to its volatilising point in a current of hydrogen selenide, cadmium selenide, Case, is obtained in pale brown, transparent crystals of sp. gr. 5.81 at 15", which, like the zinc selenide obtained under similar conditions (Abstr., 1900, ii, 345), seem to belong to the hexagonal system. A chocolate-brown selenide of the same composition is obtained by the action of hydrogen selenide or alkali selenides on solutions of cadmium salts. The yellow compound obtained by Fabre by the action of sodium selenide on a solution of cadmium iodide, is a double salt of the composition C'd12,3CdSe, which is decomposed by the action of light in the presence of water.The chloride and bromide form similar but less stable compounds. Cadmium selenide, even when crystallised, is easily decomposed by acids, burns readily when heated in oxygen, and is decomposed by chlorine at a moderate temperature, T. H. P. L. J. S. C. H. B. Thallium Chlorobromides. By VICTOR THOMAS (Compt. rend., 1900, 131, 892-8995, Compare Meyer, Abstr., 1900, ii, 655 ; Cush- man, ibid., 725).-Thallium chlorobromide, Tl,C!,Gr,, is obtained by the action of excess of bromine on thallous chloride, and forms small, transparent, sulphur-yellow prisms which seem to be rhombic. They alter somewhat when exposed to air at the ordinary temperature and are decomposed by water, especially on heating.Oxy-acids liberate a large quantity of halogens ; bromine converts the salt into a compound or compounds of the type TI,X,, whilst when heated it yields salts of the type T12X,. The action of varying quantities of bromine on thallous chloride also yields compounds of the types T12X, and T12X6, and these will be described subsequently. C. H . B. Combination of Nitrogen with Metals of the Rare Earth Group. By CAMILLE MATIGNON (Compt. rend., 1900, 131, 837-839. Compare Abstr., 1896, ii, 299; 1900, ii, 726).-Winkler has shown that metallic magnesium liberates the metal from the oxides of thorium, cerium, and lanthanum, and this is now found to be true for the oxides of praseodymium, neodymium and samarium.A mixture of the oxide of the metal and metallic magnesium was strongly heated in anINORGANIC CHEMISTRY. 61 atmosphere of the gas to be investigatedj; it was found that nitrogen, but not argon, is rapidly absorbed by thorium, cerium, lanthanum, praseodymium, neodymium, and samarium. The heat of formation of the oxides of thorium and cerium is greater than that of the oxides of the other metals, the oxide of samarium being the least exothermic. Direct Combination of Hydrogen with the Metals of the Rare Earths. By CAMILLE MATIGNON (Compt. rend., 1900, 131, 891-892). -Neodymium, praseodymium, and samarium combine directly with hydrogen when the metals are liberated in the presence of this gas by the action of magnesium on the corresponding oxides. The hydrides thus formed are dissociated when strongly heated.Samarium Carbide. By HENRI MOISSAN (Compt. rend., 1900,131, 924-926).-Xamarium carbide, SmC,, obtained by heating a compressed mixture of samarium oxide, Sm,O,, with sugar carbon in the electric furnace, has a more metallic appearance than neodymium and praseo- dymium carbides (Abstr , 1900, ii, 726), but small particles are shown by the microscope to consist of transparent, yellow, hexagonal crystals ; it has a sp. gr. 5.86. It is not reduced by hydrogen a t 1000°, but is decomposed by chlorine when gently heated, and by bromine or iodine at a dull red heat. In oxygen a t 400°, the carbide undergoes complete combustion, and it is also attacked by sulphur a t a much higher tem- perature. I n its action on water, samarium carbide resembles yttrium carbide, the gaseous products consisting of acetylene (71 per cent.), olefines (8 per cent.), and hydrogen and paraffins (21 per cent.).The carbide is readily decomposed by acids, and by hydrogen sulphide or By WILLIAM H. EMERSON (Trans. Amer. Inst. Hining Engineers, l900,29,230--248).-Numerous comparative tests were made of the abrasive power of different samples of corundum from Georgia and North Carolina, and partial chemical analyses were made of the same material. There appears to be no close connection between abrasive power and chemical composition. H. R. LE S. C. H. B. hydrogen chloride at a red heat. N. L. Abrasive Efflciency of Corundum. L. J. S. Presence of Ferrous Oxythiocarbonate in the Water of the Rhone. By HENRI CAUSSE (Compt.rend., 1900, 131, 947-949).-At certain periods during the last four years, it has been noticed that the water of the Rhone restores the colour of Schiff’s reagent and exhibits other reactions characteristic of aldehydes. The reactions are first observed in June or July, reach a maximum in September, and disappear later in the year ; they are not given by the water after distillation, or after exposure to air, which causes the formation of an ochreous deposit. Synthetic experiments show that the substance to which the reactions are due is probably ferrous oxythiocarbonate, CO<o>Fe, formed by the combination of carbon dioxide with ferrous sulphide, the latter being the result of the reduction of sulphates by organic matter. S N. L.62 ABSTRACTS OF CHEMICAL PAPERS.Action of Steam and of Mixtures of Steam and Hydrogem on Molybdenum and its Oxides. By MARCEL GUICHARD (Compt. rend., 1900, 131, 998--1001).-The brown molybdenum dioxide, MOO,, resulting from the action of hydrogen on the trioxide a t 470', is com- pletely reduced by a current of the gas a t 600' ; on the other hand, finely divided molybdenum is not oxidised by steam a t temperatures below 700'. From these observations, it follows that the steam produced by the action of hydrogen on the oxides of molybdenum at 600-700° has no tendency to reverse the action, and may be considered as an inert gas; above 700°, however, it is a reagent and the inverse change becomes possible, When molybdenum and its dioxide are heated at these temperatures in a mixture of hydrogen and steam, both reactions, oxidation and reduction, occur simultaneously, and the state of equilibrium finally attained depends on the partial pressures of the constituents of the gaseous mixture.The metal or its dioxide is not affected a t 800' by a current of the gaseous mixture containing its constituents in approximately molecular proportion ; when the pro- portion of steam is larger than this, the metal is almost wholly oxidised to dioxide, whilst excess of hydrogen brings about a complete reduction of the oxide. Bismuth Phosphates. By CLEMENTE MONTEMARTINI and U. EGIDI (Gcczxetta, 1900, 30, ii, 377--381).-The only phosphate obtain- able from bismuth solutions by precipitation and subsequent washing is the ortho-phosphate, BiPO,, which is stable towards water even after boiling for some time, and is almost insoluble in sodium pyro- phosphate solution.T. H. P. General Method of Separating the Metals that accompany Platinum. By EMILIE LEIDIE (Compt. rend., 1900, 131, 888-891). -The residues from the manufacture of platinum and iridium are roasted in the air, heated in hydrogen, washed with dilute hydro- chloric acid, again heated in hydrogen, and then mixed with sodium chloride and heated in chlorine at an incipient red heat. The residue and the volatilised products are treated with water, and the solution allowed to remain until the silver and the greater part of the lead and bismuth have separated as chlorides. The solution is heated at 100" and mixed gradually with excess of sodium nitrite, which precipitates the iron and gold, and afterwards with sodium carbonate, which pre- cipitates lead, copper, bismuth, &c.After boiling for some time, the liquid is filtered, mixed with sodium hydroxide and distilled in a current of chlorine. The osmium and ruthenium are thus volatilised, and can be separated in the ordinary way. The residual liquid is acidified with hydrochloric acid, again mixed with excess of sodium nitrite, and a large quantity of ammonium chloride added, when the iridium and rhodium are precipitated as double ammonium nitrites. The precipitate is dissolved in hot hydrochloric acid, evaporated t o dryness, dissolved in water and mixed with excess of ammonium chloride, which precipitates iridium, but not rhodium. The precipitate is dried and heated a t 450° with its own weight of sodium chloride, which converts the iridium into soluble sodium iridiochloride, and any co-precipitated rhodium into the insoluble anhydrous chloride. G. T. M.MINERALOGICAL CHEMISTRY, 63 The rhodium ammonium chloride is separated by crystallisation, dissolved in water, and converted first into the double sodium nitrite and afterwards into the double ammonium nitrite, which is pre- cipitated, whiJst any traces of iridium that may be present remain in solution. The mother liquor from the iridium and rhodium contains platinum and palladium, and is evaporated t o dryness, heated with concentrated hydrochloric acid to decompose the nitrites, again evaporated to dryness, and strongly heated. The residue is washed with water, dis- solved in aqua regia, evaporated, redissolved and a current of nitric oxide passed into the liquid in order to reduce the palladium and iridium chlorides, after which the liquid is saturated with ammonium chloride to precipitate the platinum. The palladium in the mother liquor is precipitated by adding mercuric cyanide. C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA9018005059

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

Organic Chemistry. Analogies between Oxygen, Nitrogen, and Carbon in similar Linkings. By EMIL ERLENMEYER, jun. (J. pr. Chem., 1900, [ii], 62, 145-1 65).-A paper which summarises the results of introducing different atomic groupings into analogous compounds, but does not lend itself to abstraction. R. H. P. Action of Bromine on 1 : 1-Dimethyltrimethylene. By GABRIEL GUSTAVSON (.I pr. Chern., 1900, [ii], 62, 270-272).-The bromine compound previously described (Gustavson and Popper, Abstr., 1899, i, 263), and obtained by the action of bromine on 1 : 1-dimethyl- trimethylene (1 : 1 -dimethylcyclopropane), is py-dibromoisobutane, CMe,Br* CHMeBr. R. H. P. Derivatives of CycZoPentadiene. By FRITZ NOELDECHEN (Ber., 1900, 33, 3348-3354).-The chlorocyclopentene obtained by the addition of hydrogen chloride to Kraemer and Spilker's cyclopenta- diene (Abstr., 1896, i, 289) interacts with aniline below 10' to form anilinocyclopentene, C,H,*NHPh, a colourless oil boiling at 152-1 53' under 25 mm., and at 260' under the ordinary pressure ; the hydro- chloride crystallises from absolute alcohol in short prisms, and melts and decomposes a t 140-142O ; the platinichloride (with l$H,O) de- composes at 140' ; the picrate melts and decomposes a t 154-155', the sparingly soluble sulphccte at 197', and the oxakate at 122'.The ucetyl derivative, C,H,*NAcPh, crystallises from water in long needles, and melts at 128' ; the benxoyl derivative separates in transparent, hexa- gonal prisms from light petroleum and melts at 76-77'. cyclo Pentenyldiphenylcarbanzide, NHPh* CO *NPh*C,H7, obtained by the action of phenylcarbimide on the base at the ordinary temperature, separates from absolute alcohol in small leaflets and melts at 112'; the analogous thiocnrbamide cry stallises from absolute alcohol in lustrous, colourless needles and melts at 130'.Anilinocyclopentene interacts with nitrous acid to form a reddish- yellow, oily nitrosoamine, which shows Liebermann's reaction, and is reduced by zinc dust and acetic acid to cyclopentenylp?ienylydraxilze, NH,-NPh-C,H7, the hydrochloride of which forms silvery scales and melts and decomposes at 2 15-217'. On heating anilinocycZopentene with hydriodic acid, or with concen- trated hydrochloric acid €or 2 hours at ZOO', aniline is formed, together with a red, amorphous, insoluble substance. On attempting to reduce the base with sodium and amyl alcohol, an isomeric anilinocyclopentene is formed, instead of the expected anilinocyclopentane ; its hydrochloride is more sparingly soluble than that of the original base, and forms long, white needles melting and decomposing a t 168'; the platini- chloride (with 2H,O) decomposes at 135'.Piperidylcyclopentene, C,H,,N* C,H7, from chlorocyclopentene and piperidine at - 5', boils at 94-96' under 23 mm., and at 206-207O VOL. LXXX: i. P62 ABSTRACTS OF CHEMICAL PAPERS. under the ordinary pressure ; it absorbs carbon dioxide from the air, yields a crystalline methiodide, and a hygroscopic hydrochloride and sulphute, the former decomposing at 190'. Abnormal Behaviour of Polyhaloid Compounds with Alco - holic Potash. By IWAN L.KONDAKOFF (J. p. Chem., 1900, [ii], 62, 166-188. Compare Abstr., 1899, i, 556).-The previous work (loc. cit.) has been repeated, and it is now shown that the action of alcoholic potash on by-dimethyl-P-butylene di bromide produces diisopropenyl, By-dimethyl-/3-butylene, and an unsaturated ether, which boils at 136--146O, and, when treated with dilute sulphuric acid, gives pinacone, pinacolin, and an aldehyde. by-Dimethyl-P-butylene di- chloride, when treated with alcoholic potash, yields diisopropenyl and the ether boiling a t 136-146'. Diisopropenyl forms two dihrontides, the one is an oil, and the other crystallises in colourless needles, which have an irritating odour and melt at 47O, both yield the same tetrabromide melting at 137'.The crystalline dibromide, when oxidised, yields two glycols, of which one has the composition C6H1202Br2, crystallises in prisms, and melts a t 94O; the other, obtained in very small quantity, melts at 1 6 0 O . The paper contains a discussion of the constitution of bromides formed by unsaturated hydrocarbons from the point of view of Thiele's theory of I' partial " valencies (Abstr., 1899, i, 554). W. A. D. R. H. P, Diethyl Peroxide. By ADOLF VON BAEYER and VICTOR VILLIGER (Bev., 1900, 33, 3387--3393).-Diethyl sulphate was shaken witb hydrogen peroxide of 12 per cent. strength (by weight), 60 per cent. aqueous potassium hydroxide being added little by little ; the tempera- ture was not allowed to rise above 20', and the operation was continued (for some 11 hours) until the presence of hydrogen peroxide could be detected no longer.The product was then made acid with sulphuric acid and fractionated; the fraction coming over at 55-75O con- sisted mainly of diethyl peroxide, that distilling a t 75-100O probably contained some ethyl hydrogen peroxide. Diethylproxide, 02Et,, boils at 6 5 O , and has a sp. gr. 0.8273 at 15'/4O; it is strikingly inert in its reactions, almost resembling an ether ; permanganate, chromic acid, and sodium amalgam do not affect it, and it oxidises alkaline pyro- gallol and potassium iodide but slowly ; it is, however, reduced quanti- tatively to ethyl alcohol by zinc in the presence of acetic and dilute sulphuric or hydrochloric acid ; the " active " oxygen in it may be determined in this way by taking a weighed quantity of zinc and measuring the deficit in the hydrogen evolved as compared with that equivalent to the amount of zinc taken.The inflammability of the vapour is most striking; it inflames in air at 250°, or 50° below the kindling temperature of carbon disulphide vapour, and when a hot copper wire is brought near it in an atmosphere of carbon dioxide, the liquid disappears rapidly, without any noise, without any flash, and without boiling. As a result of this internal eombustion, form- aldehyde, carbon monoxide, and ethane are formed, A mixture of the vapour with air or oxygen explodes more violently than a mix- ture of hydrogen with air or oxygen. On the other hand, the liquidORGANIC CHEMISTRY, 63 could not be made to explode by hammering, or by the use of mercury fulminate. The ready reduction of diethyl peroxide to ethyl alcohol is regarded as strong evidence in favour of the formula HO*OH, rather than O:OH,, for hydrogen peroxide. Optically Active Forms of a-Bromopropionic Acid.By LUDWIG RAMBERG (Ber., 1900,33, 3354-3356).-0n adding cinchonine gradu- ally to an aqueous solution of a-bromopropionic acid, thick prisms or plates of the salt, C,,H,,ON,,2(C,H,O,Br), of the 1-mid separate ; the pure acid appears to have La], - 7.55" at 24O, the d-acid, isolated from the mother liquxs of the foregoing salt, having [a], + 7.44'. These values, however, are to be more accurately determined. By FRITZ FICHTER and WERNER LANGGUTH (Annalerz, 1900, 313, 371-381. Compare Wallach, Abstr., 1900, i, 589).-The paper contains experimental details relating to the pre- paration of 8c-hexenoic acid (Abstr., 1897, i, 590), and of ys-hexenoic acid (Abstr., 1897, i, 14).Action of Water on Heptylamine Soaps. By FRIEDRICH KRAFFT and R. FUNCKE (Ber,, 1900, 33, 3210-3212).-Whan heptylamine oleate (m. p. la0), elaidate (m. p. 45O), erucate (m. p. 21-5'), or brass- ate (m. p. 44.5') is brought into contact with water a t a temperature above the melting point, globular or thread-like bodies are produced, which grow in size when surrounded with water, but collapse in contact with a strong salt solution, the surface of the globules acting as a semi- permeable membrane. By cooling below the melting point, the globules disappear and crystals are again formed ; within certain limits of tem- perature, globules and crystals may both be observed. Transformation of Maleic Acid into Fumaric Acid, By JULIUS SCHMIDT @el*., 1900, 33, 3241-3243.Compare Wislicenus, Vei*hccnd. K. Ges. Wiss. Leipxig, 1895, 489).-Maleic acid, dissolved in dry ether, is not affected by the nitrous fumes evolved from a mixture of arsenious oxide and nitric acid; an aqueous solution, cooled below loo, when similarly treated, yields a mixture of unaltered substance and fumaric acid, whilst at the temperature of the water-bath 70 per cent. of the maleic acid is transformed. Fumaric acid is not produced when an aqueous solution of its cis-isomeride is heated on the water- bath, and no alteration results from the addition of nitric acid free from nitrous acid (compare Edmed, Proc., 1899, 15, 190).C. F. B. W. A. D. 8E-Hexenoic Acid. M. 0. F. T. M. L. a. T. M. Dicrotonic Acid. By HANS VON PECHMANN (Ber., 1900, 33, 3323-334 1) .