摘要:

J O U R N A L HORACE T. BROWN LL.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. H. B. DIXON M.A. F.R.S. WYNDBAM R. DUNSTAN M.A. F.R.S. bl. 0. FORSTER D.Sc. Ph.D. F.R.S. C. E. GROVES F.R.S. J. T. HEWITT M.A. D.Sc. Ph.D. OF A. MCKENZIE M.A. D.Sc. Ph.D. R. MELDOLA F.R.S G. T. MORGAN D.Sc. A. SCOTT M.A. D.Sc. F.R.S. Sir EDWARD THORPE C.B. LL.D. F. R. S. THE CHEMICAL SOCIETY. E. F. ARMSTRONG Ph.D. D.Sc. G. BAROER M.A. D.Sc. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. T. EWAN BSc. Ph.D. J. V. EYRE Ph.D. W. H. GLOVER Ph.D. E. GOULDING D.Sc. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY D.Sc. E. HOKTON B.Sc. Z. KAHAN B.Sc L. DE KONINGH. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. ABSTRACTS O F PAPERS ON ORGANIC CHEMISTRY. G. T. MORGAN D.Sc. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. PI1.D. W. ROBERTSON. E. J. RUSSELL D.Sc. S. B. SCHRYVER D Sc. Ph.D. G. SENTER Ph.D. B.Sc. W. P. SRERTCHLY. C. SMITH D.Sc. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKER Ph.D. B.A. G. S. WALPOLE B.Sc. M. A. WHITELEY D.Sc. W. 0. WOOTTON B.Sc. 1909. Vol. XCVI. Part I. LONDON GURNEY dz JACKSON 10 PATERNOSTER ROW. 1909.RICHARD CLAY & SONS LIMITED BREAD STREET HILL E.C. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90996FP001

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

J O U R N A L HORACE T. BROWN LL.D. F.R S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. H. B. DIXON M.A. F.R.S. WYNDHAM R. DUNSTAN M.A. F.R.S. M. 0. FORSTER D.Sc. Ph.D. F.R.S. C. E. GROVES F.R.S. OF A. MCKENZIE M.A. D.Sc. Pl1.D. R. MELDOLA F.R.S. G. T. MORGAN D.Sc. A. SCOTT M. A. D.Sc. F.R.S. Sir EDWAKD THORPE C. B. 0L.D. F. R. S. THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON PHYSICAL INORGANIC 11 INERALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. AXD - E. F. ARMSTRONG Ph.D. D.Sc. G. RARGER M.A. D.Sc. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. Ph.D. T. EWAN B.Sc. Ph.D. J. V. EYRE Ph.I). W. H. GLOVER Ph.D. E. GOULDING D.Sc. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTOR M.D. F.R.S. T. A. HENRY DSc. E. HOKTON B.Sc. Z. KAHAN B.Sc. L. DE KONINOH. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. G. T. MORGAN D.Sc. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. Ph.D. W. ROBERTSON. E. J. RUSSELL D.Sc. S. B. SCHRWER D.Sc. Ph.D. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc. L. J. SPENCER M.A. R. V. STANFORD M.Sc. 1’h.D. J. J. SUDBOROUGEI Ph.D. DSv. A. JAMIESON WALKER Ph.D. B. A. G. S. WALPOLE B.Sc. M. A. WHITELEY D.Sc. W. 0. WOOTTON B.Sc. 1909. Vol. XCVI. Part 11. LONDON GURNEY 6 JACKSON 10 PATERNOSTER ROW. 1909.RICHARD CLAY & SONS LIMITED BREAD STREET HILL E.C. AND BUNQAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90996FP003

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

36 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Hydrate of Iodine Oxyfluoride Fluoroiodates and Iodoxy- fluorides. RUDOLF F. WEINLAND and FERDIKAND REISCHLE (Zeitsch. anorg. Chern. 190P 60,163-172. Compare Weinland and Lauenstein Abstr. 1899 ii 363).-Iodine oxy$uoride hydrate IOF,,5H20 or IF3(OH)2,4H20 is obtained in colourless needles by dissolving iodic acid in a solution of hydrofluoric acid in glacial acetic acid and evaporating. The same compound contaminated with iodine is obtained when alcohol is used as solvent. The crystals fume in the air giving off hydrogen fluoride. Four salts containing pyridine have also been prepared. When 1 mol. each of iodic acid and pyridine are dissolved in an acetic acid solution of hydrofluoric acid and the solution evaporated over sulphuric acid pyridine trzjhoroioclate IF3(OH)2,C,N H separates in colourless prismatic needles.When a concentrated aqueous solu- tion of this salt is allowed to crystallise slowly pyridine dqjhoro- iodate IF,O(OH),C,N H is obtained in colourless crystals. When the pyridine salt first mentioned is dissolved in a mixture of hydro- fluoric acid and glacial acetic acid and 1 mol. of iodic acid 1s added pyridine pentaJEuorodi-iodate IF,O( OH) ,C,NH,,IOF,,H,O is obtained. Finally from a solution of 2 mols. of iodic acid 1 mol. ofINORGANIC CHEMISTRY. 37 pyridine and excess of hydrofluoric acid in alcohol pgridine hepta- Juorodi-iodate IF,( OH),C,NH,,IOF is obtained in colourless needles. All the pyridine salts are stable in air. The following five compounds are obtained by dissolving the corresponding iodo-compounds (iodobenzene and the iodotoluenes) in very concentrated alcoholic hydrofluoric acid.Phenyl iodoxyJtuoride hydroJEuoride C,H,*IOF,,HF the p-bromo-derivative C6H,Br*IOF2 HF and 0- m- apd p-tolyZiodoxy$uoride hydrofluoride C6H,Me*IOF2,H F all form colourless crystals which readily give up hydrogen fluoride. The compound IOF,,C,H,*IOF separates in colourless needles from a solution of 1 mol. of iodobenzene and 3 mols. of iodic acid in alcoholic hydrofluoric acid; it is readily decomposed by water. Ozone. 111. STEPHAN JAHN (Zeitsch. anoi-g. Ckem. 1908 60 292-336. Compare Abstr. 1905 ii 16; 1906 ii 292).-The sources of error in measurements of the electrical potential of ozone are discussed. The velocity of rotation of the electrode is without influence and the anomalies are therefore not to be explained by diffusion (compare Luther and Inglis Abstr.1903 ii 406). The effect is shown to be probably due to the adsorption of ozone by platinum. Measurements of potential were made against hydrogen with platinum electrodes in sulphuric acid with and without the addition of cobaltic sulphate. The results show that over the interval where Co”’ forms 2.5-8*0% of the total Co the potential of the cell corresponds closely with that required by the. ratio Co’” Co”. When Co”’/Co” = 1 the potential is 1.785 volt a value employed in calculating the ozone potential. The E.M.F. of a cell in which the reaction 0,+H,=H20+0 occurs is probably 1-90 volt at Oo. An equation is given by means of which the temperature-limits of stability of ozone may be determined derived from the Gibbs-Helm- holtz equation but the uncertainty of the values for potential and for specific heat is so great that no accurate calculation can be made.It appears however that ozone should be formed from oxygen by the action of heat alone in quite measurable quantity a t a temperature of 2000’ (compare Fischer and Marx Abstr. 1906 ii 224 606). G. S. C. H. D. Ozone. IV. STEPHAN JAHN (Zeitsch. anorg. Clzem. 1908 60 337-357. Compare preceding abstract).-The development of heat in the decomposition of ozone has been measured by a method similar in principle t o that of van der Meulen’s soda-lime being employed as catalyst and a current of ozonised oxygen of constant composition led through the calorimeter. The catalyst was contained in a glass tube connected with a copper spiral tube in a vacuum-jacketed vessel.The heat of dissociation of ozone is found to be 34,100 cal. per gram-molecule with a probable error of 1%. Investigation of the System Sulphur-Iodine. F. OLIVARI (Atti R. Accad. Lincei 1908 [v] 1’7 ii 512-521).-The freezing- C. H. D.38 ABSTRACTS OF CHEMICAL PAPERS. point curve of mixtures of sulphur and iodine is of the type of a cryohydric curve the eutectic point corresponding with 80.8 atom % of sulphur being a t 65.7'. The formation of compounds by fusion of these two elements is hence excluded the supposed melting point of the two iodides S,I and S,T2 being the cryohydric point. Cryoscopic measurements of sulphur dissolved in iodine show that the molecular weight has the value 256 corresponding with 5 in dilute solution but increases as the concentration is raised ; there is therefore no isomorphism between the two elements.The specific volume curve for mixtures of sulphur and iodine is a straight line joining the specific volumes of the two elements. The supposed iodides S21 and SI obtained by crystallisation from solution are mechanical mixtures of sulphur and iodine as also is probably the iodide S&. T. H. P. Absolute Sulphuric Acid its Preparation from Sulphur Trioxide and Water its Specific Electrical Conductivity and that of more Dilute Acid. DAVID 31. LICHTY (J. Amer. Chm. Xoc. 1908 30 1834-1846).-During a study of the decomposition of oxalic acid by sulphuric acid (Abstr.1907 ii 445) it was observed that the rate of decomposition was decreased to a surprising extent by the addition of only 0.01% of water to sulphuric acid supposed to beof 100% strength. Since analytical methods are not sufficiently accurate to determine the presence of very small quantities of water recourse was had to determination of the specific electrical conductivity of the acid. This method however could not serve t o establish the composition of the acid since the exact conductivity of any one concentration was not known. A method has therefore been devised for the preparation of absolute sulphuric acid by the direct interaction of sulphur trioxide and water in stoicheiometricel proportions. The specific conductivity of the acid obtained in this way has been determined a t 25O and found to be 0°01041 reciprocal ohm which is also the minimum specific con- ductivity of concentrated sulphuric acid.It has also been found that the maximum f. p. of concentrated sulphuric acid is identical with th6 f. p. of the absolute acid namely 10.43-10*45°. It is proved therefore that the preparation of absolute sulphuric acid may be based on the minimum specific conductivity and on the maximum f. p. It is shown that for acid of not less than 95% strength the results of analysis by means of conductivity determinations are accurate to within 0.01%. A table of specific conductivities is given which may be used for analytical purposes. Mixed Anhydrides of Sulphuric Acid. AMI~ PICTET and GEORaES KARL (Bull. 8oc. chim.1908 [iv] 3 1114-1126 ; Arch. sci. phys. nat. 1908 26 437-454).-1n preparing the mixed anhydride of nitric and sulphuric acids (S03)*N205 already described (Abstr. 1907 ii 758) there is also formed some sulphonitrous anhydride (S0,),(N20,) m. p. 198-200' b. p. 302-305O/728 mm. which is better prepared by dissolving sulphur trioxide and nitrogen trioxide separately in carbon tetrachloride and mixing the two solutions. It E. G.INORGANIC CHEMISTRY. 39 is a hard colourless substance crystallising in needles. Its properties are very similar to those of the nitryl tetrasulphate described previously and like the latter it gradually liquefies but does not fume in moist air. Since Provostaye's nitrosyl sulphate (Alan. Chim. phys. 1840 [ii] 73 362) has m. p. 217-230' and distils at 360° according to various authors it is suggested that it cannot have the formula ( S03)2N203 generally assigned to it but should probably be represented as (S03)6(N203)3 D'Arcy's observation (Trans. 1889 55,157) that boron and sulphur trioxides do not combine when heated together in open vessels is confirmed but combination takes place when the operation is carried out in a closed vessel boryl sulphate SO,(Q*BO) being formed at 115-120° boryl disuZphate (SO,),,B,O at 230° and mixtures of the two a t intermediate temperatures.Both are colourless amorphous bulky brittle hygroscopic substances which have no definite melting point do not fume in moist air but dissociate when heated leaving eventually residues of boron trioxide. They dissolve in water yielding solutions of boric and sulphuric acids.Boryl disulphate reacts with alcohol to form alkyl borates and alkyl-sulphuric acids. I n the last respect its behaviour differs somewhat from that of other mixed anhydrides (compare Friedel and Ladenburg Compt. rend 1865 64 84 ; Pictet and Geleznoff Abstr. 1903 i 309 601 ; Pictet and Bon Abstr. 1906 i 3). When chromium trioxide and sulphur trioxide are heated in closed tubes at 75' or a t a higher temperature a yellow mass of the mixed anhydride SO,ICrO is formed together with some chromium sesqui- oxide from which it could not be separated. F. OLIVARI (Atti R. Accad. Lincei 1908 [v] 17 ii 389-391).-Cryoscopic measurements of solutions of selenium in iodine (compare Timmermans Abstr. 1906 ii 429) give for the molecular weight of selenium the values 150*2-167*7 the number calculated for Se being 158.4; thus selenium has the molecular weight corresponding with Se at 4' (compare Beckmann Abstr.1904 ii 235) with Se at 42' (compare Beckmann and Sfeiffer Abstr. 1897 ii 363) and with Se at 113.9' (compare also Pelliai and Pedrina Abstr. 1908 ii 833). Volumetrio Composition of Gaseous Ammonia and Atomic Weight of Nitrogen. PHILIPPE A. GUYE and A. PINTZA (Compt. rend. 1908 147,925-928).-Ammonin prepared from pure ammonium chloride and lime was decomposed by a hot platinum wire and the nitrogen and hydrogen obtained were passed after purification into a vacuous vessel of about 39 litres capacity until the pressure was about one atmosphere at 0'. The loss in weight of the complete generating apparatus being known the weight and density of the mixed gases could be calculated.One litre of the mixed gases a t 0' and 760 mm. was found to weigh 0.37989 gram when corrected for traces of sulphur dioxide and trioxide. Knowing the densities of hydrogen and nitrogen and making allowance for their slight expansion on mixing the volumetric ratio of nitrogen t o hydrogen in ammonia is 1 3.00172. It follows that the atomic weight of nitrogen is 14.014 (0 = 16). T. A. H. Molecular Weight of Selenium. T. H. P.40 ABSTRACTS OF CHEMICAL PAPERS. Consideration of the sources of error however showed that any value from 14.002 to 14.022 might well have been obtained. The authors consider their method less accurate than direct gravimetric determinations.R. J. C. Oxidation of Ammonia by Potassium Permanganate and the Effect of Ammonium Salts on the Reaction. MORDKO HERSCHKOWITSCH (Zeitsch. physikal. CTLern. 1908 65 93-96). -Dilute solutions of ammonia and of potassium permaoganate in varying concentrations with or without the addition of ammonium salts have been heated for definite periods in a large flask a t 40° and the relative proportions of nitrogen nitrous and nitric acids in the mixture determined. Increase in the proportion of ammonia increases both the nitrogen and the nitrous acid and diminishes the nitric acid; increasing the concentration of both reagents has much the same effect except that the proportion of nitrous acid is not much altered. Addition of ammonium salts diminishes the aniounts of nitrogen and nitrous acid and greatly increases the nitric acid.Ammonium salts are formed in the course of the reaction even when none are present originally and in order to eliminate their action experiments have been made in which excess-of alkali is added previously. I n these circumstances less nitrous acid and more nitrogen are formed. G. S. The Kydrazinates of some Metallic Salts. HARTWIG FRANZEN and 0. VON MAYER (Zeitsch. anorg. Chem. 1905 60 24'7-291).- Hydrazinates of metallic salts have been prepared by Curtius and Schrader (Abstr. 1895 ii 10) and by Hofmann and Marburg (Abstr. 