-Dimethyl dicrotonate (dimethyl P-methyl-a-ethylidene- glutarate), formed by the action of sodium methiodide on dimethyl crotonate, is a colourless oil boiling a t 120' under 15 mm. and at 130' under 20 mm. pressure; it is also formed when dicrotonic acid is treated with diazomethane. Diethyl dicrotonate is prepared from diethyl crotonate, and boils at 137.5' under 18 mm. pressure. Dicrotonic acid, CHMe:C(CO,H)*CHMe*CH,*CO,H, prepared from the ester by hydr- olysis, crystallises in white, compact needles melting at 129O, and boils f 264 ABSTRACTS OF CHEMICAL PAPERS. at 210' under 21 mm. pressure, partial decomposition into water and anhydride taking place.The acid is dibasic to soda, and has a con- ductivity K 0 00281. The difference of equivalent conductivity of the sodium salt at dilutions of 32 litres and 1024 litres is 11.9, an abnormally low value for a dibasic acid. The barium salt crystallises with 1H,O in lustrous scales; no acid salts could be obtained. Mono- ethyl dicrotonate, CHMe:C(CO,H)*CHMe*CH,* CO,Et, is obtained by the action of alcoholic sodium ethoxide on dicrotonic anhydride, and is an oil boiling a t 174" under 16 mm., at 186' under 34 mm., and at 192' CHMe FH2 under 44 mm. pressure. Dicrotonic anhydride, CHMe:C< formed when the acid is distilled under atmospheric pressure or treated with acetyl chloride, crystallises in white needles melting at 38--39O and boiling a t about 300'.The constitution of the acid is shown by the fact that on oxidation with potassium permanganate it yields acetaldehyde and methylsuccinic acid. GO-o*co ' P-Methyl-a-ethylideneglutaranilic acid, CHMe:C(CO,H)*CHMe*CH,* CO *NHPh, is obtained by the action of aniline on the anhydride, and crystallises in lustrous prisms melting a t 178-179O. Dicrotonic acid readily combines with bromine t o form an unstable dibromide, which loses hydrogen bromide when heated with water and forms 6-6romo-/I-methylhexolactone-y-carboxylic acid, CHMeBr*C(C02H)<o-CO>CH,, CHMe which crystallises in colourless prisms melting at 140'. When its solution in sodium carbonate is boiled, hydrogen bromide and carbon dioxide are eliminated with formation of P-methylhexenobctone, MeCH:C<CHMe'QH2, which is a colourless oil boiling at 247'.The corresponding acid, Ps-dimeth yllmvulic acid, CH,Me*CO* CHMe*CH,* CO,H, is a thick oil boiling a t 153-254' under 20-21 mm. pressure. The phenylhydraxone is a thick oil, wbilst the semicar6axonet C7H!,0,:N*NH* CO *NH,, is a characteristic, white, crystalline powder melting at 152'. When heated, it yields a pyridazinone, probably a homologue of the 3-methylpyridazinone, which is formed in a similar manner from the semicarbazone of lavulic acid. Pa-Dimethyllaevu- lic acid can be prepared synthetically from acetonedicar boxylic acid, and its formation in this way affords further confirmation of the con- stitution of dicrotonic acid. Ethyl dimethylacetonedicarboxylate reacts with ethyl bromoacetate to form triethy Z aa,-dimethykacetonedicarboxy- acetate, CO,Et*CHMe*CO*CMe(CO,Et)*CH,*CO,Et, which boils a t 19 1 -5O under 16 mm.pressure. CHBrMe*CH(CO,H)*CHMe*CH,* CO,H, is formed by the combination of hydrogen bromide with dicrotonic acid and crystallises in aggregates of needles; the acid readily loses bromine, and could not be obtained quite pure. When distilled, it forms crotonic acid together with a smaller amount of /3-methyl-yrS-IZex- 0-co P-Methyl-y-bronaoethylglzctaric acid,ORGANIC CHEMISTRY. 65 enoic acid, CHMe:CH*CHMe*CH,*CO,H, which is also formed when the acid is heated with water. It is a colourless liquid with a rancid smell, and boils at 209-210°. With bromine, it forms y8-dibromo- P-methylhexoic acid, CHBrMe*CHBr*CHMe*CH,*CO,H, which crystal- lises in rhombic tablets and melts at 135-1 36'.~-lllet?~~l-a-et?~ylglutar~c acid, CO,H*CHEt*CHMe*CH,*CO,H, is formed by the reduction of p-methyl-y-bromoethylglutaric acid and crystallises in colourless prisms melting at 100-101' ; K= 0-0067. By FRITZ FICHTEB and SYLVAIN HIRSCH (Ber., 1900, 33, 3270-3276).-Bromo-as- dimethylsuccinic acid, which could not be obtainea pure by von Baeyer and Villiger (Abstr., 1897, i, 597), yields on distillation the >0, which forms stout needles, melts at 45', pure anhydride, and boils at 121-123' under 13 mm. pressure. On evaporating its aqueous solution in a vacuum, the pure acid, C',H,O,Br, is obtained as a hard, crystalline crust melting a t 153'; if the anhydride is dissolved in benzene containing water, slender needles of the acid with $C,H, separate, which melt at 133", and effloresce in the air, the acid thus obtained melting at 143O.The B-lactone of as-dimethvlmalic acid distils at 145-150' under A. H. The P-Lactone of as-Dimethylmalic Acid. $%Te2-C0 CHBr*CO .I 13 mm. pressure, being converted into the isomeric ccnhydride, yMe,*CO >0, a colourless oil which is also formed on distilling OH* OH-CO as-dimethylmalic acid under the same conditions, although decom- pcsition occurs at atmospheric pressure. Since the anhydride readily absorbs water from the air to form dimethylmalic acid, it differs essentially from the isomeric lactone which crystallises from water unchanged. W. A. D. Ey MAX CONRAD (Bey., 1900, 33, 3432-3438).--Methyt oxalyldimethylacetoacetate, CO,Me*CO*CH,* CO C Me,.CO,Me, prepared by the action of sodium on an ethereal solution of methyl oxalate and methyl dimethylacetoacetate and purified by converting into the copper compound, is a pale yellow oil which has a sp. gr. 1.193 at 17'/15O, boils and partially decomposes a t 270-278", has a distinct acid reaction, mixes readily with ether, alcohol, or benzene, and gives a cherry-red coloration with alcoholic ferric chloride. The calcium derivative, Ca(CloH,,O,),, dissolves in ether, softens a t 115O, and melts at 125'; the cobcclt derivative, Co(CloHl,O,),, melts a t 98-100' ; the copper derivative, Cu(Cl,Hl,O,),, melts at 128-130' ; the compound with ammonia, Cl,HpO,N, forms minute, white needles, and melts at 1 10". Methyl anz~z~zo-o~~6~?/ldirnethylcccetoacetate, CO,Me*C(NHPh):CH* CO*CMe,* CO,Me, or CO,Me*CO*CH:C( NHPh).CMe,* CO,Me, crystallises from methyl alcohol in large, well-formed, sulphur-yellow prisms aod melts at Sl'; t h e monoxime, C10H150GN, crystsllises from hot water and melts at 9 lo.Oxidyldimethylacetoacetic acid forms colourless crystals, melts at 180' with evolution of carbon dioxide, and Oxalyldialkylacetoacetic Esters.66 ABSTRACTS OF CHEMICAL PAPERS, also loses carbon dioxide in aqueous solution a t 70--80°, giving an isobutyrylpyruvic acid. Methyl bromo-oxalyldimetliylacetoacetate is a yellow oil ; it forms a copper derivative, Cu(CloH12Br06),, crystalking from ether in green S FH* CO *CO,Me or needles. The thiaxyl derivative, NH:C<N: C,CMe,.CO,Me - 1 A S FH*CO*CMe,* C0,Me , prepared by the action of thiocarb- NH: c<N : C* c O,l\le amide on the &bromo-ester, crystallisea from hot water in white needles and melts a t 138'.By the action of potassium acetate on the bromo-ester in methyl alcoholic solution, methyl oxalate and the acetate of methyl hydroxydimethylacetoacetate are produced as decomposition products of methyl acetoxyoxalyldimethglacetoacetate. Ethyl oxalyldiethykucetoucetate, CO,Et*CO*CH,* CO*CEt,* CO,Et, is a colourless oil which forms a copper derivative and gives a red color- ation with alcoholic ferric chloride. By distillation, it gives ethyl aa-dieth yZacetonedicarboxyZute, CO,Et*CH; CO*CEt,* CO,Et, boiling at 275-285'. T. 11. L. Glycuronic Acid. I. By CARL NEUBERG (Ber., 1900, 33, 3315-3323).-Several of the compounds described by the author have been previously described by Giemsa (this vol., i, 11).Glycurono- lactane (glycurone) is best obtained by boiling euxanthic acid with dilute sulphuric acid. GZycuroneamylmercaptal was only obtained in the form of a viscid oil. Glycurorzethiosemicurbaxone, OH*CH<~~~~J>CHXIH(OH)*CH:N*NH*CS-NH,, crystallises from water in fascicular groups of needles melting at 223O, and is insoluble in the ordinary organic solvents. Glycurone- diphenylhydraxone, C6H,0, :N,Ph,, crystallises in needles melting at 150'. Glycuroneoxime is converted by acetic anhydride and sodium acetate into the tetraacetyl derivative of the seminitrile of d-saccharic acid, which has not, however, been obtained pure. Glycuronic acid forms characteristic salts with many of the alkaloids.The cinchonine salt, C6H,,0~,Cl,H,,N,0, crystallises in characteristic white needles melting at 204O, and has [.ID + 138.6'. The quinine salt softens at 175', melts a t 180°, and has [a], - 80.1'. The brucine salt crystallises in very slender needles uielting at 200', and the styychnine salt closely resembles it. Glycurone can readily be separated from the sugars by means of its thiosemicarbazone, and glycuronic acid by the aid of the cinchonine salt, whilst the acid is best detected in presence of the sugars by means of the p-bromophenylhydrazine compound. Acidimetry of Aldehydes and Ketones. By A. ASTRTJC and H. MURCO (Compt. rend., 1900, 131, 943-945).-A number of alde- hydes and ketones of simple and mixed function were examined as to their behaviour towards the indicators helianthin A, phenolphthalein, and Poirrier's-blue.The simple aliphatic and aromatic aldehydes are neutral towards all three indicators. Glyoxal, the only simple dialdehyde examined, reacts A. H.ORGANIC CHEMISTRY. 67 with one equivalent of alkali, but the process is slow. Halogenated aldehydes, such as. chloral hydrate, chloral alcoholate, and bromal, are neutralised by one equivalent of alkali. Hydroxybutyraldehyde and aldehydic sugars are neutral towards all three indicators, whereas tsalicylaldehyde, p-hydroxybenzaldehyde, methylprotocatechuic alde- hyde (vanillin), and methybnoprotocatechuic aldehyde (piperonal) are neutral towards helianthin but monobasic towards phenolphthalein or Poirrier’s-blue. The simple aliphatic and aromatic ketones are without action on either of the three indicators.Acetylacetone is exactly monobasic fowards Poirrier’s-blue, but behaves less definitely with phenol- phthalein. The exact titration of methylacetylacetone is impossible with either of these indicators. Acetonylacetone is neutral. Chloro- acetone and bromoacetophenone are neutral towards helianthin and monobasic towards phenolphthalein or Poirrier’s-blue. The ketonic sugars are neutral, Pyruvic and lzevulic acids are exactly monobasic towards phenolphthalein or Poirrier’s-blue, but with helianthin the neutral point is reached before one equivalent of alkali has been added. N. L. Search for other Sugars than Xylose and Dextrose in the Products of the Hydrolysis of Wood from the Trunks of Trees.By FRANCIS H. STORER (Bull. Bussey Inst., 1908, 2,437-467). -The author has submitted samples of wood from the trunks of the sugar maple (Acer saccharinurn) and birch (Betula populqolia), and from the root of the former tree to the action of hydrochloric and sulphuric acids under various conditions, and determined the cupric- reducing and rotatory powers of the solutions thus produced, in order t~ obtain, if possible, indications of the presence in wood of substances hitherto undeteoted. Cotton cloth was also subjected to the same treatment. The results of these experiments led to the following conclusions, When strong sulphuric acid is allowed to act on cellulose, and the product boiled with dilute acid, the whole of the cellulose is not readily converted into dextrose, as has been frequently stated.The oompounds which carbohydrates form with sulphuric acid are very difficult to decompose by long continued boiling, and, as a general rule, a considerable part of the organic matter with which the strong acid a t first united is not changed into dextrose when sub- sequently boiled with the dilute acid ; some part of this undecomposed substance remains admixed with the dextrose syrup, and tends finally to contaminate the solid dexfrose. I f the calcium or barium salts of these compounds of carbohydrates with sulphuric acid are boiled for a long time, some quantity of the salts is liable to remain undecomposed and render the dextrose syrup impure; when such syrups are con- centrated, crystals of two kinds are obtained, one of which consists entirely of inorganic! matter, Bdchamp (AM.chim. phys., 1831, [ii], 48, 502) appears to have mistaken the latter substance for sugar, and it is probably due to the same cause that Berthelot (Ann. chim. phys., 1859, [ iiiJ, 55,293) was led to state that the dextrose from wood differs from all other dextroses.68 ABSTRACTS OF CEEMICAL PAPERS. The quantity of dextrose which is usually said to be obtainable from a given weight of cellulose is largely in excess of that observed by the author ; such statements, however, are generally based merely on the reducing power of the product of hydrolysis, whereas in the solutions obtained, substances other than dextrose are present which are capable of reducing considerable quantities of Fehling's solution.The portion of the product of hydrolysis which is insoluble in alcohol is usually regarded as ' dextrin,' but its high reducing power suggests the presence of a sugar analogous to isomaltose. If, however, pure dextrose is treated with sulphuric acid under conditions similar t o those observed in the hydrolysis of wood, a part of the residue ob- tained is insoluble in aloohol, and resembles the ' dextrin ' from wood ; it may be, therefore, that in each case some of the dextrose is converted by the alcohol into the insoluble dextrose anhydride. The difficulties attending the study of the hydrolysis of cellulose are greatly increased by the reversion of dextrose to dextrin which may occur in the process. By LOUIS HENRY (Be?.., 1900, 33, 3169-3171.Compare this vol., i, 16, and Strauss, ibid., 17).- A number of amino-alcohols have been prepared by the reduction of the corresponding nitro-compounds with tin and hydrochloric acid, or from cyano-alcohols by reduction with sodium and alcohol. They are somewhat viscid liquids with a fishy odour, and dissolve in water, but, with the exception of methyl-a-aminoethylcarbinol, are insoluble in ether : E. G. Formation of Amino-alcohols. Boiling point. Sp. gr. P-.Aminoethyl alcohol, y-Aminopropy 1 alcohol, 6-Aminobutyl alcohol, P-Aminoisopropyl alcohol, Methyl-a-aminoet hylcar binol, Whennitroacetone is kept for some time it turns brown, whereas OH*CH,*CH,*NH ,.................. 171' I1.022 at20° OH*[CH,],*NH, ..................... 18'7-188 1.020 a t 12 OH*[CH,],*NH ,..................... 206 0.967 at 12 OH*CHMe*CH,*NH ,............... 160-161 0.973 a t 18 OH*CHMe*CHMe*NH,. ........... 159-160 0.9423 at 18 nitroethyl alcohol remains iolourless even when kept for some years. J. J. S. Hydraaides and Azoimides of' Organic Acids. XVII. Syn- thesis of ay-Diaminopropane and aC-Diaminohexane from Glutaric and Suberic Acids respectively. By THEODOR CURTIUS and HANS CLEMM (J. p. Chem., 1900, [ii], 62, 189-211).-Glutaric di- hydraxide, CH,(C1H2*C0*NH*NH2),, obtained by boiling hydrazine hydrate with ethyl glutarate, crystallises in silky leaflets which melt at 176O, reduces Fehling's solution, forms a colourless hydrochloride, and when shaken with benzaldehyde yields dibe~xylideneglzctaric dihydv- axide, which crystallises from glacial acetic acid in small needles melt- ing at 231-232O.Glutaric diccxoimide, CH,(CH,*CO*N,),, is obtained by adding a cold solution of sodium nitrite to a cooled solution ofORGANIC CHEMISTRY. 69 glutaric dihydrazide hydrochloride under ether ; it is a clear, mobile, explosive oil with a suffocating odour, does not solidify at -15', is decomposed by sodium hydroxide, yielding sodium azoimide ; when treated with ethyl alcohol, it yields diethyl trimethyleneurethane, CH,(CH,*NH*CO,Et),, which is a viscous oil boiling and decomposing at 290-300°, and solidifying to feathery crystals after standing in a freezing mixture for some time; when heated in a sealed tube a t 100- 110' for some hours, it yields trimethylenediamine hydrochloride. Glutaric diazoimide, when slightly warmed with water, explodes with the formation of small quantities of trimethylenecccrbamide which melts at about 250'.The corresponding suberic compounds were obtained by analogous methods. Xuberic dilhydraxide, C2H4( CH,*CH,*CO*NH*NH,),, crys- tallises in large, colourless, lustrous leaflets which melt at 185--186O, and yields a dibenzylidene compound which crystallises in small, white needles and melts at 197". Xuberic diuxoimide is obtained in compact crystals which melt at 25' and explode when heated further ; when treated with alcoholic ammonia, it yields suberamide, which crystallises from alcohol and melts at 216' ; when treated with aniline, it yields hexumeth ylenedicarbunilide? C,H,,( NH*CO*NHP h),, which crys tallises in long, thin, colourless prisms and melts at 220' ; when treated with anhydrous alcohol, it yields diethyl hexamethylenediuvethane, which crystallises in long, lustrous, colourless needles melting a t 84' ; with alcohol in the presence of water, it yields the urethaieecarbarnide, CO(NH*[CH,]G*NH*C02Et),, which is a colourless, crystalline com- pound melting a t 132' ; when treated with water, it yields hexrxmetlbyl- enecurbamide, which crystallises in long, lustrous, colourless needles melting a t 84'.a[-&mainohezane dihydrochloride, C,H,,(NH2),,2HC1, best prepared by the hydrolysis of diethyl hexamethyleneurethane with concentrated hydrochloric acid, crystallises in colourless needles, melts at 248', and when treated with solid potash yields at-diumino- hexane (hexamethylenediamine), which cry stallises in silky, colourless leaflets, melts at 42', boils at 100' under a pressure of 20 mm., is very hygroscopic, and absorbs carbon dioxide with the formation of a car- bonate; it forms a diacetyl derivative which crystallises in small needles melting a t 125-126', a dibenxoyl derivative which crystallises in colourless plates melting at 157--158O, apicvate, C,H1,N,,2C6H3O7N3, which decomposes at about 200', an oxalccte, C6Hl6N2, 2H,C,0,,H20, which melts and decomposes a t 1 6S0, a pZ~ctinichZoride,C~H~~N~,H,PtCl, which decomposes between 222' and 2 2 4 O , an uurichlorzde which crys- tallises in long, compact, lustrous yellow prisms, and a mercui-ichloyide, C6H,BN,,2HC1,4HgCl,, which crystallises in long leaflets and melts at 228-230°, all of which are analogous to the salts and derivatives of pentamethylenediamine ; it dissolves uric acid, and has a very similar physiological action to piperazine and urotropine.The melting points of the diamines, like those of the dibasic acids, of the normal hydrocarbons containing an even number of carbon atoms are higher than those containing an uneven number, whilst the boiling points increase regularly with nurn ber of carbon atoms. C6H12( NH*C02E t)2, R. H. P.70 ABSTRACTS OF CHEMICAL PAPERS. Hydraeides and Aeoimides of Organic Acids. XVIII. Synthesis of a0-Diaminooctane from the Azide of Sebacic Acid. By THEODOR CURTIUS and WILHELM STELLER (J. pr. Chem , 1900, [ ii], 62, 212-231).--Xe6acic dihydraxide, C,H,(*[CH,]*,CO*NH*NH,),, obtained by the action of hydrazine hydrate on diethyl sebacate, crys- tallises in lustrous, rhombic leaflets, melts at 184-185', and when dry hydrogen chloride is passed into its anhydrous alcoholic solution, yields a dihydrochloride which forms rhombic crystals melting acd de- composing about 250' ; it condenses with benzaldehyde, forming di- benxylidenesebacic dihydruzide, which melts at 158-159', forms a tetrat6enxoyZ derivative which melts a t 250°, and when treated with an alcoholic solution of iodine ( 2 mols.iodine to 5 mols. dihydrazide) CO*NH yields s-sec-sebacic hydrazide, C,Hl,<co.&H, which crystallises from alcohol and melts at 142'. Xebacic diaxoimide, C,H,,(CO*N,),, ob- tained by the action of nitrous acid on the dihydrazide, is a stable, colourless compound, which melts at 33-344 and is not explosive.When treated with aniline, it yields octomethylene dicarbamanilide, C,Hl,(NH*CO*NH*Ph),, which crystallises in flat, right-angled needles melting at 206-2@7' ; when treated with water, octomethylenecadj- amide is formed, which is an insoluble, bluish-white powder decomposing at 216' ; when treated with moist ethyl alcohol, s-dioctomethylenedi- ethylurethanecarbmnide, CO(NH*[CH,],*NH*CO,Et),, is obtained as an amorphous compound melting at 132-133'; when treated with abso- lute ethyl alcohol, diethylootometl~ylenediurethane, C,H,,(NH*Co2Et),, is formed, and crystallises in feathery aggregates melting at 78-80' ; when treated with methyl alcohol, the corresponding dimethylurethane which melts a t 114-115' is obtained.Octomethylenediamine dihydrochloride is best prepared by boiling either the diethyl- or dirnethyl-urethane with concentrated hydrochloric acid for six hours. The derivatives and salts of octomethylenediamine are analogously constituted to those of hexaruethylenediamine (see preceding abstract) ; the dibenxoyl derivative crystallises in silky prisms and melts a t 140', the pic~ate melts at 182-183', the oxalate crystallises in lustrous, white lamins and melts at 223', the rnercuri- chloride crystallises in pinkish aggregates and melts at 189-19 lo, the ccurichloride forms microscopic crystals and melts at 188-189O ; it also forms a characteristic salt with cadmium chloride, which crystal- lises in white aggregates from hydrochloric acid, and does not melt below 300O.When treated with nitrous acid, the diamine yields a greenish oil, which has the odour of octyl alcohol, and is probably octometh y Zeneg lyco 1. Hydrazides and Azoimides of Organic Acids. XIX. Syn- thesis of apy-Triaminopropane from Tricarballylic Acid. By THEODOR CURTIUS and AuausT HE~SE (J. pr. Chem., 1900, [ ii I, 62, 2 3 2-2 46). -Tricar ball y lic trih ydrazid e, C,H,( GO NH* NH,),, obtained by the action of hydrazine hydrate on triethyl tricarballylate, is a crystalline substance melting at 195--196O, and forms a very soluble trihydrocMoride, which melts and decomposes a t 1 48O, a tripicrate which crystallises in small, yellow plates and melts at 1739 and condensation R. H. P.ORGANIC CHEMISTRY. 71 products with benzaldehyde and salicylaldehyde, which are white, microcrystalline substances melting at 2 18' and 205-206" respec- tively; when treated with nitrous acid, it yields tricarballylic triaxomide, C,H,(CO*N,),, which is a clear, explosive oil; this, when treated with anhydrous ethyl alcohol, yields triethyl glycei.yltr iurethane, C,H,(NH*CO,Et),, which melts a t 91-92' ; when treated with water, diglycerylca~bamide, CO NH*C,H5<zE>CO),, which is a white, crystalline substance, is formed.u/3y-Triaminopropane, C,H,(NH,), (compare Gabriel and Michels, Abstr., 1893, i, 31), is a colourless oil which boils at 92-93' under 9 mm. pressure, and forms a trihydi*ochloYide, which is obtained by the hydrolysis of the urethane with hydrochloric acid, crystallibes, with H,O, in colourless, compact plates, and, when anhydrous, begins to sinter at 220°, and melts and decomposes about 250'; it forms an uurichloride, C,H,(NH,),, 3HCl,AuCl,, which melts and decomposes at 210-212', a platinichlokiik, C3H,(NH,),,3HC1,PtCl,, which crystal- lises in needles and decomposes a t 220°, a tvipicrate, which crystallises in long, yellow needles and does not melt below 270', and a tribermoyl derivative, which is a microcrystalline substance melting at 206-207', and is particularly suited for the purification of the base, as when hydrolysed with strong hydrochloric acid it yields the hydrochloride in a pure state.By BRONISLAW PAWLEWSKI (Ber., 1900, 33, 3164).-Pure canarin is readily formed when ammonium persul- phate is added gradually to a solution of ammonium thiocyanate con- tained in an open dish.When a woollen fabric is dipped in ammonium persulphate solution and then in ammonium thiocyanate and the operations repeahed several times, the fabric becomes dyed intensely with canarin. J. J. S. By CARL D. HARRIES and NAURUS WEISS (Ber., 1900, 33, 3418--3149).-The hydrochloride of the ethyl ester of glycine, when treated with potassium cyanate, is converted into ethyl hydantoate, which crystallises in compact needles, melts at 1 3 5 O , and when treated with nitrous acid yields a nitroso- derivative melting at 66-67'; this ester, when heated at 135' for seven hours, or when warmed with 25 per cent. hydrochloric acid, is converted into hydantoin. The hydantoin formed by the latter method melts at 21'7-220' instead of at 215'. Quantitative yields are obtained in all the stages from glycine.By JULIUS TAFEL and ARTHUR WEINSCHENK (Ber., 1900, 33, 3378-3383).-Methyluracil, CO<CEZFG>CH, was dissolved in 50 per cent. sulphuric acid and reduced electrolytically either at 15' or at 50°, between prepared lead electrodes (Abstr., 1900, ii, 588), with a current concentration of 120-150 amperes. The resulting liquid was freed from free sul- phuric acid and evaporated under diminished pressure ; the residue was extracted with boiling chloroform, in which methyltrimethylem- ( R. H. P. Formation of Canarin. A Method of Preparing Hydantoin. R. H. P. Electrolytic Reduction of Methyluracil.72 ABSTRACTS OF CHEMICAL PAPERS. carbarnide, CO<NH-cH, NH*CHMe>CH2, dissolved, whilst the suIphate of ay-diamimo62ctafie, NH,-CHMe*C H,*CH,*NH2, remained behind. Methyltrimethylenecarbamide melts at 200-202°, and is neutral in reaction; it forms a picrate, which was analysed; it is not easily hydrolysed, but when heated with concentrated hydrochloric acid a t 200' (or less well with 30 per cent.sulphuric acid), it loses carbon dioxide and forms diaminobutane. ay-Diaminobutane boils a t 140.5-141*5° under 738 mm. pressure, and has a sp. gr. 0.86; its hydrochzoride, which melts a t 170--172O, and picrate, which is very insoluble and explodes when heated, were analysed. These reactions afford a convenient means of preparing ay-diamino- butane. Methyluracilis reduced electrolytically in the mannerdescribed; the resulting liquid is freed from so much sulphuric acid that three parts of the latter still remain for every 1 part of methyluracil, the liquid is concentrated unkil only 10 C.C.remain per 1 gram of uracil, and the residue is heated for 6 hours a t 2 0 0 O . By JULIUS TAFEL and ARTHUR WEINSCRENK (Ber., 1900, 33, 3383-3387).-Barbituric acid, or malonylcarbamide, CO<NH.Co>CH2, was reduced electro- lytically at 1 6-21°, and the product worked up as in the case of methyl- uracil (preceding abstract). The residue after the evaporation con- tained trimethylenecarbamide, CO<NH. KH-CH CHi>CH2, and hydrouracil, CO<:EZ;6>CH2 ; the latter remained behind when the residue was extracted with cold water, whilst the trimethylenecarbamide dis- solved, and could be recovered from the solution by means of its picrate, which is almost insoluble in cold water.Hydrouracil melts at 274O, and in small quantities sublimes unchanged; it does not dissolve more readily in dilute hydrochloric acid than in water, but it does so in aqueous sodium or barium hydroxide; from these solutions, i t is precipitated by carbon dioxide. By CHARLES CLOEZ (Compt. rend., 1900, 131, 899-90l).-When a disub- stitution derivative of benzene contains a basic group NH, or NR,, and the second group is neutral (Me,Cl) feebly acid (OH) or acid (CO,H), nitration takes place in the para- or ortho-position with respect to the amino-group. Nitration in the meta-position is obtained only in presence of a large excess of sulphuric acid. When the benzene derivative contains an OH group with the groups Me, C1, NO,, or COH, nitration takes place in the ortho- and para- positions, but if the hydroxyl group is converted into an alkyloxy- group, nitration will take place also in the meta-position.With the derivatives CO,H : OH = 1 : 3, three compounds are obtained with the NO, group in the position 2 or 4 or 5. When the derivative contains a Me or C1 group with a NO,, CO,H, or COH group, nitration takes place in the ortho- or para-position with respect to the C1 or Me group. C. F. B. Electrolytic Reduction of Barbituric Acid. NH*CO C. F. B. Nitration of the Disubstitution Derivatives of Benzene.ORGANIC CHEMISTRY. 73 With o-nitro- or p-nitro-benzoic acid, the second nitration takes place in the meta- or para-position with respect to the first nitro-groups. C. H. B. Nitro-derivatives of o-Dinitrosotoluene and o-Dinitroso- xylene.By THEODOR ZINCKE and P. DROST (Annalen, 1900, 313, 299-316. Compare Abstr., 1899, i, 75 1).-Nitro-o-dinityosotoluene [Me : NO, : (NO),= 1 : 2 : 3 : 4 or 1 : 6 : 3 : 41, prepared from 3 : 4-di- nitrosotoluene and fuming nitric acid, crystallises in pale yellow needles which melt and decompose a t 164'; it is also formed when the imide of o-nitro-p-toluidine is added to fuming nitric acid and the product heated in a brine bath, 2 : 6-Dinitro-3 : 4-dinit rosotoluene, obtained by the action of fuming nitric acid on a solution of the nitro-deriva- tive in concentrated sulphuric acid, crgstallises from concentrated nitric acid in silky yellow needles melting and decomposing at 133'. produced when dinitro-p-diazotolueneimide is heated a t 11 O', crystallises from glacial acetic acid in lustrous, yellow leaflets melting a t 145'; dinitro- p-diaxotolueneimide, formed on dissolving nitrodiazotolueneimide in fuming nitric acid, crystallises from alcohol in colourless needles aud melts at 97'.5-Nityo-2 : 3-dinitrosotoluene crystallises from alcokol in yellow leaflets and melts at 70'. 5-Nitro-o-diaxotolzceneimide [ 5-nitrot oluene- 2-tcxoimide], NO2*C6H3Me*N3, melts a t 69O, and when treated with fuming nitric acid is converted into 3 : 5-dinitrotoluene-5-axoimide, which crystallises from alcohol in pale yellow needles, and melts a t 61' ; the latter substance yields 5-nitro-2 : 3-dinitrosotoluene when heated on the water-bath. Nitrodinityosotoluene [P Me : (NO), : NO, = 1 : 2 : 3 : 41, obtained by dissolving 2 : 3-dinitrosotoluene in fuming nitric acid, forms pale yellow, feathery crystals and melts at 162'; a mixture of concen- trated sulphuric and nitric acids converts it into dinitrodinitrosotoluene (? Me : (NO), : (NO,),= 1 : 2 : 3 : 4 : 61, which melts and decomposes a t or 1 : 3 : 4 : 2 : 51, produced by the action of fuming nitric acid on 3 : 4 : 5- nitro-m-xyleneazoimide, crystallises from alcohol in white leaflets melting at 82'; when heated at l l O o , it yields nitrodinitroso-xylene, which crystallises from alcohol in yellow needles, and melts at 116'.1 : 3 : 4- tolylenefurazan and nitric acid, crystallises in long, yellowish needles, and melts at 83'. Dinitroaminocresol [? Me : OH : (NO?), : NH, 7 1 : 2 : 3 : 5 : 41, formed when dinitro-p-tolueneazoimide, is dissolved in concentrated sul- phuric acid, crystallises from boiling water in small, red needles, and melts a t 172', when it decomposes ; the acetyl derivative forms yellow crystals, and melts a t 171'.Dinitroaminocresol [Me : OH : (NO,), : NH, = 1 : 4 : 3 : 5 : 2 or 1 : 6 : 3 : 5 : 21, obtained from dinitro-o-tolueneazo- imide, crystallises from boiling water in small, yellow needles. The compound C7H705N3, a bye-product of the nitration of nitro- p-tolueneazoimide, separates from alcohol in lustrous crystals, and Nitro-o-dinitrosotoluene [? Me : (NO), : NO, = 1 : 3 : 4 : 51, 122-1 23'. Dinitro-m-xyleneaxoimide [Me, : N, : (NO,), 7 1 : 3 : 4 : 5 : 6 Nitrotolylenejhrazan, N0,.C,H2Me<N>0, N prepared from74 ABSTRACTS OF CHEMICAL PAPERS, melts, decomposing, a t 146'; the acetyl derivative melts and evolves gas at 142O. Electro-chemical Reduction of Mononitro-compounds in slightly Alkaline Solutions. By EARL ELBS (Zeit.E'lectrochenz., 1900, 7, 133 and 144).-The author gives a r6sum6 of the results ob- tained in the reduction of 56 mononitro-compounds by the metbocl described by him (Abstr., 1899, i, 270). He shows that, in every case, these results are in harmony with the following representation of the electrolytic reduction of nitrobenzene, due t o Haber and Schmidt M. 0. P. (Zeit. phy.sikml. Chenz., 1900, 32, 271) : e PhXNPh- PhN-NPh' \I \G PbNH*OH. &HPh*sHPh I The vertical arrows indicate electrolytic reductions, the slanting ones indicate purely chemical reactions which take place between the different products.The nature and relative quantities of the final products will, of course, depend on the properties of the compound undergoing reduction. pNitroaniline, for example, yields p-phenylene- diamine, owing to the fact that the nitroso-compound first formed changes very readily into quinoneimide oxime, which can only lead to the diamine ; m-nitroaniline, on the other hand, yields m-diaminoazo- benzene, owing to the fact that the meta-compounds have no tendency to form quinone derivatives. The nitroso- and hydroxylamine com- pounds formed by the direct reduction, therefore, react yielding the azoxy-compound which is further reduced. The azo-compound is always formed by oxidation of the hydrazo- compound; in cases, therefore, where the latter is not readily formed the azo-compound is not produced.The dinitro-compounds behave in an entirely different manner. Isolation of Sulphonic Acids by Vacuum Distillation. T. E. By FRIEDRICH ERAFFT and w. WILKE (Bey., 1900, 33, 3207-3209. Compare Krafft and ROOS, Abstr., 1892, 1219.)--In addition to the sulphonic esters, a number of sulphonic acids can be purified by distillation, when the cathode-light' vacuum is used (Abstr., 1896, ii, 464). The boiling points and melting points of the acids are as follows : B p. at Height of M. p. 0 mm. vaponr column. ............ Benzenesulphonic acid 66' 135' 90 mm. Toluene-p-sulpbonic acid ......... 35 147 65 ,, p-Xylenesulphonic acid.. .......... 48 149 55 ,, p-Chlorobenzenesulphonic acid.. .68 148 60 ,, p-Bromobenzenesulphonic acid.. . 103 155 60 ,, T. M. L.ORGANIC CHEMISTRY. 75 up-Dichlorostyrenes and some Acetylenes. By FRANZ KUNCHELL and R. KORITZKY (Bev., 1900, 33, 3261-3264. Compare Abstr., 1 9 00, i, 6 3 8) .-aap-Dic~~loro-p-ethylstyrene, C,H,Et*CCl: CHCI, prepared by heating chloroacetyl-p-ethylbenzene with phosphorus pentachloride, is a colourless oil boiling at 265"; i t has a sp. gr. 1.2565 a t 17". p-Ethyll0henylchZoroacetyZene, C,H,Et*Ci CCI, obtained by boiling the preceding compound with alcoholic potassium hydroxide, is a yellow oil with an odour of oranges boiling a t 160-170" under 35 mm. pressure ; it has a sp. gr. 1.0871 a t 17". p-Ethylphenylacetylene, C,H,Et*CICH, readily produced by treating up-dichloro-p-ethylstyrene with sodium in ethereal solution, possesses an odour of anise, boils a t 110" under 10 mm.pressure and has a sp. gr. 0.9086 a t 18". p-Czcmyl chloromethyl ketone, which crystallises from alcohol in needles and melts a t 55-56", yields up-dichloyo-p-isopopylstyrene, colourless oil boiling at 190-ZOOc under 23 mm. pressure and having a sp. gr. 1.2736 a t 17". p-isoPropplphenylchloroacetylene, CHMe,-C6H,*C ICCl, a yellow oil boiling at 170-180" under 30 mm. pressure, has a sp. gr. 1,0852 a t 17". p-isoPropyZphenylacetyZene, a liquid having an ethereal odour, boils a t 110-120° under 10 mm. pressure and has a sp. gr. 0.9124 a t 17". ap-Dichloro-2 : 4 : 6-trimethyZstyrene7 C,H,Me,*CCl:CHCl, is a colourless oil boiling at 285-289' under atmospheric pressure ; i t has a sp.gr. 1.1998 at 17". 2 : 4 : 6-17rimethy~hertylchloroacetylene, C,K,Me,*CICCl, a pale yellow oil boiling at 180-190" under 20 mm. pressure, has a sp. gr. 1.0349 at 18". 2 : 4 : 6-~rimethylphenylacety~ne, C,H,Me,*CiCH, has an ethereal odour and boils a t 168-175' undm 20 mm. pressure; it hapa. sp. gr. OWi'31 at 17O. cymyl chkwomethyl ketone, CHMe,*C,H,Me*CO* CH,CI, crystallises fromalcoho1 in needles and melts a t 18-20". up-Dichloro-2 (or 5)-methyZ- 5 (or 2)-isopropylstyrene, CHMe,*C,~H,Me*CCl:CHCl, obtained from the preceding ketone, is a colourless 011 boiling at 268" under atmospheric pressure and having a sp. gr. 1.1296. 2 (or 5)-MethyL5 (or 2)-isopopyl- phenyZchEoroacetylene, CHMe,*C,H,Me*CICCl, a yellow oil, boils at 2 1 5 O under 40 mm. pressure and has a sp.gr. 1.0512 at 17". 2 (or 5)-Methyl- 5 (or 2)-isopropylphenyZacetykne, CHMe,*C,H,Me-CICH, boils a t 128-130" under 50 mm. pressure and has a sp. gr. 0.8882 at 174 The sodium derivatives of tbe above unchlorinated acetylene, obtained in ethereal solution, are very unstable substances, being de- composed even by rubbing on a porous tile; water converts them into the corresponding acetylene and sodium hydroxide. G. T. M, Some Chloromethoxystyrenes. By FRANZ KUNCKELL and K. ERAS (Ber., 1900, 33, 3264-3265. Compare preceding abstract).- a/3-DichZoro-pmethoxystyrene, OMe*C,H;CCl:CHCl, prepared from chloroacetylanisole and phosphorus pentachloride, is a colourless oil boiliaqg at 1 5 5 O under 12 mm. and at 268"mder atmospheric pressure ; it solidifies on cooling and has a sp.gr. 1.291 at 18". B~sdichlo~oethyleneanisole, OMe*C,H,(CCl: CHCl),, obtained from di-76 ABSTRACTS OF CHEMICAL PAPERS, chloroacetylanisole boils a t 160-170° under 17 mm. pressure and has a sp. gr. 1.460 at 21'. I n the case of these methoxystyrenes, the removal of hydrogen chloride by alcoholic potash takes place only in sealed tubes ; sodium fails to withdraw the halogen atoms even at the temperature of the water-bath. G. T. M. Condensation Products of Indene. By JOHANNES THIELE (Ber., 1900, 33, 3395-3401).-The so-called condensation product obtained by Marckwald (Abstr., 1895, i, 535) from indene and benz- aldehyde is shown to be the additive product hydroxybenzylbenzyl- ideneindene, C2,H1,0, and Marckwald's acetate, produced by the action of acetyl chloride, is its chloro derivative, C2,H17C1, which with moist silver oxide yields the hydroxy-compound, and when reduced with zinc dust and acetic acid yields a colotirless, crystalline compound, (C2,H,&, which melts a t 212-213', and is probably a polymeride of benzyl- benzylideneindene.Benxylideneindene, CH<3g>C:CHPh, ob- tained in small quantities by the condensation of benzaldehyde and indene in the presence of alcoholic potash, crystallises in yellow leaflets, melts at 88O, and with concentrated sulphuric acid gives a yellowish-green coloration. Indene and cinnamaldehyde condense readily in the presence of alcoholic potash, with the formation of cin- namylidensindene, CH<Eg:>C:OH*CH:CHPh, which crystnllises in yellowish-red needles, muel& a t 190°, and gives a brown coloration with concentrated sulphuric acid, and an additive compound, C2?H@, which is analogous to hydroxybenzylbenzylideneindene, crystallises in slender, yellow needles, melts a t 160-161°, and gives a green cdora- tion with sulphuric acid.Ethyl indeneoxnlate and p-nitrobenzoyl chloride condense in acetone solution in the presence of pyridine, -I forming ethyl p-nityobenxoylindeneoxalate, which is a yellow, crystalline compound melting 2 113--114" ; the corresponding benxoyl compound is a red oil. Indeneoxalic acid, ob- tained by the careful hydrolysis of the condensation product of ethyl oxalate and indene, crystallises in small, lustrous, red prisms and melts and decomposes at 153-154'. R. H. P. The Phenanthrene Series : Action of Nitrous Acid on Phen- anthrene.By JULIUS SCHMIDT (Bey., 1900, 33, 3251-3260)- Nitrodihydrophenanthrene oxide, O(C,,H1,,*N02)2, obtained in colourless, cubical crystals by saturating a benzene solution of phenanthrene with the fumes evolved from arsenious oxide and nitric acid, melts at 154-155'; it is extremely insoluble in the organic solvents, and, when recrystallised from benzene, separates in transparent prisms containing 1 mol. of benzene and melting a t 134-135'. The sub- stance gives the Liebermann reaction for nitroso-compounds, and on freatment with sodium methoxide yields a nitrophenanthrene meltingORGANIC CHEMISTRY. 77 at 116-11 To, which is not identical with the mononitro-derivatives obtained by the direct nitration of the hydrocarbon.Bismortonitrodih~drop~enanthrene, NO2* C14Hlo Ci4HlO *NO,, which separates from the benzene mother liquor in the preceding experiment, consist’s of small needles melting a t 199-200°, and crystallises from alcohol in pyramidal prisms; it also gives the Liebermann reaction, and develops a brownish-green coloration with cold concentrated sul- phuric acid, which becomes deep green on warming, and changes to yellowish-brown on the addition of alkali. Nononitrobbphenanthran (mononitrobisdi~ydrophenanth?.yZene~, C,4H1~: C1,Hg*N02, produced by heating the preceding compound for 10 minutes a t 200-205*, crystallises from benzene in lustrous, yellow prisms and melts at 210-212°. The author proposes to employ the term “phen- anthran ” for the bivalent radicle, C14H19, derived from dihydrophen- anthrene, and the preceding compound is named in accordance with this nomenclature.Dinitrobisphenant~~ran, N02*C14Hg:C, ,H,*N02, results from the action of sodium ethoxide on bismononitrodihydrophenanthrene ; i t slowly decomposes at 300’ and has not been obtained crystalline owing t o its insolubility in the ordinary solvents. By MOSES GOMBERG (Bw., 1900, 33, 3144-3149 ; J. Amer. Chem. Xoc., 1900,22, 752-757. Compare E. and 0. Fischer, Abstr., 1879, 384).