1899 i 486). A number of new methods of preparation are now described. On the addition of hydrazine to a solution of a cobalt- ammine salt reduction always takes place nitrogen being evolved and the hydrazine compound of a cobaltous salt being precipitated.The double compounds form crystalline powders insoluble in water soluble in acids or ammonia. Sulphates and nitrates tend t o combine with 3 mols. of hydrazine whilst chlorides bromides and oxalates with the exception of nickel chloride and bromide and of calcium and strontium bromides retain only 2 mols. The following compounds have been prepared With 3N,H Nickel chloride bromide sulphate nitrate and dithionate ; cobaltous sulphate and nitrate ; zinc nitrate ; cadmium nitrate ; calcium bromide ; strontium bromide. With 2N2H Nickel chloride bromide and oxalate ; cobaltous chloride bromide and oxalate ; zinc chloride bromide iodide oxalate and sulphate ; cadmium chloride bromide iodide oxalate sulphate carbonate and phosphate ; ferrous chloride and oxalate ; manganous chloride sulphate and nitrate ; cupric oxalate ; calcium chloride and nitrate strontium chloride ; barium chloride and bromide.One mol. of hydrazine replaces 2 mole. of ammonia. Full &alyses and descripiions of the compounds are given. C. H. D.INORGANIC CHEMISTRY. 41 Chlorine Azide [Chloroazoimide] N,Cl. FRITZ RASCHIG (Ber. 1908 41 4194-4195).-ChZoroacxoimide N,Cl is liberated as a colourless gas having an odour similar to hypochlorous acid when an aqueous solution of sodium azoimide (1 mol.) and sodium hypochlorite [l mol.) is acidified even with weak acids such as acatic acid or boric acid. It is slightly soluble in water forming a yellow solution and explodes with extraordinary violence when brought i n t o contact with a flame or glowing splinter and sometimes spontaneously with the production of a pale blue flame.It is decomposed by aqueous sodium hydroxide thus N,Cl + 2 NaOH = NaN + NaOCl + H,O. W. H. G. Preparation of Crystalline Silicon. A. J. KIESER (Chem. Zeit. 1908 32 1161-1 162).-With the object of ascertaining whether combination takes place between aluminium and silicon when methods involving the use of aluminium are employed for preparing silicon careful tests have been made for aluminium in the silicon and for ailicates in the slag. For the first tests crystalline silicon was prepared by Vigouroux's method and for the second the slag from Wohler's method was examined. I n each case the quantity of aluminium and silica respectively obtained was so small as t o make it evident that combination between aluminium and silicon does not take place.J. V. E. New Formation of Liquid Alloys of Potassium and Sodium. GEORGE F. JAUBERT (Bull. Xoc. chinz. 1908 [iv] 3 1126-1131 ; Ber. 1908 41 411G-4120*).-The liquid alloys ob- tained by the action of (1) sodium on potassium hydroxide and (2) potassium on sodium hydroxide are described. When sodium hydroxide is melted in a vacuous Jena flask with potassium reaction occurs a t 200-250° bubbles of gas (hydrogen 0) are evolved the temperature rises to 300° and a layer of the alloy NaK having the appearance of mercury is formed and floats on the excess of alkali hydroxide used. When potassium hydroxide (6 parts) and sodium (11 parts) are melted together in the same way at 250-275" the alloy NaK is formed but by modifying the quantities of the hydroxide and metal used and raising the temperature to 350° the chief product is the alloy NaE,. BQth alloys are liquid and do not solidify even at 10".They oxidise rapidly in cold air especially if fresh surfaces are continually exposed and even when kept under liquid petroleum the potassium slowly oxidises. The alloy NaK is now made commercially and is being applied in a number of industries. T. A. H. Cesium Chromates. FRANS A. H. SCHREINEMAKERS and D. J. MEYERINGH (Chem. TkekbZacl 1908 5 81 1-816).-The following chromates of cmium have been prepared (at 30") Cs2Cr0 ; Cs,Cr,07 ; Cs,Cr,O, and Cs2Cr4018. Their properties are similar to those of the corresponding chromates of potassium ammonium and rubidium. The mono- and di-chromates dissolve in water without decomposition ; * and Ann. Chim.anal. 1909 14 1-5.42 ABSTRACTS OF CHEMICAL PAPERS. the tri- and tetra-chromates are decomposed by water. The solubility of the monochromates of ammonium potassium rubidium and casium increases in the order given ; that of the dichromates di- minishes in the same order. A. J. W. Action of Carbon Dioxide under Pressure on Metallio Hydroxides at 0'. FRANK K. CAMERON and WILLIAM 0. ROBINSON (J. Physical Chem. l908,12,561-573).-The authors have determined the solubility of carbon dioxide in water at various pressures in presence of an excess of the solid hydroxides or carbonates. Succes- sive small quantities of carbon dioxide were forced into a tube con- taining the hydroxides or carbonates vigorously stirred with a small known weight of water and curves were obtained connecting pressure with weight of carbon dioxide in the apparatus.Breaks in these curves at any pressure indicate absorption of carbon dioxide by the solid phase that is the formation of solid carbonates or hydrogen carbonates. The only authentic solid hydrogen carbonates appear to be those of the alkali metals excluding lithium. Calcium ferrous iron and magnesium do not form solid hydrogen carbonates a t Oo even under 5 atmospheres pressure. The hydroxides of aluminium ferric iron and glucinum do not appear to combine with carbonic acid The authors regard the solubility of calcium carbonate in carbon dioxide solution as due to R specific solvent action of the carbon dioxide-water mixture rather than as indicating the formation of a hydrogen carbonate (compare however Raikow,uAbstr.1905 ii 85). R. J. C. The Solvent Action of Carbon Dioxide up the Carbonates of the Heavy Metals. CLARENCE A. SEYLER (Analyst 1908 33 454-457).-1t has been shown by Free (Abstr. 1908 ii 848) that the solubility of basic copper carbonate increases with the concentra- tion of the free carbon dioxide and the author now shows that Free's results exhibit regularities similar to those found for other carbonates and that these can be deduced from the principles of chemical equilibrium. The solubility of the basic carbonates of zinc and lead is governed by the same law. In all three cases the effect of a hydrogen carbonate would be to diminish the solubility according to the law Jn/r x HCO = constant when the carbon dioxide is kept constant.The protective action of calcium in solution as hydrogen carbonate on waters which act on lead and zinc is thus explained. w. P. s. Mixed Barium-Strontium Chromate Precipitate. LIONEL H. DUSCHAK (J. Amer. Chem. Soc. 1908 30 1827-1833).-Hulett and Duschak (Abstr. 1904 ii 616) have stated that the occlusion of barium chloride by precipitated barium sulphate is most easily explained by regarding the precipitate as an isomorphous mixture of barium sulphate with one or more complex barium salts and that cases of isomorphism in which one component owing to its ready solubility is present in only a minute quantity are probably not uncommon.INORGANIC CHEMISTRY.43 A study has now been made of the precipitate of mixed barium and strontium chromates formed as an intermediate product in the separation of barium and strontium by the usual analytical method. The results of the experiments show that a crystalline precipitate of barium and strontium chromates of definite composition is formed in a saturated solution of barium chromate containing given concentra- tions of strontium chromate and acetic acid. It has been found that diffusion takes place within this substance and that therefore it must either be regarded as a solid solution or else diffusion must be recognised as a-possible property of isomorphous mixtures. E. G. Silico-thermic Experiments. PAUL ASKENASY and CHARLES PONNAZ (Zeitsch.EZektrochem. 1908 14 810-81 I).-Barium peroxide and silicon react very violently when the reaction is initiated by means of a fuse. By using coarsely-powdered barium peroxide (50 parts) and silicon (15 parts) a barium silicide with 30% of barium is obtained. The mixture (with less silicon and a little sodium peroxide) may also be used to fuse iron or copper or powdered ferro-silicon or titanium silicide may be used in place of silicon. T. E. Estimation of the Valency of Glucinum by Colloidal Experiments. ANT. GALECKI (Zeitsch. Ekktrochem. 1908 14 767-768).-The quantities of barium calcium potassium glucinum magnesium lanthanum and aluminium salts required to coagulate a colloidal solution of arsenic sulphide are compared. Glucinum behaves in exactly the same way as barium calcium and magnesium very much larger quantities of potassium salts and very much smaller quantities of aluminium or lanthanum salts being required to produce the same effect.The results point to glucinum being bivalent. T. E. Compounds of Lead with Nitrous Acid. ALBERTO CHILESOTTI (Atti R. iiccad. Lincei 1908 [v] 17 ii 377-384 474-483. Compare Abstr. 1908 ii 948)-When treated with water the basic salt Pb(OH),,Pb( NO,),,H,O undergoes hydrolysis yielding the compound 3Pb0,N203,zH20 (Zoc. cit.). The latter then undergoes further hydrolysis during which the ratio Pb:NO increases to a value indicating the formation of the salt 4Pb0,N20,,H,0. The experiments carried out up to the present time show that the following basic salts must be regarded as definite compounds Pb(OH),,Pb(NO,) and its hydrate with 1H,O ; 3PbO,N,O or 2Pb0,Pb(N0,)2 and 4Pb0,N2O,,H,O ; the first two of these salts may be regarded as derivatives of ortho-nitrous acid H,NO,.The salt 3PbO,N,O may be prepared as follows The basic salt Pb(N02),,Pb(OH)2,H,0 is treated with increasing quantities of water the limpid yellow solution formed being replaced by water by which means an almost colourless turbid liquid is obtained from which the suspended substance is gradually deposited ; the substance then remaining undissolved consists of the salt 3P bO,N2O3,xH2O. Study of the electrolysis of the salt 4Pb0,N20,,N,0,,3H20 in44 ABSTRACTS OF CHEMICAL PAPERS. dilute acetic acid shows that the ions NO,’ or the molecules of the neutral nitrite Pb(NO,) do not form complex cations with lead and that the ions NO,’ and NO,’ move for the most part independently of one another and in proportions corresponding with the stronger dissociation of Pb(NO,) and with the greater mobility of the NO,’ ion; the current is carried only in small proportion by lead ions.I n order to ascertain whether lead nitrate combines with the nitrite in small proportion to form complex anions the author uses a method devised by Miolati and Pizzighelli (Abetr. 1908 ii 595). Con- ductivity measurements of solutions containing lead nitrite and nitrate show that the specific conductivity curve changes direction when the two salts are present in molecular proportions. It is hence probable that to a certain small extent these two salts combine in the proportion Pb(N03) Pb(NO,) to form a complex salt.Attempts to separate such a complex salt in the solid state from solutions containing the components in molecular proportions were unsuccessful. T. H. P. Optical Investigation of the Copper Complex in Ammonia and Pyridine Solutions. ARTHUR HANTZSCH and PHILIP WILFRED ROBERTSON (Ber. 1908 41 4328-4340. Compare Abstr. 19OS ii 447 646).-The method previously described has been extended t o the coppertetrammine complex and the following conclusions have been arrived at. All cupric compounds whether in aqueous or alcoholic ammonia solutions are optically identical and contain exclusively the coppertetrammine complex Cii(NH3)4 ; the base is coppertetrammine hydrate CU(NH,),(OH)~ and not the diammine hydrate.The colour is not materially altered whether the temperature degree of dissociation or solvent is changed and apparent departures from this are ascribed to chemical change; as for example the formation of a triammine- aquo-complex C U ( ~ H3)3. The solutions in aqueous pyridine of copper salts are likewise identical ; the complex is less stable than that with ammonia and is probably CUE;,. Copper acetate in pure or alcoholic pyridine contains another less intensely coloured complex probably Cu yy2 The chemical influence of the solvent is exhibited in the water and methyl ethyl and amyl alcoholic solutions of copper acetate probably due to the addition of solvent to the unsaturated complex Cu(OAc),. Copper forms in solutions only the complex CLIR and has co-ordina- tion number 4.W. R. (OH,) (OAc),’ Scandium. SIR WILLIAM CROOKES (Phil. Trans. 1908 209 A 15-46. Compare Abstr. 1908 ii 695).-About thirty scandium salts both of inorganic and organic acids have been prepared and analysed and their properties are described in detail. Some of the inorganic salts have already been described by previous observers. The chloride Sc,CI and the corresponding bromide crystallise with 12H,O ; the fluoride is anhydrous. Scandium potassium sulphate,INORGANIC CHEMISTRY. 45 Sc,(S0,),,3K,S04 is contrary t o the statement of Cleve and in agreement with Nilson only slightly soluble in a satura%ed solution of potassium sulphate. The selenate Sc,(Se04),,8H20 rhombic prisms loses 6H,O at looo and becomes anhydrous at 400O; it decomposes at a yellow heat.The nitrate Sc(N0,),,4H20 prismatic crystals is rendered anhydrous on heating over a water-bath and decomposes at a high temperature. When dried in a vacuum at looo for seventeen hours a basic nitrate Sc(OH)(NO,),,H,O is obtained and another basic nitrate Sc,O(NO,) is obtained by heating the nitrate for twelye hours in a hot-air oven at 120°. The majority of the organic scandium salts were prepared by interaction of scandium hydroxide and the corresponding acid. Most of the salts with fatty acids are more soluble in cold than in hot water. The formate (HCO,),Sc*OH,H,O occurs in hard lustrous crystals soluble in hot water and in alcohol. (C2H,02),Sc*OH,2H,0 forms fine white crystals which on being kept for some days lose 1 H20. The propionate (C,H,O,),Sc*OH occurs as a voluminous white powder easily soluble in alcohol ; the butyrate (C,H70,),Sc*OH the isobutyrate with 2H20 and the isovalemte (C,H902),Sc*OH,2H20 are also amorphous and soluble in alcohol Scandium oxulate Sc2(C204),,5 H20 occurs as a crystalline powder which loses 2H20 over sulphuric acid at the ordinary temperature 3H20 in air at looo and 4H,O in air at 1 4 0 O .It is moderately soluble in a solution of ammonium oxalate on which fact a method of separating scandium from other rare earths may be based. The succinate C2H4[ CO,Sc(OH),],,H,O is a white powder insoluble in water and alcohol ; the picrate (C6H,O7N,),Sc*0H,14H2O occurs in yellow needle-shaped crystals which explode faintly on heating. The salt loses 9H,O at 100'. The benzoate (C,H,*CO,),Sc and the o-toluate ( C,H4Me*C0,),Sc*OH,3H,0 form crystalline powders ; a basic o-toluate %C,H70,Sc,Sc(OH) obtained by using excess of the hydroxide occurs as a white powder.The m-and p-toluates both with 3H,O form white curdy precipitates insoluble in water ; the phenylacetate ( C7H7*C0,),Sc*OH,3H20 is also practically insoluble in water. The pyromellitate C H2[ CO,Sc(OH),] 2H20 a white amorphous powder loses 1H,O a t looo and the remaining molecule at 1409 The camphorate C,,H,,O,:ScOH is a white insoluble powder which is very electrical in the dry state. The atomic weights of the closely-related elements scandium yttrium and ytterbium are approximately simple multiples of that of boron and as they occur together in nature it is suggested that the elements of lower atomic weight may be formed from those of higher atomic weight by successive sub-division.Photographs of those parts of the spectrum containing the more prominent scandium lines are given. Scandium. I. RICHARD J. MEYER (Zeitsch. avzorg. Chem. 1908 60 134-151).-The extraction of scandium from wolframite (from Zinnwald Saxony) is described. The mineral contains 0.14-0*16% of rare earths in which scandium oxide predominates. The ore is The acetate G. S.46 ABSTRACTS OF CHEMICAL PAPERS. first fused with sodium hydroxide and extracted with water; the residue (chiefly the oxides of iron manganese calcium and lead) con- tains practically all the scandium (0*30-0*33% of the oxide). Two methods have been used for separating the scandium from the mixed oxides (1) To a neutral or slightly acid solution of the oxides a saturated solution of oxalic acid is added and the mixture kept for twenty-four hours.The precipitate which is richer in the rare earths than the original mixture is washed ignited dissolved in excess of hydrochloric acid and excess of hydrofluoric acid is added. The precipitate thus obtained is quite free from manganese and consists of the fluorides of lead calcium iron and of the rare earths. The remaining metals are removed by special methods and the rare earth residue finally obtained contains about 95% of scandium oxide. According to the second method the mixture of oxides is dissolved as completely as possible in hydrochloric acid solid sodium silico- fluoride is then added and the mixture boiled for half an hour when a precipitate containing all the scandium and practically none of the other rare earths is obtained.Iron calcium etc. are then removed as before and finally a very pure scandium oxide is obtained. The other rare earths except thorium can be separated from scandium by adding sodium thiosulphate to a neutral solution and boiling for some time; the precipitate consists of scandium thio- sulphate. The final product was tested for purity spectroscopically and by an atomic weight determination; it contained about 1% of thorium oxide for which no quite satisfactory method of separation has been found. G. S. Heats of Combustion of Aluminium Calcium and Magnesium. FRANK E. WESTON and HENBY R. ELLIS (Trans. Paraday Xoc. 1908 4 130-133).-Both magnesium and calcium reduce aluminium oxide on ignition with a fuse; magnesium also reduces lime.Lime and magnesia are partly reduced by aluminium and calcium respectively at high temperatures. C. H. D. Aluminium Carbide. PAUL ASKENASY W. JARHOWSHY and A. WANICZEK (Zeitsch. Blektrochem. 1908 14 81 1 - 4 1 3).-When pure crystalline aluminium carbide is heated above the melting point of aluminium in air or in an indifferent gas metallic aluminium exudes from it. In making the carbide from alumina and carbon in the electric furnace the best yield of carbide is obtained by rapidly cooling the contents of the furnace. When the cooling is slow the product consists mainly of the apparently unchanged mixture. The authors believe that the reaction Al,C Z 4A1+ 3C has a transition point; at high temperatures the carbide is the stable system at lower temperatures it decomposes into the metal and carbon.At the melting point of aluminium the velocity of decomposition is very con- siderable. These observations explain the presence of hydrogen in the gas evolved by the action of acids on aluminium carbide and also the fact that a copper-aluminium alloy is formed when it is fused with copper. T. E.INORGANIC CHEMISTRY 47 Fused Alumina in the Amorphous State and Reproduc- tion of Blue Colour of Sapphires. LOUIS PARIS (Compt. rend. 1908 147 933-935).-Pure alumina in the oxyhydrogen flame although it is only superficially fused absorbs chromic oxide through- out its mass giving artificial rubies. Oxides of cobalt iron etc. which would give a blue coloration are insoluble in pure alumina.Nickel oxide however dissolves giving a greenish-blue colour. If a small percentage of another oxide such as lime is added to the fused alumina cobalt and other colouring oxides dissolve giving a blue product the optical properties of which show it to be amorphous whereas pure alumina and artificial rubies are crystalline. Stones weighing as much as 20 carats can be obtained indistin- guishable from natural sapphires except by a slight difference in refractive index. R. J. C. Reproduction of the Blue Colour of Oriental Sapphires. AUGUSTE VERNEUIL (Compt. ?*end. 1908 147 1059-1061).-The author contends that the process described by Paris (preceding abstract) does not accurately reproduce the colour of Oriental sapphires.w. 0. w. Alum. ROBERT MARC (Zeitsch. anoyg. Chem. 1908 60 193-207). -Whilst a specimen of alum obtained from Kahlbaum had a solubility in water of about 10 grams per litre at 17" being independent of the degree of supersaturation before cooling and it readily formed super- saturated solutions a specimen obtained from Merck was less soluble had very little tendency to form supersaturated solutions and the solubility depended on the degree of supersaturation before the excess. of salt was caused to separate by inoculation; the higher the super- saturation the greater the final solubility. It was then found that the alum which separated from dilute solutions contained more alkali that is it was more basic than that separating from more concentrated solutions.The original alum of Merck however was of the usual composition as was that of Kahlbaum. No adequate explanation of these phenomena has so far been found. Of the commercial alums examined only Merck's showed the peculiarity in question. G. S. Solidihation Curves of Certain Molten Silicates. EMIL DITTLEB (Monatsh. 1908 29 1037-1074).-The freezingpoint curves for mixtures of aegirite and nephelin labradorite and nephelin and labradorite and diopside have been determined. Comparative measurements were made for mixtures of the minerals and of the artificial substances. In general the melting-point curves for mixtures of the artificial products are higher than those for the minerals. The melting points of the crystalline mixtures lie in all cases approximately on a straight line whilst in the case of the glaases the melting points are considerably lower than those of the two components.The order in which the silicates separate out is magnetite augite q i r i t e labradorite diopside nephelin and sodium augite. This succession is in agreement with Rosenbusch's rule.48 ABSTRACTS OF CHEMICAL PAPERS. The experimental data lead the author to doubt whether the solidification of complex silicate mixtures is even approximately regulated by the factors which determine the same process in the case of simple sptems. RUDOLF F. WEINLAND and P. DINHELACHER (Zeitsch. anorg. Chem. 1908 60 173-17'7).-Meyer and Best (Abstr. 1900 ii 77) have obtained double salts of manganese tetra- and tri-chloride with potassium chloride by leading hydrogen chloride into a solution of potassium permanganate in glacial acetic acid.The authors now show that these and corresponding double salts can be obtained by the action of aqueous concentrated hydrochloric acid on permanganates. The compound MnC1,,2KCl is best obtained by adding calcium permanganate and a concentrated solution of potassium chloride to a 40% aqueous solution of hydrochloric acid cooled with ice and salt ; it forms small dark red crystals. The corresponding rubidium and ammonium salts have been obtained in the same way. From the solutions from which the double salts of quadrivalent manganese have separated double salts of tervalent manganese of the type MnC13,2KC1 are obtained on adding excess of the alkali chlorides in concentrated aqueous solution.The rubidium caesium potassium and ammonium salts have been prepared; all except the rubidium salt have been described by previous observers. H. M. D. Action of Hydrochloric Acid on Permanganates. G. S. Action of Chlorine on Ferroboride and Manganese Boride at High Temperature. JOSEF HOFFMANN (Zeitsch. alzgew. Chem. 1908 21 2545-2546).-When Goldschmidt's ferroboride is heated to 300-400' in a long combustion tube in a current of dry chlorine there is produced near the heated substance a small quantity of a dark green sublimate having the composition Fe,Cl,B. The chief product however condenses farther away on the cooler parts of the tube as a brown solid and is probably a complex substance composed of boron chloride and ferrous chloride. A still more volatile compound was condensed in a U-tube connected to the combustion tube and kept in a cooling mixture; this was a pale yellow highly refractive liquid b. p.24-28' which appears to be impure boron chloride. Manganese boride heated in dry chlorine in a similar manner also gave complex manganese boro-chlorides but in such small quantities that a t present it has not been possible to ascertain their composition. J. V. E. Composition of Colloidal Ferric Hydroxy-chlorides. L~OPOLD MICHEL (Compt. rend. 1908 147 1052-lO54. Compare Malfitano Abstr. 1906 ii 450)-This paper contains details of the method adopted for studying the composition of colloidal ferric chloride solutions by filtration through collodion membranes. Experiments have been made to determine the ratio Fe Cl in the micro-cells of ferric hydroxy-chloride to which the membranes are impermeable and in the filtrate which constitutes the intercellular liquid.From theINORGANIC CHEMISTRY. 49 analytical data obtained the author arrives at the conclusion that the colloidal solution contains several physical units of variable com posi tion. I n one series of experiments carried out on an ochreous solution of ferric chloride containing a precipitate the intercellular liquid was found to be of uniform composition throughout. The micro-cells suspended in the top layer contained iron and chlorine in the atomic ratio Fe C1= 2.4 1 whilst in the lower layer containing the sediment the ratio was 4.5 1. In the stable colloidal solution obtained by adding ferric chloride to boiling water a separation of micro-cells of different composition was Complex Metal Ammonias. VIII.Transformation of Hexamminetrioldicobalt Salts into Octamminedioldicobalt Salts. ALFRED WERNER (Ber. 1908 41 3879-3884. Compare Abstr. 1908 ii 42 43).-It has been found possible to pass from a hexamminetrioldicobalt salt having the constitutional formula (I) t o an octamminedioldicobalt salt having the formula (11) that is t o replace an “01-bridge” in the former by 2 mols. of ammonia and thus obtain further confirmation of the correctness of these formuls effected by means of the centrifuge. w. 0. w. Hexamminetiioldicobalt sulphate (compare this ’voi. ii 43) is converted by cold 50% nitric acid into dinitratohexamminedioldicobalt nitrate [N0,(NE3),Co(OH),Co(NH,)3N0,](N0,)2,3H20 which crys- tallises in pale violet glistening scales.Its aqueous solutions quickly decompose ; consequently other salts of this series could not be prepared in a pure state. A freshly-prepared solution when treated with sodium dithionate slowly deposits nitratoapuohexammine- dioldicobalt dithionate ~E~o~NH~~~Co~oH~~Co~NH~~~N0,1,(as small pale violet scales. An aqueous solution of the nitrate which has been kept for some time when treated with sodium sul phate yields diaquohexa~nrninedioldicobalt sulphate an intense bluish-violet sparingly soluble salt which could not be obtained pure. The nitrate is converted by liquid ammonia and subsequent treatment with ammonium bromide into octammine- dioldicobalt bromide (compare Abstr. 1907 ii 965).Complex Metal Ammonias. IX. Decammine-p-amino- dicobalt Salts. ALFRED WERNER (Ber. 1908 41 3912-3921. Compare Abstr. 1908 ii 42).-When octammine-p-amino-01-dicobalt nitrate is treated with nitric acid in the cold nitratoaquo-octammine- [ C O ~ ( N H ~ ) ~ ( O H > ( O ~ ~ ) ~ I ( S ~ ~ ) ~ ~ 01 3H2Q W. H. G. p-ccminodicobalt nitrate [(NH,)4Co*NB,Co(N4](~O~)~ = 2 0 is ob- tained quantitatively as a violet salt. This on addition in small quantit& to well-&red liquid ammonia is converted into the decammine-p-amminodicobalt nitrate a small quantity of the octammine- VOL. XCVI. ii. 450 ABSTRACTS OF CHEMICAL PAPERS. p-amino-ol-dicobalt nitrate being regenerated. The constitution of this salt was determined independently of the octammine series as chloro- pentammine-cobalt and hexammine-cobalt salts are obtained by the action of a mixture of hydrochloric and sulphuric acids from which the deduction is made that five molecules of ammonia are attached to each of the cobalt atoms thus [(NH,),CO*NH,*CO(NH,)~]C~~ + HC1= [ c o ~ H 3 ) ~ c l ~ + [Co(NH,),]Cl,.That the decammine salt is not an imino-derivative wf the type [(XH,)5Co*NH(HCl)-Co(NH3)5]C14 is shown by its behaviour towards alkalis the elements of hydrogen chloride not being withdrawn. These salts have all a bluish-red colour and correspond with the rhodochromium salts [Cr,(:?),"JX from which the conclusion is drawn that the hydroxyl in the chromium compound plays *he same part as the p-amino-radicle in the cobalt derivatives. The nitrate Y(NO,),,(Y = [(NH,),*Co*NH,*Co(NH,),lf forms dark bluish-red needles ; the chZoi*ide YCI,,H20! precipitated from the solution of the nitrate by addition of ammonium chloride crystallises in glistening reddish-violet needles and is not decomposed on boiling with concentrated hydrochloric acid. It is only decomposed by the mixture of sulphuric acid and hydrochloric acid by long-continued heating.The bromide Y Br,,H,O forms slender reddish-violet needles ; the dithionate Y2(S20,),,6H20 forms a rose-red powder which on heating a t 60-80° loses 4H20 and is converted into the hexammine and hydroxyl pentammine salts. This was shown by treatment with aqueous ammonium bromide when the hexammine bromide was precipitated. The filtrate on addition of alcohol deposited a bluish-red powder free from sulphur which on boiling with hydrochloric acid gave chloropent ammine-cobal t chloride.The sulphate Y,( SO,) 3H,O crystallises in red needles and thin prisms. W. R. True Peroxide of Nickel. GIOVANNI PELLINI and D. MENEGHINI (Zeitsch. anorg. Chem. 1908 60 178-190).-A nickel peroxide of the formula NiO,,xH,O has been obtained as follows. A dilute solution of nickel chloride is cooled to - 50° an equal volume of 30% hydrogen peroxide added and finally potassium hydroxide in alcoholic solution. The precipitate is washed several times with cold alcohol and then with ether and forms a greyish-green powder stable in the air. The pure peroxide has not been obtained but in one case the ratio N i 0 was as high as 1 1.98. The same peroxide is obtained by the action of hydrogen peroxide on free nickel hydroxide but the reaction is comparatively slow a large proportion of the hydroxide remaining unchanged.The proportion of water associated with the peroxide has not been determined. The greyish-green peroxide gives all the reactions of hydrogen peroxide and its behaviour is quite different from that of the peroxide of the same formula described by Bellucci and CIavari (Abstr. 1905 ii 823) ; it is therefore suggested that the former oxide has the con- 0 0 0' atitution Ni< I and that described by Bellucci Ni< 0 G. s.INORGANIC CHEMISTRY. 51 Chromium Compounds. VII. Hydrates of Chromium Fluoride and an Example of Go-ordinate Isomerism among Hydrates. ALFRED WERNER and W. COSTACHESCU (Ber. 1908,41 4242-4246).