-The triphenylmethane obtained by so many authorities by the action of benzene on carbon tetrachloride in the presence of aluminium chloride is due to a second- ary decomposition of the triphenylchloromethane, which is the first product formed. A 70-87 per cent. yield of the latter may be ob- tained by heating together carbon tetrachloride, benzene, and alumin- ium chloride, and a t the end of the reaction running the well cooled mixture on to a large quantity of powdered ice contained in a vessel surrounded by a good freezing mixture.For a good yield, it is essential that the original substances should be thoroughly dry, and that the product should never be left in con- tact with water for any length of time. Triphenylmethyl. An hstance of Tervalent Carbon. By Moms GOMBERU (Ber., 1900, 33, 3150-3163 ; J. Anzer. Chem. Xoc., 1900, 22, 757-771).-Triphenyl-bromo- or -chloro-methane is not acted on by metallic sodium, but zinc, mercury, or ‘‘ molecular ” silver remove the bromine or chlorine and, in the absence of air the unsaturated hydro- carbon triphenylmethyl, CPh,, is quantitatively formed, but when air is not completely excluded, a considerable amount of triphenylmethyl peroxide, CPh,*O*O*CPh,, is produced.The author recommends the action of pure powdered zinc on a benz- ene solution of the chloro-compound, the operation being conducted in an apparatus free from rubber or cork connections. When the benz- ene solution is concentrated at 30-35’ in an atmosphere of dry car- bon dioxide, a solid residue of the unsaturated hydrocarbon is left ; it does not melt at 60°, dissolves readily in benzene or carbon disulphide, and when a solution is kept for several weeks large, transparent crystals G. T. M. Preparation- of Triphenylchloromethane. J. J. s. VOL. LXXX. i, 978 ABSTRACTS OF CHEMICAL PAPERS.are deposited ; it has not been found possible to obtain these in a pure form, as they rapidly absorb oxygen. Triphenylmethyl peroxide is readily produced when the hydrocarbon is left exposed t o the atmosphere, when air is aspirated through a benz- ene solution of the hydrocarbon, or when the benzene solution is treated with an aqueous solutionof sodium peroxide. It is only spar- inglysoluble intheusual solvents, but may be crystallisedfromchloroform or carbon disulphidein the form of six-sided plates melting a t 185-1 8 6 O ; it is stable in the air but slowly decomposes when its solutions are boiled, When dissolved in cold concentrated sulphuric acid, it gives a yellow solution which quickly darkens, and on dilution triphenylcarbinol is precipitated. When nitrated, it yields Izexanitrotrip~e~~ylmethyl peroxide, O,[C(C,H,*NO,),],, melting a t 2 10' and sparingly soluble in most solvents.Triphenyliodomethccne, CPh,I, is readily obtained when a carbon disulphide solution of the unsaturated hydrocarbon is treated at O0 with a solution of iodine in the same solvent, and is best isolated in an atmosphere of dry carbon dioxide. It is unstable, readily darkens and loses iodine, melts at about 1 3 5 O , and by water, especially in t,he presence of alkalis, is transformed into the carbinol ; boiling with alcohol converts it into triphenylmethane. The corresponding brorno- and chloro-compounds cannot be obtained by a similar process as bromine and chlorine form substitution as well as additive products. J. J. 8. Action of Ethyl Acetonedicarboxylate on Aniline.By EMIL BESTHORN and E. GARBEN (Ber., 1900, 33, 3439--3447).-Ethyl- p-arzilinogl~taconc~te, CO,Et*CH,* C(NHPh):CH*CO,Et, prepared by the interaction of aniline and ethyl acetonedicarboxylate a t the ordinary temperature, crystallises from methyl alcohol in transparent crystals melting at S7", bnt melts at 97-98' when crystallised several times from dry ether; the variation in melting point is explained by the supposition that two isomerides are produced ; the ester is insoluble in water but soluble in organic solvents, .gives a yellowish-brown coloration with aqueous alcoholic ferric chloride, and is hydrolysed by cold dilute mineral acids. Three products are formed when ethyl acetonedicarboxylate is heated with aniline in a sealed tube a t 100'.Acetonedicccrboxydianilide, CO(CH,* CO-NHPh),, crgstallises from absolute alcohol in small, colourless needles, melts, evolving gas, at 155', gives a violet coloration with ferric chloride, and dissolves without decomposition in cold dilute sodium carbonate ; concentrated sulphuric arid gives sulphanilic acid, but the anilide condenses in presence of 80 per cent. acid on the water-bath to 2-quinolone-4-acetic acid. The monoanilide of ethyl P-anilinoghtaconate, NHPh*CO*CH,*C(NHPh): CH* CO,E t, sepzrates from methyl alcohol in well-formed crystals, and when crystallised from dry ether melts a t 129-130'; with ferric chloride, it gives a yellowish colour, rapidly passing to violet as the compound is hydrolysed by the acid of the ferric chloride. The monoanilide of ethyl acetonedicarboxylte, NHPh*CO*CH,*CO*CH,*CO,Et, which is best prepared by the action of cold dilute hydrochloric acid on the preceding compound, crystallises from dry ether, melts at 75-76", dissolvesORCfAh'IC CHEMISTRY, 79 slightly in hot water and separates on cooling in minute felted needles; it dissolves unchanged in cold dilute sodium hydroxide, and can be reprecipitated a t first by carbon dioxide, but hydrolysis of the ester gradually takes place ; it is converted into 2-quinolone-4-acetic acid by warming with concentrated sulphuric acid during 2 hours on the water-bath, NH*C H CO-CH 2-&wino~one-4-ncetic acid, I ' '>C*CH,* CO,H, is only slightly soluble in water and organic solvents, crystallises from hot water in white, felted needles, melts, evolving gas, at 205-206') and by further heating is converted completely into lepidone and carbon dioxide.The ethyl ester, CI3Hl3O3N, crgstallises from benzene in colourless, flat needles, melts at 172--173", and forms soluble crystal- line salts with mineral acids. By W. GROTHE (Arch. Phai*m., 1900, 238, 587-600).-ChIoroncetyl derivat ives of amines, NHR*CO*CH2C1, were prepared by mixing chloroacetic acid with the amine and cooling well, after which the product was mixed with excess of phosphoric oxide. I n the case of rnethylaniline, chloroacetyl chloride was adiied to the well-cooled amine; indeed, this method is preferable in all cases for work on any but quite a small scale. There were prepared (the temperatures given are melting points) : the chloroacetyl derivatives of aniline ; 0- and p-toluidine ; 1 : 3 : 4-xylidine, 109' ; 1 : 2 : Ei-xylidine, 153' ; p-phenetidine, 148' ; methylaniline, 70'.These chloroacetyl derivatives form sulphonacetyl compounds, NHR*CO*CH,*SO,*R, when boiled with sodium benzene- or p-toluene- sulphinate in alcoholic solution, When these compounds are boiled with 10 per cent. alcoholic potash, they are hydrolysed in all cases to the amine, NH,R, carbon dioxide, and a sulphone, CH,*SO,*R. Those prepared are : the phenylsulphonacetyl and p-tolylsuZphonacetyI derivatives of aniline, 142' and 168' respectively ; o-tohidine, 150' and 129O ; p-tohidine, 153O and 157' ; 1 : 3 : 4-xylidine, 141Oand 153-154' ; I : 2 : 5-xylidine, 143' and 160' ; p-phenetidine,,151° and 156' ; methyl- aniline, 125' and 11 2'.Action of Potassium Hydrosulphide, Potassium Cyanide, and Potassium Thiocyanate on Chloroacetanilides. By W, GROTHE (Arch. Phcurm., 1900,238,600-614).-When potassium hydro- sulphide is added gradually to a chloroacetanilide, NHR*CO* CH,CI, both in alcoholic solution, a dianilide of thiodiglycollic acid, (NHR*CO*CH,),S, is obtained. I n this way were prepared (the num- bers given are melting points) : thiodiglycollgl derivatives of aniline ; o-toluidine, 190' ; p-toluidine, 194' ; 1 : 3 : 4-xylidine,^ 194' ; 1 : 2 : 5-syl- idine, 210' ; .p-phenetidine, 221' ; methylaniline, 115'. By oxidation with potassium permnnganate in acetic acid solution, fhese derivatives can be converted into sulphones, (NHR*CO*CH2),S02 ; the yield is not always good, however.There were prepared : sulphono- diacetyl derivatives of aniline, 220-225' ; o-toluidine, 225-226' ; p-tohidine, 221' ; 1 : 2 : 5-xylidine, 237' ; p-phenetidine, 239' ; methyl- aniline, 152'; from 1 : 3 : 4-xylidine the corresponding derivative could not be obtained. T. M. L. Anilides of Alkylsulphonacetic Acids. C . F. B. 9 280 ABSTRACTS OF CHEMICAL PAPERS, By mixing the chloroacetanilides with potassium cyanide in aqueous alcoholic solution, cyanoacetanilides, NHR*CO*CH,*CN, can be ob- tained in some cases. There were prepared : cyanolccetyl derivatives of aniline ;. p-toluidine, 180' ; 1 : 2 : 5-xylidine, 167O; methylaniline; the corresponding derivatives of o-tolnidine, 1 : 3 : 4-xylidine) and p-phenet- idine could not be obtained.When these derivatives are heated with hydrochloric or sulphuric acid, they are hydrolysed to the amine, BH2R, carbon dioxide, acetic acid, and ammonia. When chloroacetanilides are heated with potassium thiocyanate in alcoholic solution, they form thiocyanoacetanilides, NHR*CO*CH,*SCN. There were prepared : thiocyanoacetyl deriva- tives of aniline, 86-87'; o-toluidine, 102-103°; p-toluidine, 125-126O; 1 : 3 : 4-xylidine, 102' ; 1 : 2 : 5-xyZidine, 133' ; p-phenetidine, 164-1 65'; methylaniline, 69'. C. F. B. Action of Potassium Thiocyanate on Chloroacetanilides. By GUSTAV FRERJCHS and HEINRICH BECKURTS (Arch. Pharm., 1900, 238, 615-616).-The thiocyanoacetyl compounds prepared by Grothe (preceding abstract) are derived from thiocyanoacetic acid, with the ex- ception of the methylanilide, which is derived from thiocarbiminoacetie acid.The products obtained from other secondary amines, for instance ethylaniline, are also thiocarbimino-derivatives. Compounds of prim- ary amines with thiocarbiminoacetic acid, on the other hand, are very unstable. I n one case, that of thiocnrbiminoacetyl-p-tozuidide, the compound could be prepared by allowing potassium thiocyanate to act on chloroacetyl-p-toluidide in alcoholic solution for a very short time only; if the solution is heated, this compound is transformed into thiocyanoacetyl-p-toluidide, which finally can be converted into p-tolyl- thiohydantoin. C. F. B. Some Reactions of Substituted Anilines. By WILLIAM OECHSNER DE CONINCK (Compt. rend,, 1900, 131, 945-946).-1n this paper, a minute description is given of the various colour changes and precipitates produced when solutions of methy laniline, dimethylaniline, ethylaniline, and diethylaniline in 97 per cent, alcohol are mixed with dilute or concentrated solutions of cupric chloride, sulphate, or acetate, and also, in the case of methylaniline, with solutions of cobalt or nickel chloride.N. L. Trinitrothymol and its Derivatives. By GUIDO MALDOTTI (Gazxetta, 1900, 30, ii, 365-370J.-Trinitrothymol, prepared by Lallemand (Ann. Chirn. Phys., 1857, [iii], 49, 150), has the normal molecular weight in freezing phenol. The following derivatives have been prepared. The benmyl compound, OISz*C6MePr(N02),, separates from alcohol in silky, pale yellow needles melting at 140' and boiling and decomposing at 250'; it dissolves slightly in water or light petroleum, and is very soluble in benzene, in which its cryoscopic behaviour is normal. The acetyt? derivative crystallises from benzene i u pale yellow scales or plates melting at 135'; it dissolves slightly in ether, more readily in light petroleum, and gives the normal molecular weight in benzene.The ethyl derivative is deposited from alcohol in rhomboidal, nacreous scales or rectangular prisms whichORGANIC CHEMISTRY. 81 melt at 75"; it is soluble in banzene, to which it gives the normal depression of Freezing point. The phenylhydraxine salt separates from alcohol in orange-yellow needles decomposing at 145" ; it behaves normally in freezing phenol solution. T. H. P. By JULIUS SCHMIDT (Beg-., 1900, 33, 32444246, Compare this vol., i, 89).-2 : 4- Dinitro-a-naphthol is produced when an ethereal solution of a-naphthol is saturated with the pas evolved from arsenious oxide and nitric acid ; Action of Nitrous Acid on a- and P-Naphthols. &naphthol, when sirnirarly treated, yields the dinitro-/3-naphthol melting at 195O.G. T. M. Addition of Aldehydoaminic Bases to Naphthols. By MARIO BETTI [with CESARE SPERONI] (Gaxxetta, 1900, 30, ii, 301--309).-The naphthols resemble the enolic form of ethyl acetoacetate in containing the grouping *CH:C(OH)* in their molecules; and further, they give, with aldehydoaminic bases, additive compounds similar to those ob- tained with ethyl acetoacetate. BenxyZidenec~niZ-,9-naphthoZ, NHPh*CHPh*C,,H,*OH, prepared from benzylideneaniline and /I-naph thol, crystallises from alcohol in aggre- gates of lustrous, white needles which melt at 170° and are soluble in benzene; it is readily decomposed by cold dilute acid but is stable towards alkali hydroxides, The presence of a drop of piperidine seems t o greatly accelerate its formation.m-NitrobenxyZidenean~~~-napht~oZ, N0,*C6~~oCH(NHPh)*Cl,H,*OH, separates from a mixture of benzene and light petroleum as a yeilowish- white, crystalline powder melting at 152O. Benxylidene-P-naphth yZc6mine-P~n~phthoZ,C,,H~* NH.0 HP h* C,,H6* OH, separates from alcohol as a white, crystalline powder which melts at 175" and is slightly reddened by the action of light. BenxyZideneaniEa-nap~t~oZ, C,,Hl,ON, is deposited by the addition of light petroleum t a its benzene solution in white crystals melting at 142' to an orange-yellow liquid.These compounds are insoluble in water and their alcoholic solu- tions give no coloration with aqueous ferric chloride, but in benzene solution they give a reddish-violet colour with absolute ethereal ferric chloride solution. On mixing benzene solutions of benzylideneaniline and picric acid, yellow needles of benxylideneaniline picrate, Cl9HI4O7N4, melting a t 173' are obtained. Condensation between @Naphthol, Aldehydes, and Amines. By MARIO BETTI (Gaxxetta, 1900, 30, ii, 3 10 -3 16)-Under suitable conditions, P-naphthol condenses with an aldehyde (2 mols.) and a primary amine (1 mol.) with elimination of 2H,O. The substances obtained in this way crystallise well, have a high melting point, can be boiled with 25 per cent.potassium hydroxide solution without undergoing change, whilst prolonged boiling with hydrochloric acid yields the aldehyde employed ; they are probably oxyazine derivatives. No condensation occurs if the P-naphthol is replaced by phenol or by diethyl malonate ; secondary amines cannot replace the primary nor can acetone be used instead of an aldehyde. T. H. P.82 ABSTRACTS OF CHEMICAL PAPERS. P-Naphthol, benzaldehgde, and ammonia yield i n almost theoretical quantity a compound, C,,H,,ON, crys tallising from alcohol in white needles which melt at 150' and are soluble in benzene; ethereal ferric chloride gives an intense reddish-violet coloration with the benzene solution. Fusion with potassium hydroxide yields ammonia, whilst long boiling with hydrochloric acid gives benzaldehyde and a substance separating in white needles. The ucetpl derivative of the condensation product is deposited from alcohol in lustrous, white crystals melting a t 188-189°, and in benzene solution gives no coloration with ferric chloride.P-Naphthol, benzaldehyde, and aniline yield a compound, C,oH,,ON, which is readily soluble irt benzene or chloroform, and separates from amyl alcohol in rosettes of small, white needles which begin to turn yellow at 160°, become orange-coloured a t 185' and melt a t 200'. From P-naphthol, furfuraldehyde, and ammonia, a compound, C20H,,0,N, is obtained, which separates from alcohol in mammillary tufts of long, white needles melting at 115' ; in benzene solution, it gives an intense violet coloration with ethereal ferric chloride.@-Naphthol, valeraldehyde, m d ammonia yield a compownd, C,,H,,ON, crystallising from alcohol in tufts of long, lustrous white needles melting at 92'; its benzene solution gives an intense violet coloration with ethereal ferric chloride. T. H. P. Etheriflcation of Triphenylcarbinols by Alcohols. By OTTO FISCHER (Bey,, 1900, 33, 3356-3357).-0n dissolving the malachite- green base in boiling methyl alcohol, the methyl ether, C2,H2,0K2, sepa- rates inwhite leafletswhich rapidly become green, and melt a t 150-151'; if the ether is dried rapidly over alkali, it does not subsequently become coloured. Acids, even acetic acid, remove the methoxyl group and yield salts of malachite-green, The corresponding ethyl ether, obtained a t a temperature of 80-1 TO0, forms concentrically grouped, colourless leaflets and melts at 162O ; the benxyl ether is obtained only a t tern peratures above 140-150°, and forms white, silky needles, which when dried over alkali, retain their colour.I t softens a t 195', melts at 19So, is coloured green by acids, and is decomposed by dilute sul- phuric acid at looo into benzyl alcohol and the sulphate of the mala- chite-green base. W. A. D. By H. COUSIN (Compt. rend., 1900, 131, 901-903).-When tribromoguaiacol, OH*C,HBr,*OMe, is oxidised with nitric acid in presence of acetic acid and some alcohol, it yields a compound, C,,H,O,Br,, which forms orange- red, flattened needles, melts a t 186-18S0, and is insoluble in water, but dissolves readily in organic solvents.When treated with reduc- ing agents, it yields a colourless compound, C,,H,O,Br,, which forms prismatic crystals melting at 170-1 72'. With ferric chloride, its alcoholic solution gives a green coloration which changes to violet on addition of a trace of sodium carbonate. Both compounds yield diphenyl when treated with zinc dust. The red compound is a Action of Nitric Acid on Tribrornoguaiacol. - - quinone which probably has the constitution oH*%HBr2*?, whilst OH*C,HBr,*OORGANIC CHEMISTRY. 83 the colourless compound is the corresponding quinol. The action of nitric acid on tribromoguaiacol is similar to, but not identical with, its action on trichloroguaiacol (Abstr., 1900, i, 487). C. H. B. Anildiacetic-o-carboxylic Acid. By DANIEL VORLLNDER and E.MUMME (Bey., 1900, 33, 3182-3183).-AniZdiacetic-o-car60xyZic ncid (diaceticanthrccnilic ncicl), C02H*C,H4*N(CH,*C0,H),, is obtained when anthranilic acid and excess of chloroacetic acid interact in neutral or alkaline solution, It crystallises from hot water in colourless tablets or leaflets and melts and decomposes at 212'. Its conductivity shows it to be powerfully acidic, but it cannot be titrated as a tribasic acid. It is not acted on by nitrous acid and its alcoholic solution is not coloured by ferric chloride. Unlike phenylglycinecarboxylic acid, it is readily esterified and with alcohol and sulphuric acid is converted into its trimethyl ester, CI1H8O6NMe3, melting a t 62". When the acid is heated with alkali hydroxides, it condenses to an indoxyl derivative which is oxidised by ferric chloride and strong hydrochloric acid to an indigotin-like dye, possibly C02H*CH2*~648==C_N*CH20 C0,H' The trimethyl ester, on treatment with sodium ethoxide, is converted into the methyl ester of an indoxylacetic acid, possibly 7 H *CO QO*Y6H4 OH*? ==? *CO,Me C,H,*N*CH,*CO,H' This is a well-crystallised substance and melts at 163O.Esters of Acylphenylglycine-o-carboxylic Acids. By DANIEL VOR- LBNDER~~~W.MEUSEL(B~?*., 1900,33,3183-3185).-1t hasbeen shown by Vorlander and Weissbrenner (Abstr., 1900, i, 295) that the acetyl derivatives of phenylglycinecarboxylic acid are readily converted by acidsoralkalis into indigotin. It was presumed that these esters might be A. L. - - derivatives of the type C , H 4 ~ $ ? ~ # $ ~ ~ C H * C 0 , R , the conversion of which into indigotin derivative; woufd be readily understood.Di- ethyl acetylphenylglycinecarboxylate may be prepared by the following different processes : 1, esterification of acetylphenylglycinecarboxylic acid ; 2, acetylation of the esters of phenylglycinecarboxylic acid ; and 3, action of ethyl iodide on silver acetylphenylglycinecarboxylate. Xoreover, the isomeric monoethyl esters, C,,H,,O,N, of acetylphenyl- glycinecarboxylic acid have been prepared ; that obtained by partial hydrolysis of the diethyl ester melts at 130--132O, and that by partial esterification of the acid a t 86-87O. These are not convertedinto indigo by dilute alkali and possess the normal constitutions, C02Et*C,H4*NAc*CH,*C0,H and C0,H*C,H4*NAc*CH2*C02Et. The authors have finally proved that it is possible to detect indoxyl derivatives by means of warm 60 per cent.sulphuric acid, which con- verts them into indigotinsulphonic acids. The authors draw the conclusion- that the diethyl esters referred to are true derivatives of acetylphenylglycinecarboxylic acid and that their conversion into indigotin is preceded by intramolecular change into i ndox y 1 derivatives. A. L.84 ABSTRACTS OF CHEMICAL PAPERS. Action of Air and Water on P-Benzylhydroxylamine. By EUGEN BAMBERGER and BOGDAN SZOLAYSKI (Ber., 1900,:33,3193-3201. Compare Abstr., 1900, i, 531).-When pure air is passed through /I-benzylhydroxylamine suspended in water for several months, it is converted into a dense, viscid oil, which finally becomes semi- solid.The product contains benzaldoxime, benzaldehyde, and benzoic . I - C HPh acid, benzglisobenzaldioxime, O<keCHOph, benzaldoxime anhydride, C,,H1,ON,, a neutral substance melt& at 21 2-21 3', benzylidene- benzhydrazide, CHPh:N-NH*COPh, dibenzoylhydrazine, C,,H1,O,N,. Bisnitrosobenzyl and azoxybenzyl could not be detected. As in the case of the oxidation of arylhydroxylamines, hydrogen peroxide is pro- duced in considerable quantities. The neutral substance above men- tioned crystallises in white, silky, felted needles, is very sparingly soluble in alcohol, and is indiEerent towards bases and acids; its nature has not yet been ascertained. Nitrosulphosalicylic Acids. By ROBERT HIRSCH (Ber., 1900,33, 3238-3241).-Sulphosalicylic acid (Mendius, Annalen, 1857,103, 45), prepared by the action of sulphuric acid on salicylic acid at looo, can be salted out from its solution, and can be crystallised from a concen- trated salt solution or from a little hot water.Contrary to Remsen's statement (Abstr., 1874, 1167 ; 1876, i, 594), the acid appears to be homogeneous, ncd only one potassium salt could be isolated. The nitration of salicylic acid (Hubner, Abstr., 1876, i, 593; 18'79, 380) can be carried out smoothly by dissolving in sulphuric acid and adding a mixture of nitric and sulphuric acids until no marked rise of tem- perature occurs on mixing, the temperature being kept below 10'. A nitvosuZjAosaZicyZic acid can be prepared by nitrating sulphosalicylic acid at 30-40° by the method just described. The barium salt, A.L. CO OH* C,H,( N0,)<s0,2>Ba, crystallises from hot water in yellowish- red needles, and is aimost insoluble in cold water. Hydroxyphenylcinnamic Acid. By MARUSSIA BAKUNIN (Gaaxetta, 1900, 30, ii, 370-377).-The hydroxyphenylcinnamic acid melting at 120" prepared by Vandevelde (Abstr., 1898, i, 670) by the interaction of sodium hydroxyphenylacetate, benzaldehyde, and acetic anhydride is a mixture of cinnamic acid and the hydroxyphenyl- cinnamic acid melting a t 181' obtained by Oglialoro (Abstr., 1881, 276). Thephenyh ester melts a t 1 0 7 O , and not, as stated by Vande- velde, at 74', which is the melting point of phenyl cinnamate. T. M. L. T. H. P. Addition of Hetomethane Derivatives to Unsaturated Com- pounds. By DANIEL VORLANDER (Ber., 1900, 33, 31 85-3187).-1t is often observed that ethyl sodiomalonate will unite with ap-un- saturated ketones when benzene or ether is used as the diluent, but not if alcohol is used.The explanation of this appears to be that the reaction is a reversible one, and that the reverse change is slower i n the non-hydroxylic solvents. Thus, whilst ethyl pulegonemalonate may be prepared by heatingORGANIC CHEMISTRY 85 pulegone with ethyl sodiomalonate dissolved in benzene or ether, it is broken up into these constituents when heated with an alcoholic solu- tion of sodium ethoxide. I n a similar manner, ethyl benzylidenebis- benzoylacetate is converted by alcoholic sodium ethoxide into ethyl benzoylacetate and ethyl benzylidenebenzoylacetate (compare also Dieckmann, Abstr., 1900, i, 623).A Saturated Dicyclic Dicarboxylic Acid. By WILHELM BRAREN and EDUARD BUCHNER (Ber., 1900, 33, 3453-3456).--Ethyl A'-tetm- hydrobenxoate prepared from the corresponding acid (Aschan Abstr., 1891, 1481 ; 1893, i, 33) is an oil boiling at 206-208O, which, when heated with ethyl diazoacetate at 110-120° for 16-24 hours or until all the diazoacetate has disappeared, yields ethyl 1 : 2-norcarandicarb- >CH*CO,Et ; this, after purification by dis- oxylate, tillation in steam, forms an oil boiling a t 159-160° under 18 mm pres- sure ; on hydrolysis with alcoholic potash, it yields cis-1 : 2-norcavandi- carboxylic acid, C7H19(C0,H),, together with a n oily mass ; the cis-acid melts at 152-15309 is readily soluble in water, alcohol or ether, and is not acted on by cold permanganate in alkaline solution.When boiled for l & hours with acetyl chloride, it yields the anhydride, C,H,,:C,P,, which crystallises from cirbon disulphide in colourless plates melting at 86-87O; when this is dissolved in sodium hydroxide solution and then acidified, it yields the original acid, and hence follows the cis- configuration of the latter. Euxanthic Acid. By CARL GRAEBE (Ber., 1900,33,3360-3362).- Although the potassium and sodium salts of euxanthic acid are of the type C~gHl~OllM, the silver salt, precipitated from the potassium salt by silver nitrate, has the composition C,,H,,O,,Ag, derived from an anhydride of the acid; the methyl estey melting at 2 1 2 O , and the ethyl ester, melting at 19S0, prepared from the silver s i l t are of a similar type, C,,Hl,Ol,*R.These esters, but not the free acid, combine directly with iodine (apparently 2 atoms at most) to form gelatinous, insoluble blue substances. With acetic anhydride, the esters yield colourless acetyl derivatives, derived not from the esters themselves, but from the anhydride, C,,H,,O,,; their composition remains to be determined. With benzoyl chloride, analogous substances are formed, A. L. QH2* CH, QH-- CH,*C H,* c( C 0,E t) J. J. S. the ultimate product beini the compound C19H11010B~5. W. A. D. Lichens and their Characteristic Constituenta. By OSWALD HESSE (J. pr. Chem., 1900, [ii], 62, 321-363. Compare Abstr., 1898, i, 531, 6 7 9 ; 1899, i, 38l).-Specimens of usnic acid obtained from Usnecc ceratina, Cladonia rangifera var. silvatica, Parrnelia caprata and Placodium saxicolum var.vulgare gave [ + 494*1°, + 494*6O, i- 492*2', and + 492.7' respectively, whilst that from Cetraria pinastri gave [uID - 494.1'. When either d- or Z-usnic acid is melted, it is instantly converted into the inactive modi6cation. The d-acid melts at 195-197', the Z-acid at 1 9 7 O , and the inactive form at 192-193'. The potassium salts of the d- and Z-acids crystallise from water with 3H,O, and from alcohol with 1H,O. The inactive modifications86 ABSTRACTS OF CHEMICAL PAPERS. obtained by fusion of the d- and Z-acid respectively and that crystallised from a mixture of the two active forms are not absolutely identical, since the potassium salt crystallises in a different form in each case; the sodium salt, however, crystallises only in one form (compare Widman, Abstr., 1900, i, 235).Ebullioscopic determination of the molecular weight of the substance obtained by the action of acetic anhydride on cl-usnic acid (Hesse, Abstr., 1895, i, 298) gave 338-339, whilst a substance of the formula (C1sH1506)2.0 requires 670 ; the author concludes that the supposed anhydride is a mixture of the lactone, C,,H,,O,, and the d-acid. A further examination of ~ccndekaricc concolor has shown that the ' dipulvic acid ' previously described consists of pulvic anhy- dride together with a smaller quantity of calycin (compare Zopf, Abstr., 1899, i, 716). CandeZaria vitellina obtained from four different sources furnished a substance composed of calycin and pulvic anhydride in varying proportions.Sticta aurata yields stictaurin,' C,,H, 20, which has the properties attributed to it by Zopf (kc. cit.). Stictch Desfontccinii a-munda contains a substance melting at 232O which, when boiled with alcohol, furnishes calycin and ethylpulvic acid. If calycin (1 mol.) and pulvic anhydride (2 mols.) are dissolved in hot glacial acetic acid, a substance, C,,H,,O,,( CX8H1004)2, separates which corresponds in every way with that obtained from Sticta auvatcc and crystallised from the same solvent ; in one case, a substance, ClsHI2O5, was produced resembling that obtained directly from Sticta ccurata by extraction with ether. From a solution of calycin and pulvic anhy- dride in molecular proportion, a substance is obtained in brick-red needles which melts at 216--217°, and agrees in its characters with that yielded by Candelaria vitellina.If, however, more than 1 mol. of calycin is mixed with 1 mol. of pulvic anhydride, the excess bf the former crystallises independently. The author concludes that the colouring mat€er of these lichens is not a definite single substance, but a mixture of calycin and pulvic anhydride in varying proportions, and that the calycin protects the anhydride from alteration. Oalycium chlorellum (C. chlorinum), yields vulpic acid and traces of leprarin. CaZyciumJEavum contains chrysocetraric acid and calycin. When Acolizcm tigilkaw is extracted with ether, and the ethereal solution shaken with aqueous potassium hydrogen carbonate, the potassium salt of acolic acid separates, whilst rhizocarpic acid remains in solution.Acolic acid crystallises in small, white needles, melts and evolves gas at 176q and is fairly soluble in alcohol, benzene, or chloro- form when hot, but only sparingly at the ordinary temperature. The ammonium, p!tassium, and 6arium salts are described. The investigation of the constituents of Cetraria islandica has been continued ; the sample examined consisted chiefly of var. vulgaris and pbtyncc. Lichenostearic acid is found to be a mixture of three acids, which the author terms a-, p-, and y-lichenostearic acid. a-lichernosteccric acid, C18H3005, is a monobasic acid which crystallises in prisms or plates, melts at 122-123', gives LaJD + 2 7 * 9 O , and is soluble in benzene, chloroform, or hot glacial acetic acid ; its potass- ium, sodium, ammonium, barium, and silver salts are described.TheORGANIC CHEMISTRY. 87 methyl ester, obtained by the action of methyl iodide on the potassium salt, crystallises in colourless needles, melts at 50.5', and dissolves readily in alcohol or ether. The ethyl ester forms long, radiating crystals, melts at 29-30', and is easily soluble in ether or alcohol. When a-lichenostearic acid is heated with aqueous barium hydroxide, i t loses carbon dioxide and is converted into lichestrone, C17H30039 the lactone of lichestronic acid ; lichestrone crystallises in white, lustrous plates, melts at 83-84', is optically inactive, and dissolves readily in alcohol, ether, acetone, chloroform, benzene, or glacial acetic acid. It dissolves slowly in solution of potassium hydrogen carbonate, with formation of lichestronic acid; this change takes place more rapidly if potassium carbonate or hydroxide is employed.Lichestronic acid, C17H,,0,, is monobasic ; it crystallises from dilute acetic acid in prisms or plates, melts at SO', is optically inactive, and dissolves very easily in alcohol, ether, benzene, or chloroform; its barium salt was prepared and analysed. P-Lichenostearic acid, C,,H,,O,, crystallises from acetic acid in leaflets, melts a t 12l0, gives [.I1, +27*9', and by the action of baryta is converted into lichestrone ; its sodium, ummonium, and barium salts are described. a- and P-Lichenostearic acids are readily distinguished by means of their ammonium salts; the ammonium salt of the former acid is sparingly soluble in cold water, whilst that of the latter acid is very easily soluble, and is precipitated in a gelatinous form on addi- tion of excess of ammonium chloride, y-lichenostearic mid, C1sH3005, or CI9Ha2O5, melts at 121-1 22O, and gives [ a ] , + 16.0' ; when its solution in benzene is heated, it is to a great extent polymerised.The ammonium salt is readily soluble in wator ; the barium salt is insoluble in water, whilst that of the P-acid is very easily soluble. Paralichenostearic acid, C,oH,,O, (Abstr., 1899, i, 386), melts at 182'. The foregoing acids are accompanied by smaller quantities of two other acids, The first of these has the composition Cl,H300,; w h y crystallised from alcohol, it melts at 140°, but if crystallised from glacial acetic acid, melts at 152'; its bn~ium salt was prepared and analysed.The second acid is dilichenostearic acid, C56HGoOlo, which melts a t 272', gives [ a ] , + 15*2', and is easily soluble in ether, amyl alcohol, or hot chloroform, and sparingly in benzene, light petroleum, or hot alcohol ; determination of the molecular weight by the boiling point method gave 659 (C,GH,oO11 requires 652) ; its sodium, ammonium, and barium salts are described. The author was unable to detect any phytosterol, or similar sub- stance, among the constituents of Cetravia iskundica. The licheno- stearic acid described by Sinnhold (Abstr., 1899, i, 13), is probably the a-acid, whilst his lichenosterylic acid appears to be lichestrone. E. G. Compounds from Lichens. VII. By WILEELM ZOPF (Annalen, 1900, 313, 317-344.Compare Abstr., 1899, i, 716).-Leparia Zate- brarum (Ach.) yields roccellic acid, atranoric acid, and leprarin, which melts at 155' ; methyl, ethyl, and propyl alcohols, under the influence of hydrochloric acid, convert leprarin into Zepravinin, melting at 135'88 ABSTRACTS OF CHEMICAL PAPERS. lepraridin, melting at 120-121°, and lepulin, melting at looo, re- spectively. Gyrophoru vellea and G. spodochroa (Ehrh.) var. depressa contain gyrophoric acid, which in the former lichen is associated with gyrophorin ; this crystallises from alcohol in minute, rhombic plates, and melts, evolving gas, a t 189'. Usnic acid has been identified in Ramalina thrausta (Ach.), Alectoria sarmentosa (Ach.), Cladonia deformis (L.), C. cyanipes (Sommerfelt), and Parmelia incurvcc (Pers.).Lecanora epnora (Ach.) contains zeorin and epccnorin, which crystallises from warm ether in lemon-yellow needles, and melts at 131-132O. Par- meZia Borreri (Turn.) yields lecanoric acid, and P. sorediata (Ach.) contains diff usin ; the greenish-yellow colour of Rhixocarpon viridi- atrum (FlGrke) is due to rhizocarpic acid. The author has isolated salazinic acid and picrolichenin from Pertusaria amara (compare Hesse, Abstr., 1899, i, 383), and corrects his former statement t o the effect that Physcia caesia (Hoffm.) contains haematomic acid. The compound in Evernia furfuracea (L), at first thought to be erythrin, is now recognised as a new substance, olivetoric acid, C,7H3608, which crystallises from 55 per cent. alcohol in long, silky needles, and melts at 141--142O; when heated with methyl alcohol in sealed tubes a t 150°, it yields oliwetorinic acid, which sinters at 65O, and melts at 88'.Disulphones. V. Acetophenone and Benzophenone Disul- phones. By THEODOR POSNER (Ber., 1900, 33, 3165-3168. Compare this vol., i, 14).-According to Baumann (Ber., 1886, 19,2S03) aromatic and aromatic-aliphatic ketones do not yield disulphones by conversion into mercaptoles and oxidation ; the author has, however, succeeded in obtaining disulphones from acetophenone and benzophenone. aa-Diethylthiol-a-phenylethane (cccetop?~enonernercaptole), CMePh(SE t)z, is readily formed when hydrogen chloride is passed into an acetic acid solution of acetophenone and ethyl mercaptan. It is an oily compound, and on oxidation yields aa-diethylsulphone-a-phenylethane(acetophen0ne- disulphone) melting a t 1 19-120° (corr.) ; this compound is identical with that described by Fromm (Annalen, 1889, 253, 135) as melting at 1OO-10lo.M. 0. F. Diethylsulphonediphenylmethane (benxophenonedisulphone), forms small, nodular crystals melting at 136-137' (corr.). Action of Nitrous Acid on Benzoquinone. By JULIUS SCHMIDT (Ber., 1900, 33,3246-3250).-Nitroanilic acid 6enxopuinons, OH*C,( N0,),:02:0,:C,€14, obtained by saturating a cooled ethereal solution of benzoquinone with the fumes evolved from nitric acid and arsenious oxide, crystallises in lustrous yellow prisms, and decomposes at 160° , it is readily soluble in acetone, ethyl acetate, or the alcohols, and dissolves only sparingly in chloroform, benzene, or toluene.An intense bluish-red coloration is developed on treating its alcoholic solution with ferric chloride. When dissolved in water, it dissociates into benzoquinone and nitroanilic acid ; alkalis decompose it, yielding the quinone and an alkali nitroanilate, sodium ethoxide in alcoholic solution giving rise to the sodium salt. A mixture of benzoquinone and liquid nitrogen trioxide after re- CPh,(SO,Et),, J. J. S.ORGANIC CHEMISTRY. 89 meining for 24 hours in a sealed tube at 12O, exploded with sufficient violence to completely shatter the wrought-iron sheath surrounding the experimental tube. 6-Acetylamino-1 : 2-naphthaquinone and the isoRosindulines obtained therefrom. By FRIEDRICH KEHRNANN and A. DENR (Bey., 1900, 33, 3295-3300).-5-Amino-2-naphthol interacts with acetic anhydride a t the ordinary temperature to form 5-acetylamino-2- naphthol, which crystallises from alcohol in greyish needles and melts a t 213-214'.On dissolving it in dilute aqueous sodium hydroxide, adding sodium nitrite, and acidifying, the nitroso-derivative, N HAc* C, oH,O: No OH, is obtained; this crystallises from water, gives a bright green sodium salt, and on reduction with stannous chloride in 20 per cent. hydro- chloric acid yields 5-acety~amino-~-arnino-2-n~6phtho~, which is readily oxidised by potassium dichromate and sulphuric acid to 5-acetgllamino- 1 : 2-naphthapuinome. This crystallises from chloroform in vermilion needles, melts a t 150-160°, is easily soluble in water, and condenses at the ordinary temperature with o-aminodiphenylamine to form principally isorosinduline No.9 (Kehrmann and Steiner, this vol., i, 101) along with a small quantity of the isomeride No. 12 (ibid., 100). W. A. D. Bromofenchone. By LUIGI BALEIANO (Gazxetta, 1900, 30, ii, 382-388).