-The compounds CrF CrP3,4H,0 2CrF,,7H20 and CrF3,9H,O are described in chemical literature.The authors have examined the compounds with 7 and 9H,O and the following new compounds CrF,,6H20 2CrF,,7H20 and CrF 3H,O. Hexaquochromium fluoride [ Cr(0H2),JF3 forms a violet crystalline powder and is obtained by adding a concentrated solution of potassium fluoride to a similar solution of violet chromium nitrate. Its electrical conductivity (in paraffin vessels) is about half that of the violet chloride and treatment with sulphuric acid gives rise to hexaquo- chromium sulphate. When the moist crystals are kept they yield the violet hydrate CrF,,9H20. This conversion occurs spontaneously when the crystals are washed especially when they are pressed slightly with a spatula. This hydrate yields hexaquochromium sulphate when treated with sulphuric acid and the formula [Cr( OH,),](OH2F) is suggested.~exapuochomium chromium hexafluorids [ Cr( OH,),]CrF is obtained as an insoluble green product when the hexaquochromium fluoride is warmed with water. A monohydrate [Cr(OH,),]CrF,,H,O is obtained by double decomposition between hexaquochromium chloride and ammonium chromium hexafluoride (NH4)&rF6. It forms a pale green crystalline powder with a pearly lustre and when heated at 105' loses a molecule of water yielding the insoluble green compound. The monohydrate is isomeric with Poulenc's salt (Abstr. 1893 ii 321) which is regarded as trifluorotriaquochromium monohydrate The hexahydrate loses 3H,O a t 60-70'. [crq;H2)JJ320 ; its aqueous solution has a distinctly acid reaction but does not give the reactions of fluorides. J.J. S. Higher Oxidation Products of Chromium. V. Per- chromates. ERNST H. RIESENFELD (Ber. 1908 41 3941-3951. Compare Abstr. 1908 i 963).-There are two classes of perchromates the salts derived from the penta-acid HCrO are blue in colour those derived from the octa-acid H,CrO are red. The salts of chromato- diperacid do not exist (Abstr. 1904 ii 410 737). A red hydrated potassium perchromate analogous to the sodium salt has been prepared by the action of chromic acid on potassium cyanide in the cold. This salt crystallises in rhombic plates and very quickly loses its water of crystallisation. The constitution of these salts has been investigated by determining their molecular weights. C,H,N,HCr05 is unimolecular and from determinations of the freezing points in aqueous solution the red potassium and ammonium perchromates have also the simple formula M,CrO,.The solutions are good electrolytes. Determination of the mo1.-wt. of the free acid is not possible because of its rapid decomposition in water; this decom- The blue pyridine perchromate 4-252 ABSTRACTS OF CHEMICAL PAPERS. position has been measured in a mixture of ether glacial acetic acid and water and obeys the unimolecular law As this argument for the simple formula in the case of the free acid is not conclusive the electrochemical equivalent of the chromium was determined and shown t o be 1Cr:GAg in the case of the red potassium salt. It is not possible to assign a formula to this salt on the assumption of the univalency of potassium the bivalency of oxygen and the sexavalency of chromium.Although hydrogen peroxide cannot be proved t o be a product of the decomposition of these salts yet alkaline gold chloride and permanganate are reduced during the change and the assumption is made that these salts are analagous to alkali peroxides. The equivalent of permanganate reduced is held to be a measure of the '' holoxide " oxygen groups. The blue pyridine perchromate decomposed very rapidly and so this could not be measured but in the decomposition of the red salts 5.5 equivalents of the permanganate were reduced. The conclusion is drawn that t h i s is due to the formation of 3H,02 and that therefore the constitutions of these acids are /O*OH 0 ECr-O*OH. \O*OH /O*OH Red.W. R. 021c'N0 Blue. Derivatives of Complex Inorganic Acids Alumino- tungststes and Aluminophosphotungstates. LLOYD C. DANIELS (J. Arner. Chem. Xoc. 1908 30 1846-1857).-Balke and Smith (Abstr. 1904 ii 179) have described the aluminotungstates 3(NH4),0,A1,03,9 W0,,4H20 and 1 1 A g,O,:! 1 (N H4!,0,4A1203,36 WO,. The present investigation was carried out with the object of ascertain- ing whether the ratio A1,0 9W0 would exist in other derivatives. The following salts have been prepared and described Copper ccluminotungstate 2Cu0 A1,0,,9W03 16$H,O ; the barium salt 8B;z0,A1203,9 W0,,7H20 ; the mercurous salt 5Hg20,A1,0,,9W0 and the zinc salts 1&Zn0,h1,03,9 WO3,8H,0 and ZnO,A1,O3,9 WO 20H,O. 9(NH,),0,2A1,0,,4P,05 9MT0,,13H,0 ; the silver salt 4Ag,0,2Al,0,,4P20,,9W0,,6H,0 ; the barium salt 4BaO,2Al20,,4P2O5,9 W0,,3K2O and the zinc salt 5Zn0,2A1,0,,4P2O5,9WO3,1 1H,O are also described.The ammonium salt 6(NH4)20,2A1203,3As,05,18W0,,14H,0 ; the barium salt 4BaO,2A1,0,,3A~,C)~ 18 W0,,12H20 and the cadmium salt 4Cd0,2A1,0,,3As205 1 S WO3,17H,O. A description is also given of the following aluminoantimonio- tungstates. The ammonium salt 6(NH4),0,2A1,03,3Sb205,18W03 1 7H20 ; the silver salt 6Ag,0,2A120,,3Sb205,18W03,1 2H,O and the barium salt 5BaO,2Al20 3s b,0,,1 S W0,,6H ,O. Ammonium aZurnino;uhosiohotungstate The following aluminoarsenotungstates have been prepared. E. G.INORGANIC CHEMISTRY. 53 Comppmds of Silicon and Uranium. Uranium Disilicide Usi,. EDOUARD DEPACQZ (Compt. rend.1908 14'7 1050-1052." Compare Abstr. 1907 ii 475 696)-The silicides of tungsten and molybdenum of the type MSi having been prepared previously the author completes the series by describing the preparation and properties of the corresponding uranium compound. Uranium disilicide USi obtained in small yield from silica and the oxide U,O by the aluminothermic method occurs as brilliant microscopic crystals DO 8 belonging to the regular system. Chlorine attacks this silicide at 500° giving the chlorides of uranium and silicon. Cold hydrogen fluoride dissolves it readily whilst oxidising agents have little action. Although stable in air at a red heat it burns slowly in oxygen a t 800° and is decomposed on fusion with alkalis alkali carbonates or potassium hydrogen sulphate.Details are given of the method adopted for the analysis of this Thorium. WERNER VON BOLTON (Zeitsch. Elektrochem. 1908 14 768-770).-The metal is prepared in minute crystals by reduction of the tetrachloride by sodium. By hammering the metal into a thick- walled copper tube 10 mm. in diameter rolling this down to 1 mm. wire and removing the copper with dilute nitric acid a spongy wire of thorium is obtained which can be rolled out to a band. The melting point is 1450' ; it burns in the air ; potassium hydroxide and nitric acid have little action ; sulphuric acid slowly attacks it yielding the sulphate and hydrochloric acid acts quickly leaving about 15% of the metal undissolved in the form of lower oxides which are possibly formed during the action. The density of the powder is 11.32 that of the rolled band 12.16.When the powder is shaken with cold 5% hydrochloric acid the first portion which dissolves (about 10% of the whole metal) forms a complex acid (ThO,),o(HC1),,. the solution of which contains neither thorium nor chlorine ions; its principal reactions are with oxalic acid or sulphuric acid a small precipitate soluble in excess is pro- duced ; ammonium oxalate gives a gelatinous precipitate insoluble on boiling ; ammonium carbonate and citric acid give gelatinous precipi- tates insoluble in excess. The metal reduced from this compound is ordinary thorium. T. E. RICHARD J. MEYER (Zeitsch. EZekts.ochem. 1908 14 809-8 lo).-The reduction of thorium oxide by carbon tetrachloride yields a metal containing considerable quantities of oxide (Abstr.1901 ii 106). The oxide left by Bolton's thorium when dissolved in acid (preceding abstract) was therefore doubtless present in the metal. This also explains the action of dilute hydrocbloric acid ; the dissolved substance was probably metathorium chloride derived from the oxide. Chlorides and Oxychloridels of Thorium. EDOUARD CHAUVENET (Compt. rend. 1908,147,1046-1048. CompareMatignon Abstr. 1901 ii 106).-Thorium tetrachloride is most conveniently prepared free * and Bull. Soc. chim. 1909 [ iv] 5 3-5. compound. w. 0. w. Thorium. T. E.54 ABSTRACTS OF CHEMICAL PAPERS from oxychloride by heating thorium dioxide in a current of carbonyl chloride. A deliquescent white powder which is formed at the same time has been proved t o be identical with the crystalline chloride by analysis and by measurement of its heat of solution in water (56.75 Ca!.at 12.6O). An aqueous solution of the tetrachloride deposits ThC14,7H,0 on evaporation (compare Kruss Abstr. 1897 ii 456). The heat of dissolution of this hydrate is 14.75 Cal. at 13.5'. When heated at 120-160' in hydrogen chloride the oxychloride OH*ThC13,H20 is obtained as a very hygroscopic powder of which the heat of dissolu- tion is 47.63 Gal. at 13.5" (compare Rosenheim Abstr. 1900 ii 351). The chloride ThCI 7H,O is converted into the oxychloride ThOCI at 250'; the heat of dissolution of the latter is 28.15 Cal. at 13'. w. 0. w. Basic Sulphates of Thorium and Cerium. OTTO HAUSER and F. WIRTH (Zeitsch. anorg. Clhem. 1908 60 242-246).-Dilute solu- tions of thorium sulphate deposit flocculent thorium hydroxide con- taining some adsorbed sulphate on boiling ; thus resembling zirconium sulphate (Abstr.190'7 ii 626). Concentrated solutions heated in sealed tubes at 160-180° deposit crystals of ThOSO,,H,O. A t 105-115O the same salt is deposited mixed with the normal hydrated sulphate. A dilute ice-cold solution of ceric sulphate deposits after twenty- four hours pale yellow crystals of 4Ce0,,3S0,,12H20 completely analogous t o the basic zirconium sulphate. Boiling saturated solu- tions of ceric sulphate deposit crystals of 2Ce0,,3S0,,4H20 which however could not be obtained in a pure state since they rapidly redissblve on cooling and some reduction to cerous sulphate takes place. C. H. D. Derivatives of Complex Inorganic Acids Phosphovanadio- molybdates.WILLIAM BLUM (J. Amer. Chem. SOC. 1908 30 1858-1862).-Wolcott Gibbs (Abstr. 1884 713) described two phosphovanadiomolybdates 8( NH,),O 2P20,,8V2O5 1 4Mo03,50H20 and 7(NH4)20,2P205,V,0,,48Mo03,30H,0 and suggested that it was probable that the vanadium pentoxide considered as V,0,*03 might replace the molybdenum trioxide of the phosphomolybdate. He was unable however to obtain a salt containing a higher proportion of vanadium pentoxide than that in the first compound mentioned. The present author is of opinion that this was probably due to the fact that an excess of ammonium vanadate was used in all the experiments. The formation and composition of the ammonium phosphovanadio- molybdates has now been further studied and the following corn- pounds have been obtained 6(NH4),0,P,0,,4V,05,1 8Mo03,52H,0 and the corresponding silver salt ; 5(NH,),0,P205 2&V,05,21 &MoO3,50H,O ; 8(NH,),O,P,O5,5V,O5 1 8M00,,45H20 ; 7(NH,),0,P,05,5~V,05,1 64Mo0,,50R2O ; 8( NH,),O,P,O W,05,1 5Mo03,50H,0,INORGANIC CHEMISTRY.55 and the corresponding silver salt ; 8(NH,)20,P205,8V20 1 4M00,,50H20 ; 8( NH,) 20,P,05 1 O& v,o 1 1 +Moo ,5 OH@ ; and 8(NH,),0,P205,1 lV205,1 1 MoO,,!XH,O. All these ammonium salts crystallise in the tetragonal system and are soluble in water. E. G. Action of Antimony Trichloride on Cobalt and on its Alloys with Antimony. F. DUCELLIEZ (Compt. vend. 1908 147 1048-1050. Compare Abstr. 1908 ii 853).-When cobalt is submitted to the action of antimony trichloride at '700-1200° cobalt monoantirnonide CoSb is formed as a crystalline non-magnetic powder Do 8.12 m.p. about 1200'. This undergoes slight oxidation in air and burns readily in oxygen ; hydrogen chloride has little action on it but hot concentrated sulphuric acid dissolves it rapidly. At 700-1 450" it attacks antimony trichloride forming antimony and cobalt chloride ; the composit'ion of the residual substance however remains unaltered. At 1200' cobalt is attacked by antimony tri- chloride and forms magnetic alloys containing less antimony than the foregoing antimonide ; this compound remains as a non-magnetic powder when these alloys are treated with sulphuric acid. Three classes of alloys of cobalt and antimony have been prepared by direct union of the elements at 500" in a current of hydrogen.(1) Magnetic alloys containing less than 67.04% antimony. When heated with antimony trichloride at SOO" or when treated with sulphuric acid these lase their magnetic properties and leave a residue of the monoantimonide CoSb. (2) Alloys containing 67.O4-8Oa27% of antimony which decompose readily on heating and form the monoantimonide when heated at 1200' in hydrogen. Substitution of antimony trichloride for hydrogen gives the same compound together with antimony and cobalt chloride. (3) Allqys containing more than 80027% antimony which on treatment with nitric acid followed by hydrogen chloride give cobult diantimonide CoSb a grey crystalline powder Do 7.76 m. p. about 700'; this closely resembles the monoantimonide in its chemical properties.w. 0. w. Atomic Weight of Bismuth. 111. Analysis of Bismuth Bromide. ALEXANDER GUTBIER and HANS MEHLER (J. pr. Chem. 1908 [ii] 78 409-420. Compare Abstr. 1906 ii 92 ; 1908 ii -600).-The bismuth bromide employed in this investigation WRS pre- pared by the action of bromine on four specimens of bismuth. The percentage of bromine present in each of the four samples of bromide was! determined by dissolving the ,latter in 2N-nitric acid and pre- cipitating with silver nitrate. As the result of eight experiments it was found that 34.81207 grams of bismuth bromide gave 43.80773 grams of silver bromide. The extreme values obtained were Bi= 208.18 and Bi = 207.88. The value 208.0 +_ 0.06 (0 = 16) for the atomic weight of bismuth determined by this method is in agreement with the result (Bi = 208.0) obtained by Gutbier and Birckenbach (Abstr.1908 ii 600) by the synthesis of bismuth oxide. W. H. G.56 ABSTRACTS OF CHEMICAL PAPERS. Atomic Weight of Bismuth. IV. Synthesis of BiBmuth Sulphate. ALEXANDER GUTBIER and RUDOLF L ~ O N JANSSEN (J. pr. Chem. 1908 [ii] 78 421-436. Compare preceding abstract).-The atomic weight of bismuth was determined in this investigation as follows a known weight of the element was dissolved in nitric acid (D 1*05) the nitrate obtained evaporated with sulphuric acid and the sulphate heated to constant weight in an electric-oven at 380". Two specimens of bismuth were used ; three experiments with one sample gave the mean value Bi= 208.04 whilst two experiments with the second sample gave Bi = 208.1'7. The extreme values obtained were Bi = 208.26 and 207.92. The atomic weight of bismuth determined by this method is 208.1 (0 = 16). From the results of the investigations of Marignac (Abstr. 1884 813) Lowe (Abstr. 1884 558) Schneider (Sbstr. 1895 ii 114) and of Gutbier and his co-workers it follows that bismuth has the atomic weight 208.0 (0 = 16). Carbonatels and Oxalates of Bismuth. LUDWIG VANINO and EMILIE ZUMBUSCH (Bey. 1908 41 3994-3999).-Attempts t o pre- pare normal bismuth carbonate and oxslate show that these substances are extremely sensitive to the hydrolytic action of water. Only by working under strictly defined conditions can substances of definite composition be obtained. The normal carbonate has not been isolated but the oxalate is obtained when a solution of bismuth nitrate and mannitol in equal molecular quantities (0.1 gram-mol. per 100 c.c.) is treated a t 25" with the calculated quantity of a saturated solution of oxalic acid and the precipitate washed with cold water. I f the mashing is performed with hot water the precipitate after dry- W. H. G. ing has the composition OH*Bi:C,O,. c. s.

ISSN:0368-1769    

DOI:10.1039/CA9099605036

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

56 ABSTRACTS OF CHEMICAL PAPERS. Minera 1 ogical C hemi stryl Action of Oxidising and Reducing Gases on the Colour of Minerals. WALTER HERMANN (Zeitsch. anorg. Chem. 1908 60 369-404).-A number of coloured minerals have been heated in oxidising and reducing gases in order to determine the nature of the constituent causing colour ; borax glasses coloured with known oxides being heated under the same conditions for comparison. . The results indicate that oxides of iron occur as colouring material in zircon corundum spinel epidote and beryl. Chromium and manganese together with iron bring about colorations in green zircon garnet and tourmaline. The results with quartz and topaz were indecisive. Organic substances when present occur together with metallic oxides so that on heating the colour due to the oxide remains.Certain minerals haIite fluorite smoky quartz amethyst and citrine lose their colour when heated in all cases and this cannot therefore be attributed to oxides of heavy metals. The colorations are mostly to be regarded as due to dilute solutionsMINERALOGICAL CHEMISTRY. 57 of colouring matters but garnet and epidote are probably coloured in themselves to some extent. The conditions prevailing in minerals are of a complicated nature. Minerals of the Fumaroles of Vesuvius. ALFRED LACROIX (Bull. Soc. frang. Min. 1908 31 260-264).-The fumaroles due to the 1901'1 eruption are still active and are of two types. Those of one type deposit sodium and potassium chlorides together with cotunnite and tenorite. These saline encrustations contain a rather large quantity of calcium chloride indicating the presence of the mineral chlorocalcite.The formula of the new mineral palmierite (Abstr. 1897 ii 628) discovered in these deposits was given previously as PbSO,,(K,Na),SO ; the published analysis agrees better with the formula 4PbS0,,3[(K,Na),S04]. It is to be noted however that the very small amount of material available for analysis was isolated from the associated aphthitalite by dissolving the latter in cold water; but as palmierite is quickly decomposed by hot water and more slowly by cold water with the separation of lead sulphate it is probable that the material analysed contained some free lead sulphate and consequently the true formula of the mineral is more likely to be PbS0,,(K,Na)2S0,.Fumaroles of the acid type deposit crystals of erythrosiderite and sassolite. EDGAR T. WHERRY and WILLIAM H. CHAPIN (J. Amer. Chem. SOC. 1908 30 1684-1687). -Vesuvianite from twenty-five different localities WRS specially examined for boric acid; in nine cases it was absent in four present only in traces,and in only four was there more than 1%. The largest amount 4.14% was found in the vesuvianite from the Wilui river in Siberia. F. W. Clarke's formula for vesuvianite is R211Ca7A12(Si0,)6 where RII may be H E2 Nag Mg Ca Fe" MnI' and especially AlOH and AlF and A1 may be replaced by FeI" &In1'' or B'II. The small amount of ferric iron (never exceeding 5%) present in vesuvianite however rather suggests that there is only a limited amount of basic aluminium capable of being replaced by ferric iron and consequently that the aluminium and boron play the part of acids.Clarke's formula mould then become Ca7(R11A10,)2(Si0,)2(Si03)4 or if part of the aluminium is basic and part acidic Ca7RI1( YLI'AlO,) (Si04)4(Si03)2. LEWIS LEIUH ~FEBMOR (Chem. Zentr. 1908 ii 1062 ; from Rec. Geol. Survey India 34 167-17l).-Gibbsite occurs in association with manganese ores at Talevadi in the Belgaum district Bombay where i t forms a layer 2-6 mm. in thickness on psilomelane in a ferruginous laterite ; the small scaly crystals form greyish-white radially-fibrous aggregates; anal. I by S. S. Rama Rau. Anal. 11 by J. C. Brown is of amorphous gibbsite resembling halloysite in appearance from Bhekowli in the 88tnrS district. C. H. D.L. J. S. Occurrence of Boric Acid in Vesuvianite. L. J. S. Gibbaite from India. Al,O,. SiO,. H,O (hygr.). H,O (comb.). Total. Sp. gr. \ / r I. 63-59 2.01 34.75 100.35 2 -40 11. 64'20 0.39 0'62 34.51 99.72 2.35 L. J. S.58 ABSTRACTS OF CHEMICAL PAPERS. Argyrodite from Bolivia. V. MORITZ GOLDSCHMIDT (Zeitsch. Kryst. Min. 1908 45 548-554. Compare Abstr. 1898? ii 436).- A description is given of some unusually large crystals (3-5 cm. across) of argyrodite found on pyrargyrite from Colquechaca. The habit is dodecahedra1 (110) or less frequently octahedral and the character of the faces as well as some ill-defined etching-figures point to holohedral-cubic symmetry D 6,235. The following analysis agrees with Penfield's formula Ag,GeS,. Ag. Cu. Hg. Fe. 8n. Ge. Sn.As. 8. H,O. Total. 75-67 0.08 0-03 0.03 0.11 6-55 0.10 0.05 17.15 0.18 99.95 In spite of the difference in crystal-symmetry argyrodite appears to fall best in the tetrahedrite group and in this case the formulae 3R,IS,R1IIR1I1S3 for tetrahedrite and 3R,IS,RdRLVSQ for argyrodite show an analogous homceomorphic relation similar to that between Fe208 FeTiO etc. Composition of Morinite. ADOLPHE CARNOT and ALFRED LACROIX (BUZZ. SOC. f r a y . Min. 1908 31 149-152).-Morinite of which a preliminary description was given by Lacroix in 1891 is found in the deposits of tin ore at Montebras dep. Creuse as small and indistinct monoclinic crystals or more usually as crystalline masses with an easy cleavage and a rose-red colour. It occurs embedded in amblygonite of which it is an alteration product and is associated with quartz cassiterite and wavellite.Analysis of the massive material gave (after deducting 1.50 SiO Om20H,0 lost at 120O) P,OP F. AI,O,. Ca." Na,O. H,O. Total. 33.50 13-20 17.~0 13.80 5 -20 17-90 101.40 * CaO 19.0; traces of Li,O MgO FeO. The formula 3A1P0,,Na,HP0,,3CaF,,8EC20 when expressed in the form (A1F)~1Na2H(P04)3,(CnF)~P0,,8H,0 shows in the first molecule a relation t o amblygonite [Al( P,0H)]11(Li,Na)P04. The alteration of the amblygonite has thus been accompanied by a loss of aluminium and a gain of calcium. The aluminium phosphates wavellite and a kind of turquoise are abundant a t Montebras and they represent the last stage in the alteration of the amblygonite. Morinite is remark- able in containing more fluorine than any other phosphate this element being usually largely replaced by hydroxyl in other minerals.Minerals of the Pegmatite-veins with Lithia-tourmaline in Madagascar. ALFRED LACROIX (Bull. SOC. franp. kfin. 1908 31 218-247).-The mineral occurrences in the neighbourhood of Mt. Bity," in Madagascar have already been briefly mentioned in connexion with the new species bityite (Abstr. 1908 ii 705); a more detailed description is now given. Beryl is represented by two varieties normal beryl of which the colour is white blue or green; and beryl rich in alkalis (cesium lithium and sodium) which is pink * Le. Mt. Ibity south of Antsirabe.-L.J.S. L. J. S. L. J. S.MINERALOGICAL CHEMISTRY. 59 The following new analyses are given. surface as dark blue fragments ; analysis by F.Pisani gave Lazulite is found on the P,O,. A1,03. MgO. FeO. H,O. Total. Sp. gr. 45.30 35.22 9.19 3-95 5.80 99-46 3-12 Another mineral found loose on the surface is doubtfully referred to hatchettolite ; this is brown and resinous with an irregular fracture transparent in thin flakes and optically isotropic D 3.95. A partial analysis by Urbain gave Cb,O (with Ta,05 and TiO,) 56.61; uranium oxide (weighed as U,O,) 14.15 ; G10 2-37 ; Fe203 1.13; Mn30 (with a little cerium and yttrium emths) 1.46 ; Tho 0.96 ; SiO 2.31 ; Pb Bi Sn Cu (weighed as sulphides) 1.52 ; oxides of alkaline earths 1.64 ; loss at 300° 11.51 ; loss on ignition 3-81. L. J. S. Alunite from RQlalmont dep. Tarn. PIERRE TEBMIER (Bull. Soc. frccnp. Min. 1908 31 215-216).-The mineral is very compact and has a pale rose colour with black patches and streaks the latter being due t o the presence of bituminous matter.Analysis by F. Pisani agrees with the usual formula K,0,3A1,0,,4S0,,6H20 SO,. A1,0,. K,O. CaO. H,O. Insol. Total. Sp. gr. 36'80 36.36 10.40 0.76 13-60 2-20 100.12 2.8 The mineral occurs as a stratum 10 cm. in thickness between schists and a bed of kaolin and has evidently been formed by the action of water containing sulphuric acid (derived by the weathering of theiron pyrites in the schists) on a rhyolite rich in orthoclase. The complete separation of these two products lo€ decomposition of the rhyolite into two sharply-defined beds is curious. L. J. S . The Scheelite of Otago. A. M. FINLAYSON (Trans. iKew Zealand Inst. 1908 40 1 lO-l22).-Scheelite occurs as yellowish- white masses in many of the veins of auriferous quartz in the gold- fields of Otago.Analysis'of a commercial sample gave wo,. CaO. MgO. FeO. Fe,O,. MnO. COP Total. W J 80'58 18.98 0.20 0-24 nil 100*00 Molybdenum is also often present in varying amounts up to 1%. The mineral sometimes occurs in contact with corroded calcite and has evidently been formed by the action of solutions containing tungstic acid on the lime minerals of the surrounding rocks. L. J. S. Tantalite and Gadolinite from Western Australia. ANDREW GIBB MAITLAND (Chem. Zentr. 1908 ii 1062; from Bull. Geol. Survey Western Austru Zia 2 3 6 5-7 4).-Mangano-tantali t e (hu bnerite) occurs as large masses weighing as much as five hundred weight in pegmatite-veins traversing greenstone in the Wodgina tin-field and60 ABSTRACTS OF CHEMICAL PAPERS.it is also found in the alluvial deposits ; anal. I by Simpson. Gadolinite occurs in granite in the Cooglegong tin-field ; anal. I1 by Davis TazO,. Cb,OE. SiO,. TiO,. Ce,O,. (La,Di),O,. Y,03 SnO,. WO,. G10. I. 68-65 15.11 - 0'40 - - - 0'48 trace - 11. - - 23.33 - 2.50 18.30 33.40 - - 12.28 Loss on ignition FeO. MnO. NiO. CaO. MgO. H,O. (He,H,N,CO,). Total. D. I. 1-63 14.15 trace trace 0.15 0.07 - 100-64 7'03 11. 10.38 - - - 0.69 - 0'32 101.20 4'14 L. J. S. Risorite a New Mineral. OTTO HAUSER (Zeitsch. anovg. Chem. 19OS 60 230-236).-The new yttrium columbium mineral from Risijr Norway (Abstr. 1907 ii 704) has been further examined and shown t o be a definite species. The mean of four analyses gives Cb205.Ta,O,. TiO,. SnO,. Tho,. UO,. (Y,Er),03. Ce(La,Di),O,. 36.21 4.00 6-00 0.01 trace 0.10 36 -28 2-88 CaO. FeO. PbO. Fe,O,. A1,03. GO,. N,He. H,O. Total. 1'93 2-61 0-20 1-20 0.81 0.23 0'90 7.11 100.67 It is a glassy isotropic mass D16 4.179 hardness 5.5 with con- siderable @radioactivity. It may be regarded as an isomorphous mixture of fergusonite with metatitanates. C. H D. The So-called Dysanalyte from Vogtsburg in the Kaiserstuhl. OTTO HAUSER (Zeitsch. an0s.g. Chem. 1908 60 237-241).-The Eaiserstuhl mineral described by Knop (Abstr. 1878 385) as dysanalyte appears t o consist of perohkite con- taminated with enclosures. TiO,. SiO,. Cb205. FeO. CaO. MnO. N%O. Ce,O,. Total. 50.93 2'21 4-86 9'22 25-60 0.23 4.37 2.80 100.22 An analysis of selected crystals gave C.H. D. Naegite. TSUNASHIR~ WADA (Chem. Zentr. 19OS ii 1063 ; from Beitrage XUT Mineralogie von Japan 1906 23-25).-A new analysis by Haga of '' naegite " (Abstr. 1905 ii 177) shows that the mineral consists largely of zirconia and silica. ZrO,. Tho,. Si02. Cb,O Ta,O,. UO,. Y,O,. Total. 55 '30 5-01 20.58 7-69 3 *03 9 '12 100.73 L. J. 5. [Analyses of Hornblende.] LOUIS DUPARC and FRANCIS PEARCE (BUZZ. Xoc. franp M h . 1908 31 94-135).-Numerous determin- ations are given of the optical constants of several rock-forming minerals and analyses of the following (I) hornblende from amphi-MINERALOGICAL CHEMISTRY. 61 bolite from the Island of Coll Hebrides; (11) hornblende from amphibolite from Chester Masaachuset ts. SiO,. TiO,. Al,O,.Cr203. Fe203. FeO. MnO. CaO. MgO. Na,O. K,O. Total. I. 51.50 0.23 2.88 0'14 6'25 5-39 0.05 13.26 16'95 1-61 0.32 98-58 II. 42.74 1-08 5.48 - 11.92 11.46 0.06 12-72 11.60 2.25 0.56 99'69 (I) corresponds with the formula 1 2R,11Si40, 3R~IR2IIfSi3Ol8 21C2KR~1Si4012 and (11) with 1 OR,11Si4012,98,11R2'1S~3012,4R21R2111Si3012. L. 5. S. Zeolites from the Basalt of Montresta Sardinia. JACQUES DEPRAT (Bull. SOC. f r a q Min. 1908 31 181-192. Compare Abstr. 1908 ii 864).-Cavities in the basalt contain heulandite stilbite mesolite chabazite and rarely arialcite and thomsonite. The following were analysed (I) heulandite crystals ; (11) stilbite crystals ; (111) mesolite as finely-fibrous radial aggregates intimately associated with chabszite. SiO,. Al,O,. CaO. Na,O. H,O.Total. I. 59.00 16.70 8'20 1-30 14'70 99-90 11. 57-70 17-10 7-70 0-50 17.60 100.60 111. 47'70 24'10 10'00. 5'80 12.41 100.01 L. J. S. [Anorthoclase] from Port Victor South Australia. H. W. GARTRELL (Chem. Zenk.. 1908 ii 1063 ; from Trans. Roy. Xoc. South Australia 27 256 -260).-The granite of this locality contains large porphyritic crystals of anorthoclase m hich are flesh-red and trans- lucent t o opaque; D 2-68. The following analysis corresponds with 0r23Ab8An Loss on SiO,. Al,O,. Fe203 MnO MgO. CaO. Na,O. K20. ignition. Total. 