-Bromofenchone, G. T. M. CH,*CH- CHMe CH,*CBr- CHMe CH,*CBr--CO or I >CMe, I 9 CH,*CH- co 1 >CMe, I obtained in small yield by gradually adding the theoretical quantity of bromine to fenchone heated at 140-150°, is a pale yellow, oily liquid which has an aromatic, terpene-like odour and dissolves in most organic solvents; it boils undecomposed at 120' under 14 mm., and at 107' under 2 mm. pressure, has a sp. gr. 1-328 a t 15'115' and [a]= - 6.8O at 9'. On reduction in alcoholic solution with zinc and sulphuric acid, it yields fenchone, but when oxidised with various oxidising reagents no definite products other than carbon dioxide, oxalic acid, and resinous acids could be obtained. Terpenes and Ethereal Oils.By OTTO WALLACH (Annalen, 1900, 313, 345-370. Compare Abstr., 1896, i, 10l).-[With H. and E. LAUFFER.]-when purified phellandrene nitrite is treated with ammonia of sp. gr. 0.93, it is very slowly dissolved, nitrous oxide being evolved ; a white solid is produced which yields nitrophellandrene when heated with water, acids, or alkalis, a.nd this disagreement with the observations of Pesci (Abatr., 1886, 1038) is due to the fact that the material employed by that investigator was not purified sufficiently. Nitrophellandrene is also produced when phellandrene nitrite is added to acetic chloride.Oxidation with nitric acid converts phellandrene nitrite into a neutral compound containing nitrogen, along with terephthalic and isopropylsuccinic acids, and an acid isomeric with the last-named sub- stance. The compound, C7H,o0,N,, melts at 88-89', and gives Liebermann's reaction for nitroso-compounds ; the acid, C7HI2O4, melts 11'. H. P.90 ABSTRACTS OF CHEMICAL PAPERS. at 85-88'. isoPropylsuccinic acid is also produced when phellandrene nitrite is oxidised with potassium pe$manganate. The constitution of phellandrene is best represented by the formula QHPrP* CH,*CH CH:CH-CH [With H. LAUFFER.]-T~~ base, C,,H17*NH2, prepared by reducing terpinene nitrosite with sodium in alcohol, boils a t 209-210°, has a sp. gr. 0,8725, and n, 1.4717 at 20' ; the carbamide derivative melts at 1729 Oxidising the corresponding alcohol converts it into the ketone, of which the oxime melts a t 96-98'.p-Cymene is the non- basic reduction product of terpinene nitrosite. [With ALFRED ScHAFER.1-when a-phonic acid is prepared by oxidising oil of turpentine, a peculiar, camphor-li ke odour is noticeable on evaporating the liquid ; this is due to nopinone, the ketone obtained by oxidising nopic acid. [With WILHELM Ro JAH~.]-P~nocamphy~amine, C, ,H,y*NH,, pye- pared by reducing pinocamphoneoxime (Abstr., 1898, I, 486) with sodium in alcohol, is a liquid which rapidly absorbs carbon dioxide; the carbamide and acetyl derivatives melt at 204' and 120' respec- tively. Pinocamphonitrile (Zoc. cit.) boils a t 224--226O, and is hydro- Qsed to pinocumpholenic m i d , C,,H1,O,, which yields the amide melting at 1 1 6 O .Whilst nitrosopinene yields a mixture of pinylamine and pinocam- phone on reduction, the additive compound with bromine is converted into dihydrocarvone and dihydrocarvylamine. Camphene. By FRIEDRICH W. SEMMLER (Ber., 1900, 33, 342(5-3432).-Camphene is never oxidised to camphoric acid, and probably contains a nucleus different from those of pinene and of ' >CH,. M. 0. F. /CH,*CH,\ pinene hydrochloride. The formula CMe/-Cke23CH is sug- \C(:CH,)-/ , a, gested for camphene. Pinene dibromide is reduced to a dihydrocamphene identical with t h a t from pinene hydrochloride ; it therefore contains the same nucleus as the latter, and is the product of an isomeric change similar to that which takes place in the action of hydrogen chloride on pinene.Bromocamphene, for which the formula CMe-CMe, -CBr is \C(: CH,)--/ suggested, is reduced by sodium and alcohol to camphene, and there- fore contains the camphene nucleus unchanged. Camphene dibromide is probably formed by the addition of hydrogen bromide to the bromo- camphene which is the first product of the action, and is reconverted into bromocamphene by distilling with quinoline. It is not, however, readily acted on by alcoholic potash, and is reduced by sodium and alcohol to a dihydrocamphene identical with that from pinene hydro- chloride; it is therefore suggested that it has the same nucleus as the /CH,*CH,\ /CHO--CH9\ - \ latter, and the formula CMe'-~Me2-CBr is suggested ; the \CHBr* CH,/ORGANIC CHEMISTRY 91 conversion of bromocamphene lnto camphenedibromide would then in- volve the conversion of a Four-membered into a five-membered ring, as in the conversion of pinene into the hydrochloride.Camphene hydrobromide, ClOHI6,HBr, separates from alcohol in well- formed crystals and melts at 133' ; it is reconverted into camphene by alcoholic alkalis, and also when attempts are made to reduce it with sodium and alcohol, The hydrochloride loses hydrogen chloride less readily, and gives a mixture of camphene and dihydrocamphene iden- tical with that from pinene hydrochloride; it is suggested that the /CH,*CH,\ hydrochloride is perhaps a mixture of CNe'-CMe23CH and \-CMeCl-/ /CH,*CH,\ CMe-CMe,-CCl. \CH,*CH 2/ Camphene alcoholate, C,,H,7*OEt, prepared by boiling a mixture of camphene, alcohol, and sulphuric acid, is an oil which boils at about 200', has m, 1.4589, a sp.gr. 0.895, and is identical with isoborneol ethyl ether (Bertram and Walbaum, Abstr., 1894, i, 204) ; this reac- tion does not take place with other terpenes, although nopinene and sabinene give small yields of an ether. isoBorneol gives a small yield of camphor when oxidised with dichromate and sulphuric acid; it may be a camphane derivative, CMe-CMe,-C*OH, or a cam- /CH,.CH,\ \CH2*CH,/ ,AH2- CH,\ \CMe(OR) T. M. L. phene derivative, CMe-CMe,-/CH, or a mixture of these. The Resin-Balsam of Picea Vulgaris, Link (Jura Turpen- tine). By ALEXANDER TSCHIRCH and En. BRUNING (Arch. Pharm., 1900, 238, 616-630).-This turpentine was examined by the methods already described (Abstr., 1900, i, 678, &c.).From a solution of it in ether, 1 per cent. aqueous ammonium carbonate extracts piceapirnarinic acid, C13H2,02, an amorphous substance, which neutrahes 1 KOH both in the cold and on boiling, After this treatment, 1 per cent, aqueous sodium carbonate extracts a mixture of acids, from the solution of which in methyl alcohol piceapimuric acid, C20H30O2, crystallises ; this melts at 144--145O, and neutralises 1KOH both in the cold and on boiling ; mono-potassium, culciurn, lead, and silver salts were prepared. From the mother liquors of this acid, two isomeric piceapimarolic acids, C,,H,,O,, separate ; these are amorphous, and can be separated with alcoholic lead acetate, which precipitates the lead salt of the a-acid, but not that of the P-acid; the acids melt a t 90-95' and 88-94O respectively; both neutralise lKOH as well in the cold as on boiling.These resinolic acids all give the colour reactions of the cholesterols. After removal of the acids and further washing with dilute aqueous potassium hydroxide, the ether was distilled off, and the residue dis- tilled with steam ; an etheveal oil came over, smelling like turpentine. There remained behind a substance of indifferent character, jworesen, C,IH360*92 ABSTRACTS OF CHEMICAL PAPERS An alkaloid can be extracted from the turpentine with hot water. The turpentine also contains a Golouring matter, and it yields formic, acetic, and succinic acids when distilled ; no methoxyl is present. In 100 parts of the drug there are contained : piceapimarinic acid, 2-3 ; piceapimaric acid, 1.5-2 ; a- and P-piceapimarolic acids (the former in larger amount), 48-50 ; ethereal oil, 32-33 ; juroresen, 10-12 ; succinic acid, colouring matter, alkaloid, water and impuri- ties, 1-2 parts.C. F. B. Synthesis of Luteolin. By STANISLAUS VON KOSTANECKI, A. R ~ ~ Y C K I and JOSEF TAMBOR (Ber., 1900, 33, 3410-3417).-When 2 : 4 : 6-trimethoxyacetophenone and ethyl piperonylate dissolved in sylene are heated with sodium for 10-12 hours a t 120°, condensation ensues with the formation of 2 : 4 : 6 t~imethoxybenxoyZ-3' : 4'-methyEene- dioxyacetophenone, C,H,(OMe);CO*CH,*CO*C~H~:O,:CH,, which crystallises in small, yellow needles, melts a t 115' and when warmed with hydriodic acid yields 5 : 7-dimethoxy-3' : 4'-methylenedioxyJlavone, which crystallises in clusters of silky, white needles, melts at 232O, and forms fluorescent solutions. As this compound is not easily converted into tetrahydroxyflavone, 2 : 4 : 6 : 3' ; 4'-pentamethoxybenxoylacetophenone was prepared by the condensation of 2 : 4 : 6-trimethoxyacetophenone with ethyl veratrate ; this is precipitated by carbon dioxide from its solution in sodium hydroxide as a white, curdy precipitate and, when treated with strong hydriodic acid, yields luteolin.Hydrolysis of Solanin. By FERDINAND SCHULZ (Zeit. Zuc?c.-lnd. Bohm., 1900, 25, 89--94).-0n hydrolysis, solanin yields about 47.53 per cent. of its weight of solanidin and 42-41 per cent. of sugar (calcu- lated as dextrose), the latter being a mixture of dextrose with a methylpentose, probably rhamnose.Oxidation of Aloin with Potassium Persulphate and with Caro's Acid. By EUGEN SEEL (Ber., 1900, 33, 3212-3214).-By the action of an excess of potassium persulphate on aloin, a red substance is produced, perhaps identical with Schaer's <aloin red ' (Abstr., 1900, i, 5 12). Caro's reagent gives a tetvahydroxymethylanthraquinone, C15H1006, which is perhaps identical with Oesterle's ' alochrysin ' (Abstr., 1899, i, 538). Crystalline Compounds in Galanga Root. By GIumPPE TESTONI (Gaxxetta, 1900, 30, ii, 327-339).-Alpinin, C17H,,0,, which Jahns (Abstr., 1882, 866) isolated, together with campheride and galangin, from galanga root (AZpinia oficinarum), is shown by the author to be a mixture of the two last-named compounds.The methyl derivative of galangin, C,,H,,O,, is also present in galanga root and crystallises from methyl alcohol in pale yellow, square plates melting a t about 300'. It dissolves in concentrated sulphuric acid, forming a deep yellow liquid which in a short time assumes a green fluorescence ; it is also soluble in concentrated potass- ium hydroxide solution, giving an intense yellow colour, whilst with sodium hydroxide the corresponding salt is precipitated in minute yellow needles. I t s diacetyl compound, C,,,H,,O7, separates from ales R. H. P. T. H. P. T. M. L.ORGANIC CHEMISTRY. 93 hol in faintly yellow leaflets melting at 175-176O and forms a di- hornaide, C2,,HlG07Br2, crystallising from acetic acid in yellow needles melting a t 202'. The methyl derivative is transformed into galangin by hydriodic acid.Jahns (Zoc. cit.) and Gordin (Diss.) prepared diacetyl- and dibenzoyl- derivatives of campheride, but the author has obtained trisu bstituted derivatives, thus confirming the constitution given by von Kostanecki (Abstr., 1896, i, 44). T'riacetylcamphsride, C,GHgOGAc,, separates from alcohol in almost white needles melting at 193-194' and the tribenzoyl compound crystallises from acetic acid in white, marnmillary masses melting at 177-178'. On methylating campheride with methyl iodide and alcoholic potash, it yields mainly a trimethyl derivative, C,,H,,O,, separating from methyl alcohol in square or rectangular yellow plates melting a t 178', whilst ethylation yields a diethyl derivative, C2,H2,00, crystallising from methyl alcohol in slender, yellow needles melting at 137-139' and a triethyl compound, U22H2406, separating from light petroleum in long, yellow needles melting at 125-126'.I n these trisubstituted deriva- tives, one of the alkyl groups enters the nucleus of the molecule and is not present in the form of a methoxy- or ethoxy-residue. T. H. P. Tiliadin, a Constituent of the Bark of Lime Trees. By WALTER BRAEUTIGAM (Arch. Pharm., 1900, 238, 555-567).-When the bark of the lime tree is extracted with ether, the extract evapor- ated, and the residue washed thoroughly with 90 per cent. alcohol, the alcohol extracts a little vanillin. If the residue is boiled with 5 per cent. aqueous potash and then dissolved in ether, the solution deposits crystalline plates as i t evaporates ; this substance, tiliadin, C21H3202, melts at 228-229', volatilises when heated cautiously, and is dextrorotatory in chloroform solution.I n many of its reactions it resembles the cholesterols, but in others it differs from them; it has not the properties of a glucoside. It does not lose water of crystallisation when heated at 125', nor will it form acetyl or benzoyl derivatives. Strong hydrochloric acid is without effect on it, even a t 160'. Boiling with aqueous alkali hydroxides is without effect ; on the other hand, alcoholic potash at 150' converts it into a substance, C,,H,,O, which crystallises in needles, begins to melt at 179--180', and volatilises when heated cautioualy. Fusion with potassium hydroxide converts tiliadin into resinous pro- ducts, but oxalic acid is not formed.Boiling with nitric acid has no effect, but a t 160' a resinoils product is obtained. Potassium per- manganate does not oxidise i t in cold acetic acid solution, but it does on boiling, and so does chromic acid ; the product is a resinoils sub- stance, with the composition C,,H,,O,. When treated with chlorine or bromine in chloroform solution, tiliadin yields products containing chlorine and bromine; with iodine, no similar product could be obtained. On the west side of the tree, the bark frequently has a green coating of an alga, Pleurococcus uulgavis; from this a substance cryatallis- ing in needles was obtained; these crystsllise out along with the VOL. LXXX. i. h94 ABSTRACTS OF CHEMICAL PAPERS, plates of filiadin in the preparation of the latter, if the bark has not been freed from the green coating.Blue Chlorophyllin. By M. TSVETT (Compt. rend., 1900, 131, 842-844).-The blue chlorophyllin was isolated from the plants by a method which is described in detail. It was obtained in a micro- crystalline state, the crystals having a black colour and a bluish lustre. The absorption spectrum of its solution consists of six bands, the fourth band being situated near the Fraunhofer line E, and the fifth commences at the line F. Composition of the Orange Pigment of Uraster Rubens. By ARTHUR BOWER GRIFFITHS and F. U'. WARREN (Bull. h'oc. Chinz., 1900, [iii 1, 23, 874--875).-The orange pigment extracted from the skin of Uyastey rubens has the composition C,,Hi,02N4 ; its solutions do not show characteristic absorption bands.Syntheses of Coumaranone (Ketocoumaran) and its Homo- logues from Phenoxyacetic Acid. By RICHARD STOERMER and F. BARTSCH (Ber., 1900, 33, 3175-3181. Compare Abstr., 1899, i, 675).-Coumaranone is most easily obtained by the dehydration of phenoxyacetic acid suspended in benzene with phosphoric oxide, and is separated from the unaltered acid by distillation with steam ; when pure, it is quite stable and has a pleasant odour of hyacinths, It sublimes at the ordinary temperature in long, slender needles and melts at 101-102'. The semicarbaxone, C,H,O,N,, separates from alcohol in yellowish crystals and melts at 231'. The oxime, C,H70,N, crys- tallises from hot dilute alcohol and melts a t 159'. l-o-Eydroxybenxylidenecoumaranone, C,,Hi003,.separates from hot dilute alcohol in slender, yellowish crystals melting and decomposing at 208' ; it dissolves in alkalis with an intense red colour. l-p-Hydvoxy- benxylidenecoumarccnone is a greenish-yellow, crystalline substance which melts and decomposes at ,242'. The two foregoing compounds are substantive dyes. During the preparation of coumaranone, a considerable quantity of a reddish- brown substance, Cl6HI0O3, is obtained as a bye-product. This has the constitution C,H4<:6x:C<g320, and is probably formed by condensation of 2 mols. of coumaranone. C. F. B. H. R. LE 8. N. L. 6-Meth ylcoumaranone, C,H3Me<CO>CH,, -0- from o-tolyloxyacetic acid, forms yellowish-white crystals melting at l02', is volatile with steam, and dissolves readily in the common organic solvents or in hot water.With Fehling's solution, it yields a red dye similar to that obtained from coumaranone. The semicurbaxone, CioH, 102N3, separates from hot dilute alcohol in yellowish crystals melting at 229'. The oxime, C,H,02N, is yellow, dissolves in ether, benzene, or alcohol, and melts at 148'. l-o-Hydroxybenzylidene-6-methyZcoumaranone, Ci,HJ203,. cry stallises from hot alcohol in yellow needles, dissolves in alkalis, yieldiug an intense red solution and sublimes and decomposes at 196'. The corresponding pava-compound forms yellow leaflets which decompose at 2 10-2 15'.ORGANIC CHEMISTRY. 95 5-MethyZcouma?anone, CgH,02, unlike the analogous substances already described, is an oil, and boiis at 106-112' under 15 mm.pressure ; its properties closely resemble those of coumaranone. The sernicarbaxone, C10H1102N3, is yellowish and melts a t 208', the oxime CgH,02N, is yellow and melts a t 151*. The 0- and p-hydroxybenzytidene derivatives, Cl6HI2O3, are yello wish-brown, the former decomposes a t 192', the latter at 212'. 4-~ethylcouma~ccnone, C9H802, is a yellowish liquid which boils with- out decomposition in a vacuum. The semicadaxone, C,,H,,O,N,, melts a t lSl', and the oxime, C,Hg02N, at 144'. The 0- and p-hydroxy- benxylidene derivatives, CI6Hl2O3, decompose at 210' and 163' re- spectively. 4 : 6-~~methy~coumc~~ccnone, C,H2Me2<Co>CH2, from ccs-m-xylyloxy- -0 acetic acid, melts at 143O. Its oxime, C1,Hl,O2N, melts at 148'. A. L. The Cinchona Alkaloids. By WILHELM VON MILLER and GEORG ROHDE [in part with JOSEF BRUXNER and ERNST FUSSENEGGER] (Ber., 1900, 33, 3214--3237).-The identity of Pasteur's cinchonicine and quinicine (Jahresber.der Chem., 1853, 473) with cinchotoxine and quinotoxine has been established. By the action of amyl nitrite and sodium ethoxide cinchotoxine is converted into an isonitroso-derivative, C,,H2102N3, which separates in crystal' aggregates from chloroform when ether is added, melts at 169-170°, and, like other secondary piperidine bases, gives a purple coloration with nitrobenzene containing nitrothiophen ; the salts do not give this reaction. The hydrochloride, ClgH2102N3,HCI, melts at 268', crystallises from alcohol or hot water in prismatic plates, dis- solves in acids and alkalis, and gives Liebermann's reaction ; the cccetccte melts at 200°, and the suZphate, nitrate, formate, and phosphccte are also crystalline.The methiodide, C19H2,02N3, MeT, crystallises from methyl alcohol in prisms and plates, melts at 2354 and, unlike most secondary bases, is not acted on by aqueous alkalis ; when treated with sodium ethoxide, it gives a base identical with the isonitroso-derivative of methylcinchonine, and i t would therefore appear that in the removal of hydrogen iodide from the methiodide the cinchotoxine is reconverted into a cinchonine derivative. By the action of an excess of amyl nitrite on cinchotoxine, MilIer and Rohde's nitrosoisonitrosocinchotoxine (Abstr,, 1895, i, 433) is produced, and not a diisonitroso-derivative ; it would therefore appear that cinchotoxine contains only one methylene group adjacent t o a carboxyl group in accordance with the formula cH2>NH, and not CH C9NH6*cH2* CMe<CH:CH:CH2) .CH2 C9NH6*CH2* Co*CH2*CH<~$cH:CH,) .CH2 OH2>NH.The action of p-bromophenylhydrazine on quinotoxine gave a mixture of substances, one of which crystallised in yellow aggregates melting a t 141' and proved t o be a p-bromophenylhydraxone, C2eH2,0N,Br ; a second product crystallising -in minute yellow h 296 ABSTRACTS OF CHEMICAL PAPERS. needles and melting 15-20' higher is perhaps the geometrical isomeride. Nityosoquinotoxine, C,,H,,O,N,, prepared by the action of nitrous acid on quinotoxine, crystalliees from a mixture of acetone or benzene with light petroleum in colourless needles, melts a t 94', dissolves in acids and gives Liebermann's reaction; the phenyhydrcczone, C2,H2,0,NS, crystallises from alcohol and melts at 140'.Xtyosoisonitrosoquzno- toxine, C2,H,,0,N,, which is also produced in the action of nitrous acid on quinotoxine, crystallises from alcohol in large, colourless prisms, melts a t 186q and dissolves in alkalis to a yellow solution. The action of methyl iodide on quinotoxine is similar to its action on cinchotoxine, the products being methylquinine (Claus and Mall- mann, Abstr., 1881, 619) and its methiodide; the anhydrous meth- iodide melts a t 180°, not at 215-218'. isoivitrosoquinotoxine, C20H2303N3, crystallises from a mixture of alcohol and benzene in yellowish aggregates, melts at 168--170°, and gives the nitrothiopen reaction.The hydrochloride, C,,H,,O,N,,HCI, crystallises from alcohol in large tablets and melts a t 244'; the acetate, suZphate, and nitvale are crystalline and do not give the nitro- thiophen reaction. The methiodide, C,,H,,O,N,I, crystallises from methyl alcohol, melts at 175', and is not acted on by aqueous alkalis. By the action of sodium ethoxide the quinine complex is reproduced, the produdt being an isonit~osomethy~Quinine, which separates as a yellow, amorphous base, melts a t 90-100', and is identical with the base prepared from amyl nitrite and methylquinine ; the identity of the bases was also proved by conversion into the methiodide, C2,H2,0,N,I, melting a t 169-170°, and the nitrate melting at 175O. Constitution of Pyridones, Quinolones, and Analogous Bases.By HERMANN DECKER (J. p r . Chem., 1900, [ii], 62,266-270). -A discussion of the formulae of pyridones and analogous bases. The author favours formulae of the ketonic type, CHeCH* CH:CH 'O>NR, T. M. L. which he considers represent the reactions of these bases better than formulae of the type CH:CH* I 8->0, which contain quinquevalent CH:CH*NR nitrogen. R. H. P. Thio-1-methylpyridone and Thio-1-methylquinolone. BY ALEXANDER GUTBIER (Ber., 1900, 33, 3358-3359).