64-54 19'34 traces 1.24 2'89 11'84 0.58 100.43 L. J. S. Cordierite-pinites from Central France. FERDINAND GONNARD (Bull. Soc. franp. Min. 1908 31 1'71-18 1)-A description is given of the occurrence of the pseudomorphs after cordierite in the depart- ments of Puy-de-DSme Loire and RhGne.The following analysis by P. Barbier is given of larg dark green crystals with a perfect cleavage and D 2.77 which occur with microcline smoky quartz and apatite in a pegmatite at Vizkzy Loss on SiO,. A120,. FeO MnO CaO. MgO. K,O. ignition. Total. 42'43-42.66 33-21-32'95 10.58 traces 2'61 4'75 6.29 99.87 L. J. S. Contact Minerals (Gehlenite Spurrite and Hillebrandite) from Mexico. FEED. E. WRIGET (Amer. J. Sci. 1908 [iv] 26 545-554).-These minerals were formed near the junction of altered limestone and intrusive basic diorite in the Velardeiia mining district in Durango.62 ABSTRACTS OF CHEMICAL PAPERS. GehZennite occurs as massive granular aggregates together with spurrite yellow garnet and calcite.It is dark grey in colour owing to abundant minute inclusions of magnetite and only rarely are small pieces free from magnetite inclusions of an amber-yellow colour ; D25 3.039. Analysis I is very similar to previous analyses of gehlenite but no simple formula can be deduced the mineral probably repre- senting a solid solution of several end members of a series SiO,. TiO,. 81,0,. Fe,O,. FeO. MnO. MgO. I. 26.33 0-03 27.82 1-43 0.50 0.01 2'44 11. 26-96 0'01 0'39 0'11 0'03 0.23 111. 32.59 0 02 0.23 0.15 0.01 0-04 - CaO. Na,O. K20. H,O. CO,. Total. I. 39.55 0-21 0.10 1.85 nil 100.27 11. 62'34 0.05 trace nil 9-73 99.85 111. 57-76 0.03 0.05 9'36 nil 100'24 Xpurrite occurs as granular masses with glistening cleavages resembling crystalline marble in appearance ; no crystals were observed The mineral is transparent to translucent and colourless to pale grey with tints of blue or yellow; lustre vitreous to resinous ; hardness 5 ; DZ5 3.014.The optical characters indicate that the symmetry is probably monoclinic ; the birefiingence is high (y - a = 0*039) the axial angle small (2E = 70°) the sign negative and there is a noticeable crossed dispersion. Lamellar twinning occurs on more than one plane perpendicular to the plane of symmetry and there are two cleavages with an angle of 7 9 O perpendicular to the same plane. Before the blowpipe the mineral becomes white and porcelain-like and is infusible. It effervesces in dilute hydrochloric acid and is readily dissolved with the separation of gelatinous silica. Analysis I1 corre- sponds with the formula 2Ca2Si0,,CaC0,.Hillebrandite possesses a fibrous structure the fibres being often aggregated as radial sperulites ; it is associated with yellow garnet and wollastonite. The material is white often with a tinge of green and porcelain-like and is translucent only in small chips ; hardness 5 4 ; D25 2.692. The optical characters of the fibres suggest ortho- rhombic symmetry. Before the blowpipe the mineral fuses to a colourless glass. I t readily dissolves in hydrochloric acid with the separation of some silica and is slowly decomposed by water. Analysis 111 gives the formula 2Ca0,Si02,H,0. Attempts to prepare the new minerals spurrite and hillebrandite synthetically have so far been unsuccessful. Mineralogy of the Feeroe Islands. MATTHEW F.HEDDLE (Chem. Zentr. 1908 ii 1061 ; from Trans. Geol. SOC. Glasgow 1906 12 1-15).-Anal. I of bluish-white spheres of faroelite from Nolso ; 11 of mesolite occurring on sphaerostilbite from Nolso ; 111 of stilbite from Bordo. L. J. S. SiO,. AI,O,. Fe,O,. CaO. Na,O. K,O. H,O. Total. I. 42-50 28.06 - 11 35 5'60 - 13.02 100.53 11. 46.80 26'46 - 9.08 5'14 - 12'28 99.76 111. 58.79 14'613 0.47 9.534 0'324 0.232 17-298 101261 L. J. S.MINERALOGICAL CHEMISTRY. 65 Phillipsite from Mont Simiouse Loipe. FERDINAND GONNARD (Bull. SOC. franp. ah. 1908 31 269-271).-Analysis by P. Barbier of crystals of phillipsite associated with chabazite and offretite lining cavities in basalt at Mont Simiouse gave SiO,. Al,O,. CaO. BaO MgO. K20. Na,O. H,O. Total. 52-10 18'33 4.96 traces 6.88 1'10 16.55 95.92 This agrees with the formula RA12Si,0,,,5H20 (where R = Ca I( Na) whilst some analyses of phillipsite from other localities have given the formulae RA12Si,0,,,5H20 RA12Si,0,2,4H20 and RA12S~,0,,13+H,0. The present mineral therefore represents an acid type of phillipsite similar to that from Giessen and the Kaiserstuhl.L. J. S. The Pumice of the Volcano of Mont Dore. ALFBED LACROIX (Compt. rend. 1908 14'7 778-782).-A description is given of the fragmentary materials more particularly the pumice of this extinct volcano. Hhyolitic pumice (anal. I and 11 by F. Pisani) with a fibrous structure occurs only in small pieces ; it consists almost entirely of a colourless glass with very few phenocrysts of anorthoclase surrounded by orthoclase. The composition is identical with that of the rhyolite (anal.111) Trachytic pumice (anal. IV) has a cellular structure and is less glassy containing phenocrysts of orthoclase anorthoclase biotite and augite together with microlites of orthoclase. SiO,. Al,O,. Fe,O,. FeO. MgO. CaO. Na,O. K20. TiO,. H,O. Total. I. 73-90 10.95 0.08 1-06 1-08 1.55 4.08 4-60 - 3'35 100*68 11. 73'90 11'93 0.15 0.87 0.13 0.34 4.10 4.62 trace 4-00 100-04 111. 75-50 13'50 0.95 - 0.39 0.99 4-35 4'15 trace 0.37 100.20 IT. 60.50 18'20 1'20 1-08 0.26 0.68 5'10 5.23 0.39 7.00 99-64 L. J. S. Rare Renfrewshire Minerals. ROBERT S. HOUSTON (Chem. Zentr. 1908 ii 1062; from Trans. Geol. Xoc. Glasgow 1906 12 354-361). -.Several minerals are described and analyses given of the following I labradorite from Gleniffer Hills south of Paisley ; IT pectolite massive and fibrous from South Quarry Craigenfeoch near Johnstone ; 111 stilbite red from near Kilbarchan.SiO,. Al,O,. Fe20,. CaO. MgO. MnO. R,O. Na,O. H,O. Total. I. 53-82 28'09 2.88 3.62 4-24 trace 2-25 3-70 2'00 100'60 11. 55.38 trace - 33'68 trace - - 7-20 3.30 99'56 111. 55'02 16.48 trace 7'24 0.58 - - 4-46 17-00 100'78 L. J. S. Weathering and Formation of Kaolinite in the Halle Quartz- porphyry VICTOR SELLE (Chern. Zentr. 1908 ii 1203 ; from Zeitu Naturw. 1907 79 321-421).-Analysis I is of the white product of weathering and 11 of the portion insoluble in concentrated sulphuric acid ; the latter consists of quartz 3.5S% and felspar 7.97%. Deduct- ing from the soluble portion the alkalis as sericite the sulphuric anhydride as gypsum and neglecting the magnesia the remainder has the composition 2A1,0,,5Si0,,4H20 whereas kaolinite has the formula 2Al20,,4Si0,,4H2O.64 ABSTRACTS OF CHEMICAL PAPERS.The mineralogical composition of the sample is given as quartz 11.56 ; felspar 7.97 ; kaolinite 71.45 ; sericite 4.06 j other minerals 4.96%. SiO,. A1,0,. Fe,O,. CaO. MgO. SO,. H,O. Alkalis. Total. I. 51.05 27.07 5.51 1-01 2.09 1-45 10.30 1.52 100.00 I 1.04 11-55 11. 8.83 1-44 0.08 0.12 0'04 - The alteration of the felspar in the rock has given rise first to mica and this has subsequently been altered to kaolinite. I n the Halle district the decomposed porphyries are richer in kaolinite nearer. the surface and minerals of pneumatolytic origin are absent. The conclusion is therefore drawn that the formation of kaolinite is dependent on the ordinary processes of weathering only these were more intense in their action in former times than at present.L. J. S. Analysis of London Clay. JOHN H B. JENKINS (Geol. Mag. 1908 Lv] 5 265-266).-1n a well-boring at East Ham the stratum of clay extends from 17 to 76 feet below the surface. The wet stiff clay of dark grey colour loses 20.1% at 120° and on ignition there is a further losseof 6.3%. The ignited material is brick-red and contains SiO,. A1,0,. Fe,03 CaO. MgO. K,O. Na,O. Total. 67.9 18.3 8.7 1 *3 1 *2 1 '6 1 '4 100.4 L. J. S. Red Porphyry [Porfido Rosso Antico]. J. COUYAT (Compt. rend. 1908 147 988-990),-The ancient quarries whence this celebrated ornamental stone was obtained by the Romans are situated along the Wadi Abu Maammel on the north-west slopes of the Jebel Dokhan in Egypt. The crystalline schists of the district are pene- trated by necks of hornblende-andesite and by veins of various other igneous rocks (this vol.ii 65). This andesite when unaltered (anal. 11) is greenish-black or ebony-black and contains phenocrysts and microlites of andesine and hornblende together with much apatite and magnetite. The hornblende (anal. I) contains some manganese ; it has a maximum extinction angle of 2 2 O and its pleochroic colours are pale yellow to green. The red porphyry (anal. 111) is found in the central more crystalliue portions of the necks and it is an altered form of the hornblende-andesite ; there is a gradual passage from one rock to the other a violet porphyry forming an intermediate zone.The simultaneous decomposition of the hornblende and felspar has given rise to much manganiferous epidote (withamite) but the red colour of the rock is mainly due to the large quantityof finely-divided hematite ; other secondary minerals are damourite actinolite and biotite. SiO,. TiO,. Al,O,._Fe,O,. FeO. CaO. NgO. MnO. Ra,O. K20. H,O. Total. 1. 44-5 1.5 1 2 5 12'2 4.0 9.5 11'1 0.4 3-9 0.5 100'1 11. 64'3 0.45 16'4 1-85 2-5 4'7 3.0 tiace 4.3 2-0 0'6 100.1 111. 64'4 0'65 i 6 . 1 3.5 1.0 5-0 2.7 trace 4.2 1% 1-1 100.25 - L. J. S.MINERALOGICAL CHEMISTRY. 66 [ Hyperethene-Augite from Lake Onega.) WALTER WAHL (Fenma HeEsingfors 1908 24 No. 3 1-94).-1n a paper on the geology of the west coast of Lake Onega Russia are given several rock analyses together with the following analysis of a pyroxene isolated from a coarse-grained quartz-diabase from Schtscheliki.SiO,. TiO,. Al,Q Fe,O,. FeO. NiO. MnO. MgO. 50.36 0'80 2'49 2'35 18.15 0'04 0.56 11'37 CaO. Na,O. K,O. H,O. Total. Sp. gr. 13-97 0-26 0.19 0'55 101.09 3'46 The crystals show a zonal structure with varying optical characters; in the inner portion 2E = 48"42' and in t l e outer 2E = '73'8' ; c c = 45". The mineral belongs to the group of enstatite-augites and is a hypers t hene-augite. L. J. 8. Gabbro and Iron-ore of the Jubrechkine Kamen Northern Urals. LOUIS DUPARC (Compt. rend. 1908 147 1061-1063).- This mountain is formed entirely of uralitised gabbro (anal I) of various types and irregularly distributed through the rock are basic segregation patches (anal.11) often of considerable size. These patches consist largely of magnetite together with hornblende and a little epidote and kaolin. SiO,. TiOP A1,0,. Fe,O,. FeO. MnO. CaO. MgO $,O. Na,O. nition. Total. I. 47-97 1'30 13'50 3-55 11'47 trace 10'63 6'51 0'26 2.78 1.60 99.57 11. 26'62 9-50 11-62 19.50 21'87 0.20 6'47 2'57 0.34 1-06 1'30 101.05 Loss on ig- L. J. S Mode of Formation of the Puy de Dame. ALFRED LACROIX (Compt. rend. 1908 147 826-831).-The structure of this extinct volcano is compared with the recent West Indian volcanoes and found to resemble that of Guadeloupe rather than Mt. PelBe. Analyses are given of domitea with biotite or with hornblende and of the frag- mentary derivatives OF these rocks. L. J.S. Eruptive Rocks of Jebel Dokhan Red Sea. J. COUYAT (Compt. refid. 1908 147 867-869).-Veins and bosses of the erup tive rocks penetrate the conglomerates and schistose sediments which rest on a granitic massif. Analyses are given of granite micro- granite micropegmstite rhyolite andesite and labradorite L. J. S. Possible Existence of a Nickel-Iron (Fe,Ni,) in Meteorites. LAZARUS FLETCHER (Min. Mag. 1908 15 147-152).-ln the analysis of the meteoric stone of Zomba (Abstr. 1901 ii 400) the repeated extractions of the nickel-iron with mercuric ammonium chloride showed that the residue became gradually richer in nickel. This was at the time attributed to the rusting of the iron in the minute particles of the alloy but is now explained by the presence of a nickel- iron constituent Fe,Ni containing 38.50% Ni(Co) which is not VOL.Xcvl. ii 566 ABSTRACTS OF CHEMICAL PAPERS. readily attacked by the mercuric solution. This constituent is identical with the '' taenite " containing 38.13% Ni(Co) isolated by reason of its insolubility in dilute hydrochloric acid from the Youndegin iron (Abstr. 1900 ii 27). From an examination of the thermo-magnetic characters of the Sacramento iron S. W. J. Smith (Phi+?. Trans. 1908 A 208 21) has recently concluded that this meteorite contains !a nickel-iron with not less than 37% Ni thus confirming the above results. Investigations on the Gases of the Wiesbaden Thermal Springs. FERDINAND HENRICH (Bey. 1908 41 4196-4209. Com- pare Abstr. 1905 ii 6 221 ; 1907 ii 150).-The gases evolved by some of the thermal springs at ,Wiesbaden have been analysed and found to contain carbon dioxide nitrogen oxygen methane hydrogen sulphide argon neon helium and radium emanation in the following proportions the values given being volume percentages. Koclkbrunnen (t = 68.7") gas absorbed by potassium hydroxide 84.8 oxygen 0.2 nitrogen 12.7 methane 0.6 rare gases (argon etc.) and emanation 1.7 ; AdZerqueZZe ( t = 64.6') gas absorbed by potassium hydroxide 77.6 oxygen 1.2 nitrogen 18.4 methane 0.8 rare gases and emanation 2.0 ; Xchutzenhofquelle ( 8 = 49.2') gas absorbed by potassium hydroxide 32.4 oxygen 0.2 nitrogen 62.05 methane 0.45 rare gases and emana- tion 4.9. The composition of the evolved gas varies slightly and irregularly throughout the year. It is probable that the gases are derived from the rocks in the vicinity of the springs since it has been found that these rocks when heated alone or with potassium hydrogen sulphate evolve oxygen nitrogen helium and argon. The oxygen is absorbed by the ferrous carbonate present in the spring-water. L. J. S. W. H G.

ISSN:0368-1769    

DOI:10.1039/CA9099605056

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

66 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemfstr y. Effects of Low Pressures on Respiration. ARTHUR BorcofV and JOHN S. HALDANE (J. Physiol. 19OS 37 355-377). Alveolar Air on Monte Rosa. R. OGIER WARD (ibid. 378-389). Effects of Want of Oxygen on Respiration. JOHN S. HALDANE and EDWARD P. POULTON (ibid. 390-407). -The experiments on the effect of low atmospheric pressure on respiration mere carried out on men partly on Monte Rosa and partly in a specially-constructed steel chamber. When the pressure is diminished the alveolar carboh dioxide pressure remains constant during short exposures. When the air pressure reaches 550 mm. or the alveolar oxygen pressure 62 mm. the alveolar carbon dioxide pressure fails and as the air pressures fall the fall in the carbon dioxide pressure occurs with increasing rapidity.In long exposures the fall in the carbon dioxide pressure occurs earlierPHYSIOLOGICAL CHEMISTRY. 67 and further ; the alveolar oxygen pressure is correspondingly higher ; the process is one of gradual adaptation to low pressures or great altitudes. The fall in alveolar carbon dioxide pressure is due to hyperpnaea dependent on the low oxygen pressure and is absent if oxygen is added to the air. The hyperpnoea is however not directly due to want of oxygen since it takes time to develop and may persist for days after the want of oxygen is removed. It is probably due to the gradual formation in consequence of insufficient oxygen of lactic acid or other substances which have the same influence as carbon dioxide on the respiratory centre so that less carbon dioxide is required to excite the centre. When the alveolar oxygen pressure falls to 30 mm.urgent symptoms are produced. Exposure to cold causes a slight rise and to heat a slight fall in the alveolar carbon dioxide pressure. If sufficient of the preformed carbon dioxide is first removed by forced breathing want of oxygen has no exciting influence on the centre and apnoea will be produced and does not cease until the alveolar carbon dioxide pressure rises to normal unless abnormal pro- ducts produced by want of oxygen reinforce the action of the carbon dioxide ; the development of these other products is however a gradual process. W. D. H. Experiments on the Gtrtseous Metabolism of Infants carried out by means of Zuntz and Oppenheimer’B Modiflca- tion of the Regnault-Reiset Respiration Apparatus.ARTHUR SCHLOSSMANN CARL OPPENHEIMER and HANS MURSCHHAUSER (Biochem. Zeitsch. 1908 14 385-406).-The experiments were carried out by means of the apparatus described by two of the authors (ibid. 361-368 369-384). I n the case of a healthy child (44-5 months old) sleeping for eight hours after feeding the oxygen utilised was 0.731 gram and the carbon dioxide excreted 0.931 gram per kilo. per hour. The respiratory quotient mas 0,911. These numbers were greater for the first three hours after the meal than for the later period. I n similar experiments when the child was awake for a part of the experimental period the oxygen consumed mas 0 853 gram and the carbon dioxide excreted 1.046 grama per kilo.per hour the respiratory quotient being 0*896. Experiments were also carried out on children during a period of fastjin pathological cases and results differing markedly from the above were obtained. S. B. S. Effeot of‘ Salt Solutions on the Heart and Respiration of the Skate. IDA H HYDE (Amer. J. Physiol. l908,23,201-213).-As a rule increase of heart-beat produced by various salts is accompanied by rise of blood-pressure and increase of respiratory activity. Am- monium chloride however increases blood-pressure without increasing cardiac force ; disodium hydrogen phosphate increases the force of the heart but not that of respiration,and urea increases cardiac and respira- tory activity without raising the blood-pressure. The aalts which are specially depressing are potassium chloride and magnesium sulphate.Many other details are added in relation t o concentration etc. of these tand other aalts W. D. H. 5-268 ABSTRACTS OF CHEMICAL PAPERS. Coagulation-time of Blood in Man. T. ADDIS (Quart. J. exp Physiol 1908 1 305-334).-Daily variations in the coagulation- time of the blood do not occur; the administration of citric acid or of calcium salts also makes no difference. The contrary result is due to errors in technique the influence of temperature having been dis- regarded in all previous measurements of coagulation-time. The coagulation-time is Rhortest between 36' and 40' ; at temperatures above and below this it increases. A new method is described in which temperature and other factors are kept constant ; the observation is made with a microscope and depends on the fact that when a current of oil streams along the side of a drop of blood a smooth flow of the corpuscles is induced.The movement stops suddenly when coagula- tion takes place. CARL I;. ALSBERG and E. D. CLARE (J. Biol. Chem. 1908 5 333-330).-The blood-clot is con- sidered to consist of the agglutinated cells of the blood only without admixture with any substance akin t o fibrin. The solubilities and the low sulphur and tyrosine contents are thought t o point to the protein present as being a member of the gelatin-elastin group. W. D. H. Blood-Clot of the King-crab. W. D. H. The Sugar in Blood. IV. The Method of Osmotic Com- pensation. LEONOR MICHAELIS and PETER RONA (Biochem. Zeitsch. 1908 14 476-4S3).-Experiments were carried out with the object of determining whether the sugar in blood exists free or combined in some form as a colloidal complex.For this purpose the total sugar was estimated polarimetrically after precipitating the proteins by colloidal ferric hydroxide. Portions of the blood were then dialysed against an isotonic salt solution (containing a small quantity of sodium fluoride) to which varying amounts of sugar had been added. After twenty- four hours the sugar was estimated in the dialysate. An increase in the latter after the dialysis would denote that the original liquid contained less sugar than the blood whereas a diminution would indicate that i t contained more. It was found that the amount of sugar in the dialysate did not alter after dialysis when it contained the same percentage of sugar as was found in the blood by the method described above; hence the sugar in the blood exists in a free state.S. B. S . The Total Sugar of the Blood. RAPHAEL L~PINE and BOULUD (Compt. rend. 1'308 147 1038-1031. Compare Abstr. 1908 ii 957).-The amount of sugar obtained from the blood-clot depends to a somewhat considerable extent on the duration of the hydrolysis by hydrofluoric acid for besides liberating the sugar the acid also slowly destroys it. The sugar obtainable from the clot is in any case a considerable portion of the total sugar of the blood. G. B. Diastases in the BIood and Body Fluids. ANTON J. CARLSON and A. B. LUCICHARDT (Amer. J. PhysioZ. 1908 23 148-164).-The diastases in blood and lymph are mere '' discards " of the tissues on the road t o destruction or elimination and serve no emential end inPIIYSLOLOGICAL CHEMISTRY. 69 the body processes.Their amount is not related to pancreatic activity to changes in the diet or to the rate of oxidation in the body. Such differences as are noticeable in different fluids or in the same fluid at different times appear to be of an accidental nature. W. D. H. The Maltase of the Blood-serum and Liver. CHOSABUR~ KUSUMOTO (Biochem. Zeitsch 1908 14 21 7-233).-This is a com- parative study of the action of the maltase of the blood and 'liver extract in different animals. The absolute and relative strength of the action varies considerably being greatest in the pig and least in the sheep of the animals examined so far as relates to the maltase of the blood but the liver extract is more powerful in the sheep than in the pig or dog.In the calf and horse the two ferments act about equally This varying action may depend on the amount of ferment present or on the presence of such inhibitory substances as anti-maltase. W. D. H. The Occurrence of Proteic Acids in Blood. J~ZEF BROWI~SKI .(Zeitsch. physiol. C h . 1908 58 134-146. Compare Abstr. 1908 ii 205).-The proteic acids described by Bondzynski in the urine of men and dogs are also present in blood; one litre of horse's serum contains 0.137 gram of oxyproteic acid. W. D. H. Cytolysis. ALONZO E. TAYLOR (J. Biol. Chem. 1908 5,311-314). -Injections of salmon sperm into rabbits renders the blood capable of causing cytolysis of the spermatozoa.The serum was inactive if the spermatozoa used were stale so also was the sera from animals inoculated with the lipoidal protamine or nucleic acid fractions obtained from the cells. W. D. H. Precipitin Reactions. W. A. ~CHMIDT (Biochem. Zeitsch. 1908 14 294-348).-1f dried serum is heated at l l O o it does not lose its power of reacting to precipitin; if heated at 130° this property is lessened and a t 150' almost entirely lost. If the serum is not-dried heating a t 70' for an hour does not destroy the property and the reaction may be obtained even after heating a t 909 These tem- peratures are higher than those given by previous observers. Passing from the precipitable substance to the precipitin this is not so thermostable; still heating at 7 5 O for several hours does not entirely destroy it and precipitin serum after heating at 70° is still capable OF producing immunisation.I f heated with alkali similar results are obtained. Various theoretical deductions from these experiments are discussed. W. D. H. Sensibilising Action of Animal Pigments. I. WALTHER HAUSMANN (Biochem. Zeitsch. 1908,14 275-278).-Vegetable extracts which contain chlorophyll act haemolytically on red corpuscles in the light but not in the dark. This is not a property confined to chloro- phyll but is also possessed by certain animal pigments and in the present paper bile pigment i s shown to possess it. This may play a70 ABSTRACTS OF CHEMICAL PAPERS. part in diseases where pigmentary changes occur in parts exposed to light such as the skin.Haematoporphyrin acts in the same way both on red corpuscles and on other animal cells such as paramaecium. W. D. H. The Influence of Neutral Salts on Haemolysis. RUDOLF HOBER (Biochem. Zeitsch. 1908 14 209-2 16).-The action of weak hypotonic solutions of neutral salts of the alkalis is to cause discharge of the haemoglobin from the red corpuscles of the ox. The anions favour haemolysis in the following order SO4<C1<Br,NO3<I and the cations in the following Li,Na<Cs,Rb<K. The action probably depends on an action on the membrane increasing its permenbili ty. W. D. H. The Hamolysin of Human Pancreatic Juice. 11. JULIUS WOHLGEMUTH (Chern. Zentc. 1908 ii 1111 ; from Bed. Klin. Woch. 1908 45 1304-1305).-Inactive pancreatic juice in spite of its lipolytic properties does not contain haemolysin.On activating with enterokinase or calcium chloride or by keeping it acquires the property of dissolving red blood-corpuscles under certain conditions. The addition of lecithin also causes the juice to acquire hzemolytic properties although it is not thereby activated as regards trypsin. Tho kmolytic properties are possibly due to the setting free by the activated trypsin of lecithin from some protein lecithide complex. S. B. S. Effect of Diet on Saliva. CHARLES HUGH NEILSON and M. H. SCHEELE (J. Biol. Chein. 1908 5 331-338).-Saliva hydrolyses starch t o maltose and maltose to dextrose and so probably contains two enzymes. A carbohydrate diet increases both actions and a protein diet lessens both in the same proportion.These facts are considered to prove adaptation to diet. The experiments were con- ducted on men. W. D. €I. Assimilation of Formaldehyde and of Glycerol and Sugar. THOMAS BOKORNY (PfEiigev’s Archiv 1908 125 467-491).