- W&-lmethyl- pyridone, CH<~H:CH>NM~, CH* CS or s<c TMe:CH* =CH-CHH' GH obtained by heating 1-methylpyridone with phosphorus pentasulphide for 4-5 hours a t 1 30°, crystallises from hot water in yellowish-white leaflets, melts at 89 -go', and distils unchanged ; it is feebly basic, dissolving in concentrated sulphuric or hydrochloric acid.Thio- 1 -methylpinolone, obtained similarly, forms long, pointed, yellowish green prisms, melts at 11$', boils unchanged above 370°, and resembles the foregoing thiopyridone. Both substances, like 1 -methylpyridone and 1 -methyl- quinolone from which they are derived, fail t o interact with hydroxyl- amine in either neutral or alkaline solution. W. A. D.ORGANIC CHEMISTRY. 97 Action of Ethyl Acetonedicarboxylate on rn-Phenylene- diamine. By EMIL BESTHORN and E. GARBEN (Bey., 1900, 33, 3448-3453. Compare Abstr., 1898, i, 450).--EthyZ 7-amino-2-puinolone- 4-acetate is obtained when molecular quantities of ethyl acetonedicarb- oxylate and m-phenylenediamine are heated together for several hours in sealed tubes at 100'; on hydrolysis with hydrochloric acid, it yields 7-amino-2-quinoZone-4-acetic acid in the form of its hydrochloride which when washed with water yields the acid, NH .C H <C(CH20C02H):~H. 2 6 4 N H -C@ ' this crystallises from water in hair-like, colourless needles inel ting at about 271°, is only sparingly soluble in the usual organic solvents, and its solution exhibits a blue fluorescence.The calcium salt contains 5H20, the ethgZ ester crystallises in needles melting a t 197-1998', is sparingly soluble and its solutions also fluoresce. When the acid is rapidly heated a t 300°, it loses carbon dioxide and yields 7-amino- lepidone (7-amino-2-hydroxylepidine); when treated with nitrous acid, it yields 7-hydroxy-2-puinolone-4-acetic acid, which crystallises from hot water in felted needles melting at about 320' ; it forms a hydrochloride which is decomposed by water, and an ethyl ester crystallising in minute needles and melting at 204-205', but after solidification at above 2204 When the acid is carefully heated, it yields 7-hydroxy- lepidone (2 : 7-dihydroxylepidine).J. J. 8. Stereoisomeric SchifI's Bases, By ALEXANDER EIBNER and FRZ. PELTZER (Ber., 1900, 33, 3460-3469. Compare Abstr., 1894, i, 410).-When aqueous solutions of o-toluidine and acetaldehyde are mixed and kept at the ordinary temperature for 24 hours, an ethyZ- idene-o-toluidine, C,,H,,N,, crystallising in small needles and melting, after repeated recrystallisation from alcohol, at 90-92' is obtained ; it dissolves readily in both dilute and strong hydrochloric acid, but yields a sparingly soluble nitrate ; when benzoylsted by the Schotten Baumann method, i t yields a 6enxoyZ derivative, C25H280N2, melting at 179', together with a small amount of the isomeric benzoyl compound melting at 230'.Its dinitroso-derivative, C,,H,,02N4, crystallises in yellow needles melting at 130' and is sparingly soluble in alcohol ; when reduced, it yields p-phonylenediamine and 2 : 8-dimethyltetra- hydroquinoline. When the base is distilled, it yields 2 : S-dimethylquino- line together with a small amount of the isomeric base melting a t 116'. If the solution of acetaldehyde and o-toluidine is warmed, shaken, or kept at the ordinary temperature for several weeks, an ethylidene-o- toluidine melting a t 116' is obtained ; this crystallises in small prisms or plates, is readily soluble in most solvents with the exception of light petroleum, forms a hydyochloride, 3 sparingly soluble nitrate melting at 155', a diacetyl derivative melting at 155', a Jinitroso-compound melting at 155', and a 6enxoyZ derivative melting a t 230'; the latter Forms a nitroso-compound melting at 190' The base itself can be distilled without undergoing any great decomposition and is not reduced when treated with sodium and amyl alcohol.The same base is obtained when the isomeride of low melting point is heated for 4 hours at 120-125', or when its ethereal solution is treated with iodine. When98 ABSTRACTS OF CHENICAL PAPERS. the condensation takes place in acetic or hydrochloric acid solution, the compound melting at 116O is alone formed.Action of Nitrosobenzene on Aromatic Hydraxines. By OSKAR SPITZER (Chem. Centr., 1900, ii, 1108; from Oesterr. Chem. Zeit., 3, 489-490).-Whilst by the action of nitrosobenzene on hydrazobenzene, azobenzene and water only are formed, with phenyl- hydrazine, nitrosobenzene yields, not only these products, but also nitrogen and benzene. The latter reaction may be used to estimate the quantity of nitrogen present as nitroso-groups in organic corn- Founds. E. W. W. Phenylmethylpyrazolecarboxylic Acids. By CARL BU LOW (Ber., 1900, 33, 3266-3270).-The acid formerly described by Bulow and Schlesinger as 1-phenyl-3-methylisopyrazole-4 : 5-dicarboxylic acid (Abstr., 1900, i, 36) is in reality 1-phenyl-5-methylpyracxole-3 : 4-dicarb- oxglic acid (compare Stolz, Abstr., 1900, i, 252) ; i t is produced, together with Knorr and Laubmann's dicarboxylic acid (Abstr., 1889, 409), by oxidising 1 -phenyl-3 : 5-dimethylpyrazole-bcarboxylic acid with potassium permanganate ; it is identical with the substance pro- duced from diethyl benzeneazodiacetylsuccinate, and yields, by the successive elimination of its carboxyl groups, 1-phenyl-5-methylpyr- azole-4-carboxylic acid (m.p. 166') and I-phenyl-5-methylpyrazole. The isomeric acid described by Knorr and Laubmann as melting a t 198' has a melting point 203-204°, and is 1-phenyl-3-methylpyrazole- 4 : 5-dicarboxylic acid ; it yields l-phenyl-3-methylpyrazole-4-carboxylic acid (m. p. 192*5-193c) and 1-phenyl-3-methylpyrazole by the succes- sive removal of carboxyl.Preparation of Pyrazole Derivatives from Azo-compounds of Diacetosuccinic Esters. By CARL BULOW and ALFRED SCHLES- INGER (Ber., 1900, 33, 3362--3369).-The following facts form an extension of a previous paper (preceding abstract). Diethyl p-toluene- uzodiucetosuccinate, C6H4Me*N,* C Ac( C0,Et) C( CO,Et):CMe*OH, ob- tained by combining p-toluenediazonium chloride with ethyl diaceto- succinate, separates from alcohol in yellow crystals, melts at 119-1 ZOO, and on boiling with water for 8 hours loses acetic acid (1 mol.), and yields tliethyl 1-p-tolyl-5-methylpyraxole-3 : 4-dicarboxylate, G 6 H 4 N e * N < T CMe. C I CO,E t ' This crystallises from dilute alcohol, melts at 50°, and on hydrolysis with dilute mineral acids or alkalis yields 1-p-tolyl-5-rnethylpyrazole-3 : 4-dicarboxylic mid, which forms slender needles, melts a t 246O, and yields an acid silver salt, C,,H,,O,N,Ag, as a white powder, insensitive to light, On heating the acid above its melting point, it loses carbon dioxide and yields a mixture of I-p-tolyZ-5-methylpyruxole and its 4-cadoxylic acid. The former is a yellowish oil, which boils at 270-280°, is volatile in steam, and yields a crystalline platinichloride melting and decomposing a t 214O; its 4-carboxylic acid is crystalline, and melts at 199-20Oo.Diethyl P-nuphthaleneaxodiacetoszcccinate, prepared from diazotised P-naphthylamine and diethyl acetosuccinate at Oo, separates from dilute alcohol in reddish-yellow crystals and melts at 108'. RiethyZ J. J. S. G. T. M. --c* CO,EtORGANIC CHEMISTRY. 99 1 -P-naphtliyl-5-methy~pyraxoZe-3 : 4-dicarboxylate crystallises from dilute alcohol in nearly colourless, lustrous leaflets and melts at 82' ; tho corresponding dicarboxylic acid melts at 250°, and on dissolving in ammonia and adding silver nitrate, yields the silver salt, CI6H1,O,N,Ag, as a heavy, white precipitate.l-P-Nccphthyl-5-methyl- pyrazole melts a t 65", boils at 320-330°, and yields a crystalline platinichloride me1 ting a t 2 17". W. A. D. Theories of Dyeing. By PAUL SISLEY (Bull. Xoc. Chirn., 1900, [iii], 23, 865--874).-In this paper, the researches of Witt, Knecht, von Georgevics, and Gillet are briefly reviewed, and a description is then given of some fresh experiments favouring Witt's dissolution theory, according to which the dyeing of a fibre is analogous to the extraction of a colouring matter from its aqueous solution by means OF an immiscible solvent.When pure, colourless rosaniline is boiled with water, a coloured solution is obtained which quickly dyes silk; in the presence of excess of alkali (1.5 grams of sodium hydroxide per litre) no coloration is produced. According to Knecht, when silk is dyed with magenta in neutral solution, the exhausted liquid contains the whole of the hydrogen chloride of the dye as ammonium chloride. The author confirms the presence of hydrogen chloride, to some extent, at least, but no ammonia could be detected in the bath. When 100 C.C. of water are boiled with 2 C.C. of normal sodium hydroxide and a little rosaniline, a colourless solution is obtained which dyes silk and yields a red colour to amyl alcohol when boiled therewith.Malachite-green, crystal- violet, and Victoria-blue behave in a similar way; aniline may be used instead of amyl alcohol, These results are shown to be due neither to impurities in the substances employed nor to the action of carbon dioxide. Their explanation is rather to be sought in von Georgevics' hypothesis, according to which the silk, amyl alcohol, or aniline bring about the molecular transformation of the colourless base OH*C(C,H,* NH,), into a coloured isomeride, OH*NH,: c,H,: C( C,H,*NH,),. The latter does not form a coloured salt with the substance of the fibre, as required by the purely chemical theory of dyeing, but forms either a solid solution with the fibre or a liquid solution with the amyl alcohol or aniline.This view is confirmed by the observations of Hantzsch on colourless and coloured modifications of triphenyl- methane derivatives. Moreover, when silk dyed with rosaniline is boiled with alcohol, the colouring matter is readily dissolved, whilst the fibre does not lose in weight. According to the chemical theory, the alcoholic extract should either be colourless or, if coloured, should contain a portion of the acid substances of the fibre in solution. The fact that in acid solutions animal fibres are dyed with the colour of the alkali salt has been adduced as an argument in favour of the chemical theory of dyeing, the fibre being here held to play the part of a base. It is now shown, however, that amyl alcohol behaves in precisely the same manner as silk in this respect, so that the facts are really in accord with the dissolution theory. Certain facts, however, appear t o contradict Witt's view that a colouring matter, in order to be fast,100 ABSTRACTS OF CHEMICAL PAPERS, must necessarily be more soluble in the substance of the fibre than in water.Thus, when silk is dyed with a very dilute solution of a colouring matter, the whole of the latter is extracted from the liquid by the fibre, whereas when a large amount of the dye is used only a comparatively small proportion of it is taken up by the silk. The relative solubilities of the dye in the fibre and in water seem, in fact, to vary greatly with the concentration. Nevertheless, it is believed t h a t experiments now i n progress will show that in many cases the behaviour of immiscible solvents is in this respect also identical with that of animal fibres.N. L. Coloured Rosaniline Bases. By HUGO WEIL (Be?., 1900, 33, 3141-3144).-In reply to von Georgievics (Abstr., 1900, i, 569), the author adheres to his previous statments (Abstr., 1896, i, 565) : 1. That the red precipitate obtained by von Georgevics is really a mixture of rosaniline with a small amount of its hydrochloride. 2. That when a solution of rosaniline carbonate is “salted out” with pure sodium chloride the solution becomes colourless and the clear iiquid after concentration gives a blue colour with litmus. J. J. 5. Relation between the Chemical Constitution of Triphenyl- methane Colouring Matters and the Absorption Spectra of their Aqueous Solutions.By PAUL LEMOULT (Compt. rend., 1900, 131, 839--842).-Aqueous solutions of dyes of the triphenylmethaue series in all cases give an absorption spectrum which contains a characteristic band of unabsorbed light in the red. The position of the centre of this red space is constant for those dyes which contain two tertiary nitrogen atoms and also for those containing three tertiary nitrogen atoms, but its position in the latter case is quite distinct from that in the former. The solutions employed had,a thickness of 6 mm., and contained a gram-mol. of the substance in 1000 litres. H. R. LE S. Relation between the Chemical Constitution of the Tri- phenylmethane Colouring Matters and their Absorption Spec- tra in Aqueous Solution.By CHARLES CAMICHEL (Compt. rend., 1900, 131, 1001--1002).-The observation made by Lemoult (preced- ing abstract) relating to the presence of fixed red bands of unabsorbed light in the spectra of triphenylmethane colouring matters containing two or three tertiary nitrogen atoms in the para-position with reference to the methane carbon atom, is only a special case of the law enunciated by Bayrac and the author (Abstr., 1896, ii, 346), who found it to hold f o r a series of indophenols dissolved in water and other solvents. The ethereal solution of an indophenol may be advantageously employed as a monochromatic screen instead of red glass. G. T. M. The Twelfth Isom eride of Roeinduline. By FRIEDRICH KEHRMANN and G. STEINER (Ber., 1900, 33, 3276-3279. Compare Abstr., 1900, i, 463).-Phenglisonaphtha~heaazonium nitrate (Abstr., 1898,i, 154),when left with fuming nitric acid for 24 hours a t Oo, Sields aORGANIC CHEMISTRY.101 mixture of 2-nitro- and 4-nit~o- 12-phenylisonuphthaphena~onium aitrates. The former, although sparingly soluble in absolute alcohol, crystallises from dilute alcohol in lustrous, yellow needles, and on reduction yields isorosinduline KO. 10 (Abstr., 1900, i, 463), a fact which determines its structure ; the latter is easily soluble in alcohol and could not be obtained pure, although the corresponding isorosinduline (No 12) [4-camino-l2-p~enylisonuphthap~enaxo~iu~], formed on reduction, was readily isolated, by taking advantage of the slight solubility of its bromide in saturated aqueous sodium bromide. The salt crystallises in well-formed, nearly black prisms, with a bluish surface-colour ; the dichromate is a dark green, microcrystalline powder.4-Acetylamino-12 -phen ylisonapht~~aphenaxolziuln 1 2-bromide is very soluble in:water, and cannot be separated by saturating the solution with sodium bromide ; the chloride, however, crystallises on adding sodium chloride in thick, reddieh-brown, prisms or plates, whilst the platini- chloride forms dark red, granular crystals. The structure of the isorosinduline No. 12 follows from its syn- thesis from 5-acetylamino-1 : 2-naphthaquinone (Kehrmann and Denk, this vol., i, S9). Constitution of isoRosinduline No 9. By FRIEDRICH KEHR- MANN and G. STEINER (Ber., 1900, 33, 3280--3284).-Details are given for preparing 2 : 5-diamino-1 : 4-naphthaquinoneimide hydrochloride (compare Kehrmann and Haberkant, Abstr., 1899, i, 62) from Ekstrand's naphthapicric acid (2 : 4 : 5-trinitro-a-naphthol), the structure of which has recently been determined (Graebe, Abstr., 1900, i, 24; Friedlander, ibid., 150); the salt is much more stable than hitherto thought, not being changed by boiling water.The diamino-a-naphthaquinone and aminohydroxy-a-naphthaquinone derived from it by the action of alkalis have the structures [02:(NH2)2 = 1 : 4 : 2 : 51 and [0, : NH, : OH = 1 : 4 : 5 : 21 instead of those originally given (Abstr., 1809, i, 62). The 5-amino-2-hydroxy-1 : $-naphtha- quinone is best prepared by heating the hydrochloride in aqueous solu- tion with dilute sulphuric acid; it does not condense with phenyl-o- phenylenediamine in alcoholic or glacial acetic acid solution, but in 80 per cent.acetic acid solution at 100° it yields 4-c~minorosindone, W. A. D. N=C H(NH,) .I b,H,.NPh 1110 >o, which was isolated iu. the form of its ucetyd dirivative. This crystallises from alcohol in golden needles, melts a t 280°, and shows a red fluorescence in alcoholic solution ; on warming with dilute sulphuric acid, it yields pure 4-aminorosindone, which crys- tallises from alcohol in bronze coloured leaflets, melts a t 253O, and can also be obtained by the action of cold alcoholic sodium hydroxide on isorosinduline No. 9 (Kehrmann and Filatoff, Abstr., 1900, i, 60). This latter fact, together with the work of Kehrmann and Denk (this vol., i, 89), show that isorosinduline No.9 is a 4-amino-7-phenyl- naphthaphenuzonium. W. A. D. Constitution of the Naphthapicric Acid melting at 145'. By FRIEDRICH KEHRMANN and G. STEINER (Ber., 1900,33,3285-3291). -The trinitro-a-naphthol (naphthapicric acid) melting a t 145O3.02 ABSTRACTS OF CHEMICAL PAPERS. (Kehrmann and Haberkant, Abstr., 1899, i, 62) can be readily separated from its isomeride melting at 190°, on account of the sparing solubility in water of its sodium salt, which crystallises in slender, sulphur-yellow needles; the following facts show that it has the con- stitution [OH : (NO,), = 1 : 2 : 4 : 71, and the substance formerly described (Zoc. cit.) as 2 : 6-diamino-1 : 4-naphthaquinoneimide is there- fore a 2 : 7-diamino-compound. The latter, when warmed with water, yields a mixture of 2 : 7-diamino-1 ; 4-naphthapinone with 4 : 7-di- amino-1 : 2-naphthaquinone, which can readily be removed by extraction with cold 10 per cent, aqueous sodium hydroxide, in the form of the sodium derivative of the tautomeric 7-aveino-2-hyd~oxy-1 : 4-naphtha- quinoneimide.The pure a-quinone forms small prisms which are chocolate-brown with a violet tinge in colour, sublimes and partly decomposes at 230°, yields an orange-yellow hydrochloride, and does not combine with ortho-diamines ; the P-quinone forms blackish-violet crystals, and yields a violet solution with dilute hydrochloric acid. Both of the quinones when boiled with dilute caustic alkalis yield 7-amino-2-hydroxy-1 : 4-naphthaquinone along with decomposition pro- ducts which render purification difficult ; the substance isolated forms brownish-red crystals, and combines with o-aminodiphenylamine N=~+,H,(NH,~ " (1 mol.) to form a 2-aminorosindone, b,:H,.NPh------->O' which yields an acetyl derivative crystallising igluitrous, red leaflets melting at 325-335', identical with the substance formed by the oxicla- tion in the air OF an alkaline alcoholic solution of Z-acetylamino- 7-phenylnaphthaphenazonium chloride (Abstr., 1900, i, 463), the latter fact determining its structure. Confirmatory evidence as to the structure of the new naph thapicric acid is afforded by the fact that the foregoing 4 : 7-diamino-1 : 2- naphthaquinone yields with o-aminodiphenylamine a 2-aminorosinduEine, identical with the substance obtained by acting on %ace tamino-7- phenylnaphthaphenazonium chloride (Abstr., 1900, i, 463) with alcoholic ammonia, and subsequently eliminating the acetyl group ; the chloride forms slender, violet-brown needles, the acetyl derivative, U2+Kl9ON4Cl, crystallises from alcohol in dark-red needles with a brownish sheen, whilst the dichromcbte, (C,,H190N4)2Cr,0 7, is a red powder. W.A. D. The Thirteenth Isomeride of Rosinduline. By FRIEDRECH KEHRMANN and M. SILBERSTEIN (Ber., 1900, 33, 3300-3307. Com- pare preceding abstracts) .-4-Anilino-6 -acet y lam ino-1 : 2-nap h t haquin- one (Rehrmann and Matis, Abstr., 1899, i, Sl) condenses with o-amino- diphenylamine hydrochloride in boiling dilute acetic acid solution to form principally 3-acetylaminophenylrosinduline chloyide (3-ncetylamino- 5 -amilkno- 7-phenyZ~p~~thaphenc~oni~m chloride), a long with a small quantity of the isomeric 12-phenyliaon~p~~t~ah~na~onium chloride ; the latter separates first in brownish-red needles, and will be described in a later communication, whilst the former is obtained only on salting out. It crystallisea from alcohol in thick, dark-red prisms with a golden sheen, and with dilute alcoholic sodium hydroxide yields the 6ase, C,,H,,0N4* OH, in brownish-red leaflets with a bronze-like lustre.ORGANIC CHEMISTRY.103 separates on boiling the acetyl derivative with alcoholic hydrochloric acid, in thick crystals with a greenish lustre ; from solutions 'contain- ing an excess of hydrochloric acid, the hydrochloride, C,,H,,N,Cl,, is obtained. sJ--C H(NH,) 3-Aminorosindone, ,IF,.NPh >0, is formed on heating 3-acetylamino-7-phenyl~os~nduline chloride with 10 per cent. sulphuric acid for 2-3 hours at 175-180°; the acetyl derivative crystallises from acetic anhydride in vermilion-red needles with a greenish, metallic lustre, does not melt or decompose a t 310°, and unites with methyl sulphate in nitrobenzene solution at 150' to form 3-acetylamino-5- methoxy-7phenylnaphthaphenazonium methyl sulphate, This is precipitated on addini ether as an orange, crystalline powder, which regenerates rosindone on boiling with water containing a trace of alkali, and yields a ylatirtichloride, (C?I,H,o?,N,~,PtC~6,. as an orange-yellow, flocculent precipitate ; on warming with alcoholic am- monia, evaporating, extracting with water, and adding sodium bromide, 3-acetylaminorosindule bromide separates.It crystallises from b d - ing alcohol in vermilion needles with a greenish lustre, and yields an insoluble microcryst alline dichromate, ( C,,H190N,),Cr,07 ; on elimina- tion of the amino-group by the diazo-reaction, it forms 3-acetylarnino-7- phenylnaphthaphenazoniurn, isolated as the chloride in the form of an orange powder, sparingly soluble in water, which in dilute aqueous solution yields, on adding nitric acid, microscopic red needles of the nitrate. isoRosinduZine No. 1 3 (3-amino-7-phenylnc6phthaphenazort~um) was obtained by heating the foregoing chloride with 50 per cent. sulphuric acid ; the bromide forms olive-green needles and dissolves in water with a brownish-red, but in alcohol with a dark-green, colora- *ion.It is somewhat unstable in solution, yielding aminorosindone on boiling ; alcoholic ammonia converts it into aminorosinduline. The above indirect method of obtaining isorosinduline No. 13 became necessary because 6-acetylamino-1 : 2-naphthaquinone with o-amino- diphenylamine yields only the isomeric isorosinduline No. 7 (Abstr. 1899, i, 525). By HANS RUPE and KARL TON MAJEWSKI {Bey., 1900, 33, 3401-3408).-The principal '' osmophoric '' groups are -OH, -0, -CHO, -COMe, -OMe, -NO,, -CN, -N3 (triazo-). Analogous compounds containing -CHO, -NO,, -CN, -N3 have similar odours. Pipronylamide, NH,*CO*C,H,:O,:CH,, obtained by treating piperonylonitrile with hydrogen peroxide, crystallises in lustrous prisms or needles, melts at 1 6 9 O , in common with piperonylonitrile has a similar odour t o piperonal, and, when treated with bromine and * A name chosen by the authors t o designate those groups the presence of which predicates an odorous substance.W. A. D. Osmophoric Groups.*104 ABSTRACTS OF CHEMICAL PAPERS. sodium hydroxide, yields p- aininocatechol methylene ether, which is a white, crystalline substance, melts a t 44-46'? boils at 144' under 16 mm. pressure, and forms a hydrochloride, and an acetyl derivative melt- ing a t 135'. Triuxopyrocatechol methylene ether, N,*C,H,:O,:CH,, ob- tained from the hydrochloride just mentioned, crystallises in yellow leaflets, melts at 128-130' and has a faint odour like piperonal as well as the anise-like odour of all triazo- (azoimide) compounds. Methyl p-triuxobenxoate, N,*C,H;CO,Me, obtained by the method described in the next abstract, crystallises in large, yellow lamins, is volatile with steam, melts a t 39-40', and has a characteristic sweet anise-like odour, very similar to that of methyl p-cyanobenxoate ; the latter ester forms colourless leaflets melting at 62'.Nethyl m-tvi- axobenxoate and metiiyl o-tyiazobenxoate are light yellow oils having odours similar t o (but weaker than) that of the p-compound. p-ITri- ccxoanisole crystallises in yellowish-white laminae melting at 36', and o-triuxounisole is a heavy, yellow oil, both having odours similar to those of the triaxobenzoates. p-Tyiuxobenzaldehyde is a colourless liquid with n strong, pleasant, anise-like odour ; p-triaxobenxonitde, however, has hardly any odour and crystallises in colourless needles, which melt a t 70'.p-Triuxoacetanilide forms colourless crystals and melts at 124'. m-Hydroxyacetophenone, obtained by the diazotisation of m-amino- acetophenone and decomposition of the resulting diazo-compound, crystallises in colourless laminae, melts a t 95O, forms a methyl ether, which is a colourless oil boiling at 128-129' under 12 mm. pres- sure, and unlike the analogous 0- and p-compounds has hardly any odour. m Cyanoacetophenone crystallises in small, white needles, melts at 98-99', and has no odour ; the corresponding m-acetylbenxoic ucid crystallises in slender, white needles, melts at 172O, is odourless, and forms a methyl ester, which is a colourless, odourless oil ; m-tri- axoacetophenone is a yellow, odourlem oil.Preparation of Azoimides (Triazo-compounds). By HANS RUPE and KARL VON MAJEWSKI (Be?.., 1900, 33, 3408--3410).-The azoimides corresponding with weak bases are most conveniently prepared by treating a solution of a diazo-salt with potassium hydr- oxylaminedisulphonate. The method gave good results with p-nitro- aniline, m-nitroaniline, methyl p-aminobenzoate, and p-bromoaniline. p-Triaxobromobenxene forms crystals melting at 20' and has a pleasant aromatic odour. Hydroxylamine hydrochloride may be used instead of potassium hydroxylaminedisulphonate, but the results are not quite so good. R. H. P. Ketochlorides and Quinones of Phenylaeiminobenzene [Phenylbenzotriazole]. By THEODOR ZINCKE and E. PETERMANN (Annalen, 1900, 313, 251-298. Compare Abstr., 1899, i, 135).- R.H. P. ~O-CCI,-~-N CCI,*CHCI*C*NPh~~' Pheny Zaziminopentachloroketotetrahydrobenxene, Y prepared by the action of chlorine on phenylaziminoaminobenzene (Nietzki, Abstr., 1896, i, 164), crystallises in lustrous, colour- less needles, and melts at 128-129' ; it liberates iodine from potassium iodide, and develops a n intense red coloration with aniline.ORGANIC CHEMISTRY, 105 QO--cCl:y-N, Phenylaximinotetrachloroketodihydro6enxene, ccl,. cc, : c.Nph>N, ob- tained when the foregoing substance is heated afone or with potassium acetate, dissolves readily in organic media, and decomposes when attempts are made to recrystallise it; the compound melts at 173-174", liberates iodine from potassium iodide, and develops an intense red coloration with aniline.Pl~en~/laxirninotrichlorosohenol, formed on reducing the last-named substance with stannous chloride, crystallises from glacial acetic acid in pale yellow needles, which melt and decompose at 2%"; the acetql derivative forms colourloss needles and obtained by reducing the pentachloroketone with stannous chloride, crystallises in colourless, prismatic needles, and melts at 177-1 78". y0-co-l;l-N Phenyluxiininodichloro-o-quinone, :ccL, C.Nph>N, is formed from trichlorophenol and tetrachloroketone on oxidation with nitric acid, and crystallises in reddish-yellow leaflets having a golden lustre ; it melts and decomposes at 210°, and gives a bluish-green solution in sodium hydroxide. The cmilino-derivative, C1,H,,O,N4C1,C,H7N, puri- fied by precipitation with water from solutions in alcohol or acetic acid, melts and decomposes at 130-140'; the axine, Cl,H,N,C1,, pre- pared from the quinone and o-phenylenedinmine, crystallises in silky needles.and melts above 250'. OH* y: c'( OH) ;c;'-N Phenylaziminodichlorocatechol, ccl : .c,Nph>N, formed when the quinone is reduced with stannous chloride, crystallises from glacial acetic acid in slender, pale red needles which melt and decompose at 217O; the diacetyl derivative forms colourless needles and melts a t 187". OH*Y:C(OH)*fi--N Phen ylaaiminochlwocutechol, C-J: c K-c. Nph >N, the other product of reducing the quinone, melts and decomposes a t 214-215". OH*fi-CO-fi--N Pheny luximinochlorohydroxy - p-pinone, CCl*CO*C*NPh>Ny pre- pared by the action of sodium carbonate on the dichloro-o-quinone, crystallises in lustrous, yellow needles which melt and decompose at 223O ; the acetyl derivative forms lustrous, yellow needles melting at 1 35-1 36", whilst the anilino-derivative, C18H,0,N,CI, and the eurhodol, C18HloON,CI, decompose at 180' and 200" respectively.Phenyl~ximinotetrcLketotet~~hyd~oben~~ne, co. c.Nph>N, obtained on oxidising the p-quinone with nitric acid, crystallises from the con- centrated acid in colourless needles which become yellow in light, and melt and decompose at 175' ; the diasine, C,,H,,N?, is sparingly solu- ble in common media, and melts above 260'. GO*CO* fl-N106 ABSTRACTS OF CHEMICAL PAPERS. OH*C*CO*C-N Phenylaaiminodihydroxy-p-quinone, oH.i.co. E.Nph>N, formed when the tetraketone is dissolved in sodium carbonate, is a red powder which gradually darkens above 200°, and melts, decomposing, at about 254'.Phe~~laximinodichlo~~otri~etotetr~hvdrobe~xene. yo-co f-h CCl 0* c10 C N P hyNt produced when chlorine ii passed into a solution of the chlorohydroxy- p-quinone in acetic acid, crystallises in small, white needles and melts, decomposing, at 150-151' ; the axine, C,,H,,0N,C12, crystallises from glacial acetic acid in grey, lustrous needles, which sinter above 210°, and decompose at 238'. prepared from the pentachloroketoni by the action of dilute sodium hydroxide, and of bleaching powder in either acid or alkaline solution, crystallises from alcohol in colourless needles melting at 148'; the sodizcm salt forms transparent prisms, and the methyl ester melts at 124'.1-Phenyl-1 : 2 : 3-triaxole-4 : 5-dicarboxylic (n-pheaylpywo-1 : 2-diaxole- N-$*C02H dicarboxylic, phenylcximinoethylenedicarboxylic) acid, N<Nph.C.CO,H' resulting from the oxidation of the foregoing acid with potassium per- manganate, has been already described by Michael (Abstr., 1893, i, 570). 1-Phenyl-4-dichloromethyl-5dichloroethylene-1 : 2 ; 3-triaxole (n-phenylimino-1 ; 2-dicczole-3-dichZoromethyl-4-dichloroethykne), N--R*CHCl, NqNPh*C*CC1:CHC1 ' produced when the monocarboxylic acid is heated alone or with acetic anhydride, crystallises from glacial acetic acid and melts a t 95-96'. The a8-diketocarboxylic acid, N<Nph.&CO.CHCI, , prepared by the action of sodium carbonate on the dichlorotriketone, crystallises in lustrous, colourless needles which darken above 105', and melt and decompose at 130'; phenylhydrazine converts i t into the diphenyt- hydrazone, C2,H,,02N7C1, which forms reddish-brown, crystalline granules sintering above 110'.4Methyldeoxyxanthine and Deoxyheteroxanthine. By JULIUS TAFEL and ARTHUR WEINSCHENK (Ber., 1900, 33, 3369-3377, Compare Abstr., 1900, i, 121 ; ii, 588).-When 4-methylxanthine is dissolved in 50 per cent. sulphuric acid and reduced electrolytically a t 1-14' between prepared lead electrodes with a current concentration of 120 amperes, the sulphate of 5-oxy-4-methyl-6 : 7-dihydropurine (4-methyl- deoxyxanthine) separates ; this salt and the p'crute were analysed, The base itself crystallises with 1H,O, and decomposes at 210-220° without melting ; although neutral in reaction to litmus, it dissolves in dilute alkalis. It is oxidised by bromine in acetic acid solution N-C*CO*CO,H M. 0. F.ORGANIC CHEMISTRY. 107 (lead peroxide is not suitable) to 5-oxy-4-methyZpurzne ; this base and its sui'phate and picrate were prepared, and the last two were analysed. Heteroxanthine was also reduced in the manner just described ; in this case no sulphate separates. The product, 5-oxy-1-methyl-6 : 7- dihydropukae (deoxybeteroxanthine), decomposes at 260-264' without. melting ; i t is feebly alkaline to litmus, and does not dissolve in dilute alkalis ; the hydyochloride, sulphate, and picrate were prepared and analysed. The base is oxidised either by lead peroxide or by bromine, in acetic acid solution, to 5-oxy-I-methylpurine (E. Fischer, Abstr., 1899, i, 175). C. F. B. Isomeric Change of Azoxybeneene. By EUGEN BAMBERGER (Ber., 1900, 33, 31 92-31 93).-TYhen azoxgbenzene is converted into p- hydroxyazobenzene by warm sulphuric acid (Wallach and Belli, Abstr., 1880, 556), a very small quantity of o-hydroxyazobenzene is formed and may be isolated by the process already described (see following abstract). A. L. Action of Diazobeneene on Phenol and Synthesis of o-Hydr- oxyasobenzene. By EUGEN BAMBERGER (Ber., 1900,33,3188-3192j.. - 0-Hydroxyazobenzene is obtained in small quantity by the action of diazobenzene on phenol and may be separated from the para-derivative by distillation with steam and purified by means of its copper salt, which is very sparingly soluble in alcohol. It is identical with the substance obtained from nitrosobenzene (Abstr., 1900, i, 531). 0-Jlethoxyaxobenxene, OMe*C,H,*N,*Ph, is obtained on adding o-anis- idine to nitrosobenzene dissolved in acetic acid. It crystallises in groups of orange-red, compact needles melting a t 40-41°, dissolves readily in most organic media even in the cold, and is converted into 0-hydroxyazobenzene by aluminium chloride. 0-Hydroxybenaeneuzo-p-toluene, OH*C,H,*N,*C,H,Me, produced in small quantity when p-diazotoluene reacts with phenol, crystallises from boiling water in thin, shining, irregular yellow tablets or leaflets with a bronzelustre melting at 100-105°. It dissolves readily in or- ganic solvents and sparingly in water. Its solution in alkali is orange- red. The copper salt, which is sparingly soluble in boiling alcohol, forms brown, silky needles which have a green, metallic lustre. On reduction with zinc dust and aqueous ammonium chloride, the dye is converted into o-aminophenol and p-toluidine. A. L. Composition of Proteids. By ALBRECHT KOSSEL and W. KUTSCHER (Zeit. physiol. Chem., 1900, 31, 165-214).-An important contribu- tion to proteid chemistry, but which hardly admits of abstraction. Impor- tant quantitative results concerning the way in which different frac- tions of the nitrogen are combined, and the yield of such decomposition products as amino-acids, ammonia, hexon ba.res, &c., are given, to- gether with quantitative methods. Protaniines, proteids proper, and albumjnoids are all brought under review. W. D. H. Decomposition Products of Proteids. By FR. KUTSCHER (Zeit. physiol. Chm., 1900, 31, 214-226).-Hausmann's method (Abstr.,108 ABSTRACTS OF CHEMICAL PAPERS. 1899, i, 653; 1900, i, 317) of determining the way in which the nitrogen is combined in proteids is untrustworthy. NOTE BY ABSTRACToR.-This has been pointed out previously by Y. Henderson (Abstr , 1900, i, 265). The Carbohydrate Group of Crystallised Egg-Albumin, , By LEO LANCSTEIN (Zeit. physiol. Chem., 1900, 31, 49-57).--It is shown that the reducing substance which can be obtained from crystallised egg-albumin is glucosamine. The direct action of concentrated mineral acid on egg-albumin does not split off the reducing substance, because of the simultaneous production of ammonia. After treat- ment with alkali, as Pavy first showed, the reducing substance is obtainable. W. D. H. The Phosphorus of Nucleins. By ALBERTO ASCOLI (Zeit. physiol. Chem., 1900, 31, 156--160).--Neither in leuco-nuclein nor in casein is any of the -phosphorus contained in the form of meta- phosphoric acid. W. D. H. A New Decomposition Product of Yeast Nuclein. By ALBERTO ASCOLI (Zeit. physiol. Chem., 1900, 31, 161--164).-Thymin has been obtained from the nucleic acid from thymus, spleen, salmon sperm, and herring roe. The amount of materal hitherto obtained from yeast nuclein did not admit of analysis. In the present research, thymin was obtained by W. Jones’ method (Abstr., 1900, i, 572) from thymus, and a similar material from yeast nuclein ; the latter substance was not thymin, but uracil. Constitution of Thymin. By H. STEUDEL (Zeit. physiol. Chem., 1900, 30, 539-541. Compare Abstr., 1900, i, 467). When thymin is methylated by Hoffmann’s method (Abstr., 1890, 31) a product, C,H,Me,O,N,, is obtained which is isomeric with Behrend’s trimethyl- uracil (Abstr., 1886, 339). It crptallises from alcohol in needles melting at 153’. When thymin is nitrated and then reduced, a substance is obtained which gives Weidel’s reaction with chlorine water and ammonia ; the author concludes that the presence of a pyrimidine ring in thymin is thus established. ‘W. D. H. W. D. H. J. J. S. Antipeptone. By FR. KUTSCHER (Ber., 1900, 33, 345’7-3460).- A polemical paper in reply to Siegfried (this vol., ‘i, 57). J. J. S. Expressed Yeast-cell-plasma (Buchner’s Zymase). By EDUARD BUCHNER (Ber., 1900, 33, 331 1-3315).-The author criticises several of the numerical results obtained by Macfadyen, Morris, and Rowland (thisvol., i, 59), and points out that the considsrable amount of autofermentation obserred by them was probably due to the presence of glycogen in the juice. The juice obtained by the author underwent very little autofermentation, the amount of carbon dioxide thus evolved being always less than one-tenth of that evolved in the presence of sugar. A. H.

ISSN:0368-1769    

DOI:10.1039/CA9018000061

出版商:RSC    

年代:1901

数据来源: RSC