-1f as is believed carbon dioxide is changed into formaldehyde by the action of chlorophyll granules the condensation of the latter substance must occur with great rapidity for except in minimal amount it is very toxic to life and to the chlorophyll apparatus. On treatment with dilute formaldehyde starch formation is increased and this occurs in the dark and under the influence of light with equal rapidity. The energy of light is necessary in the formation of formaldehyde from carbon dioxide. Oxygen is not essential either for the assimilation of formaldehyde gyycerol or sugar.W. D. H. Metabolism of Glycine in Liver Affections. HERMANN JASTROWITZ ( A ~ c h . exp Path. Pharm. 1908 59 463-472).-1n normal persons the administration of 20 grams of glycine does not lead to its appearance in the urine but in those wit4 liver diseasePHYSIOLOGICAL CHEMISTRY. 71 and in dogs suffering from phosphorus poisoning if glycine is given a good deal escapes conversion into urea and passes into the urine W. D. H. Liebig’s Extract of Meat. R. ENGELAND (Zeitsch. Nab. Genussm. 1908 16 658-664).-The following bases were separated and identified in Liebig’s extract of meat the method employed being a modification in part of that described by Kutscher and Steudel creatinine neosine carnitine (Abstr. 1905 i 726) vitiatine ( A bstr.1907 ii 708) histidine methylguapidine and alanine. W. P. S. The Assimilation of Carnitine in the Animal Body. R. ENGELAND (Zeitsch. Nahr. Genussm. 1908 16 664-666),-1t is shown that carnitine when administered to dogs is entirely decom- posed and is probably converted into dimethylguanidine as this base was detected in the urine. I n the case of rabbits it appears that carnitiue is reduced during its passage through the body but the small quantity of base recovered from the urine did not allom of its identity being established with certainty. w. P. s. Hydrolytic Enzymes of Invertebrates. HERBERT E. ROAF (Bio-Chem. J. 1908 3 462-472).-Glycerol extracts of the di- gestive glands of various invertebrates (arthropods molluscs echino- derms) were employed or in some cases the alcohol precipitate from such extracts.Enzymes capable of hydrolysing starch and glycogen fats and proteins were found. The addition of these extracts to milk and oxalated blood-plasma caused coagulation Variations as to the preseme and activity of all these ferments occur and many results are stated quantitatively. I n relation to the proteo- clastic enzymes the Congo-red fibrin method of the author was mainly employed ; variations are noted in the reaction of the medium which gives the best results W. D. H. Is Choline Present in the Cerebro-spinal Fluid of Epileptics? S. KAJIURA (Quart. J. exp. Physiol. 1908 1 29 1-296).-Relying on Rosenheim’s periodide test which is both trustworthy and sensitive choline was not found in the cerebro-spinal fluid in cases OF epilepsy.The detection of a few fragments of aniso- tropic crystals by Donath’s micro-polariscopic test is not in itself suficient evidence of the presence of choline; treated in the same way with platinic chloride etc. the same result may be obtained with normal cerebro-spinal fluid or even with distilled water. W. D. H. Chemico-physical Investigations on the Crystalline Lens. 111. Imbibition of the Crystalline Lens in Water and in Water Vapour. FILIPPO BOTTAZZI and Noh SCALINCI (Atti R. Accad Lincei 1908 [v] 17 ii 445-454. Compare Abstr. 1908 ii 966 1054).-The penetration of water into the crystalline lens and the swelling and increase in weight of the latter is due to some extent to a process of imbibition and not as is usually supposed,72 ABSTRACTS OF CEEMICAL PAPER& solely to the osmotic pressure of the lens.As there is not an imbibition equilibrium between the lens and the water in which it is immersed the water penetrates the lens at first rapidly and subsequently more slowly. The lens tends towards a maximum of imbibition which is however only attained if the capsule is ruptured. Tn tbis imbibition there are two distinct periods in the first of which vfiter penetrates the lens and causes it to swell uniformly whilst in the second the water accumulates between the lens and the capsule. pxperiment shows that tbe percentage increase of weight of a lens from which the capsule has been removed is less than in the case of a lens which retains its capsule. When no capsule is present the lens increases rapidly in weight during about the first half-hour of ixpxpersion after which the increase is first checked for a time and then proceeds more gradually; this is due to the diffusion from the lens of the soluble facoprotein the loss thus caused being sufficient to compensate for a time the increase in weight due to imbibition When suspended in saturated water vapour at 3S0 the crystalline lens does not increase but gradually diminishes in weight a process of disimbibition taking place.From this point of view the crystalline lens may be regarded as a block of solid hydrogel since swollen gelatin behaves in the samB way when suspended in water vapour (compare Schroeder Abstr. 1903 ii,. 721). The amount of dis- imbibition of the lens in water vapour is for a definite time directly proportional to the initial weight of the lens whilst the increase in weight of a lens due to imbibition in water is inversely proportional t o that weight.The mechanism of the process of disimbibition i s esseqtially different from that of the process of imbibition. T. H. P. Effect of Stimulation of the Accelerator Nerve on the $aline Metabolism of the Isolated Heart. WILLIAM H. HOWELL and W. W. DUKE (Amer. J. Plysiol. 1908 23 174-179).-A com- paratively small supply of Locke’s fluid was continuously perfused through isolated cats’ hearts by the method described by Locke and Rosenheim. Neither the calcium nor the potassium in the guid showed any variatiop in amount after a perfusion lasting for hours and after long-continued excitation of tbe cardiac accelerator nerve.N o trace of hypaxant4iae mas discovered in the fluid although Burian describes this substance as being pontinuously formed in skeletal muscle asd inpreased in amount during its contraction. The difference may be due t o aq esswtial difference between the two kinds of rpuscle or to the presence of dextrose in Locke’s fluid. The heqrt however gives off creatinine (or creatine) to the circulating fluid. W. D. 4. Action of Barium Chloride on the Nprmal Heart and the Heart which has Undergone Fatty Degeneration. Rmmo DE NICOLA (Chem. Zentr. 1908 ii 961 ; from Arch. Farm. sperim. 1908 7 130-138).-Barium chloride is a myocardial poison with marked action on the muscle but influences little or not at all the heart movements of an organ which has undergone fatty degeneration and only causes death by exhaustion. S.B. $.PHYSIOLOGICAL CHEMISTRY. 73 The Sugar Utilised in the Isolated Heart. MARIO C u m (C?lem. Zentr. 1908 ii 1194 ; from Zeitsch. ally. PlrySiol. 1908 8 371-404).-=-The relationship between the amount of work done by an isolated heart and the amount of sugar utilised from a Ringer- Locke solution was investigated. The apex of the heart (from rabbits cats and a fox) which was pcrfused in a Langendorff apparatus was weighted by different loads and from the number and size of the uontractions the amount of work performed was calculated. It was found in the case of the rabbit that for the same amount of mechanical work the larger was the amount of sugar utilised the greater the load attached to the heart.A direct proportionality between the lilugar utilised and the work of the heart; could not however be ascer- tained The hearts of cats and of foxes utilised no sugar under the same conditions of experiment. In these cases glycogen seems to disappear the fresh hearts of cafe and foxes containing more of this carbohydrate than was found in those organs which had been employed in the perfusion apparatus A similar difference was not found in the case of rabbits The conclusion was drawn that in herbivora the sourue of musoular energy is the sugar whioh is obtained directly from the food-stuff s or by degradation of other carbohydrates whereas in the case of carnivora the source is the glyoogen of the musules which has been prepared from the proteios of the food- stuffs.s. B s. Fate of Glyoerol in the Body FELIX REACH (Biochem. Zeitsch. 1908 14 279-285),-The liver was perfused with Ringer'g solution by a method similar to that used by Loch and Rosenheim in their investigations on the utilisation of sugar by the beating heart. It is shown that the liver has the power of synthetically forming aceto- acetic acid in small quantities from glycerol This is not in contra- diction to the antiketogenio action of glycerol. W. D. H P. C . ROMKEEI (Biochem Zeitsch. 1908 14 254-254).-The author claims to have proved by four distinct methods that the walls of liver cells are permeable to dextrose The mall of the nucleus on the other hand appears to be impermeable to dextrose. These facts have an important bearing on the reversible hydrolysis of glycogen to dextrose C,H,,O + H,O = C,H,,O,.J J. S. ALONZO E TAYLOR (J. Biol. Chem. 1908 5 315-318).-Flask experiments on the liver of the giant clam show a post-mortem conversion of its glycogen into sugar which is believed to be analogous to what occurs during the life of thg animal. The conversion is a function of two Variables and is proportional directly to them namely the masses ~f glypogen and of glycolytic ferment in the liver cells. The Animal Fats and the Extract by Light Petroleum from the Liver. YUTAKA NUKADA (Biachem. Zeitsch. 1908 14 419-429). -The content of animal fats in lower fatty acids was estimated by kydrolysing the fgts adding to t40 soaps just sufficient acid to Liver Cells and their Permeability to Sugar Conversion of Glycogen into Sugar by the Liver W.D. H.74 ABSTRACTS OF CHEMICAL PAPERS. neutralise the alkali used and washing the separated fatty acids with water until the washings were no longer acid (“filtration method ”). The volatile acids in the washings were also estimated by distillation. The acetylation number was determined by similar processes. The acetylation numbers of the fats fatty acids and light petroleum extracts were determined. It was found that the fatty acids in the fats from adipose tissues which are soluble in water and volatile with steam amount to 0.4 to 0.7% of the total. These fats contain when fresh only small quantities of substances with a free hydroxyl group ; with the age of the fat however the number of these groups increases.On hydrolysis of the fats substances containing free hydroxyl groups are obtained amongst which are cholesterol and appreciable quantities of hydroxy-acids. Liver extracts contain cholesterol but not cholesterol esters ; hydroxy-acids also seem to be present. S. B. S. The Influence of Radium Emanations on Autolysis. SIMON LOWENTHAL and E. EDELSTEIN (Biochem Zeitsch. 1908,14,484-490). -Radium emanations appreciably increase the rate of autolysis of tissues especially in the expressed juices from certain carcinomatous growths. S. B. S. The Influence of Inorganic Colloids on Autolysis. V. M. ASCOLI and G . IZAR (Biochetm. Zeitsch. 1908 14 491-503).-1n the experiments colloidal silver prepared by Bredig’s method was employed. It was used in two forms ‘‘ stabilised ” by the addition of gelatin and ‘‘ non-stabilised.” Both forms increase the rate of autolysis of liver tissue whereas the former alone when in very small doses causes a rise of temperature when administered to animals.Both forms however when given in sufficient doses cause this rise of temperature the “stabilised ” to a greater extent than the “non- stabilised.” The addition of defibrinated blood inhibits the effect of the non-stabilised blood on liver autolysis but not that of the stabilised; serum on the other hand exerts the same effect on both forms of colloidal silver. The addition of sodium chloride inhibits the action of the non-stabilised colloid but not that of the stabilised. 8 B. S. The Preparation and Chemical Properties of the Xanthoma Substance with some Investigations of the Fat-like Doubly- refracting Substance in Large White Kidneys.J. PRIKGSHEIM (Biochem. Zeitsch. 1908 15 52-75).-The material for investigation of the xanthoma was obtained from the dura mater and the skin of a woman who suffered from chronic icterus with hypertrophic cirrhosis of. the liver. The material was extracted with alcohol and then with acetone and from the latter solvent crystals separated which after repeated recrystallisations from the same solvent melted at 67.5’. The dura mater material contained 14.2% of this substance. It was free from phosphorus and nitrogen and yielded on hydrolysis with sodium ethoxide in benzene solution a residue which on recrystal- lisation from alcohol melted at 144.5’ and gave the characteristicPHYSIOLOGICAL CHEMISTRY.15 cholesterol reactions. The fatty acids obtained by hydrolysis were not identified; the lead salts were partly soluble in ether. There is evidence therefore that the doubly-refracting substance is an ester of cholesterol. Similar substances melting at 54’ and 5 2 O were obtained from the kidneys of a woman who had died from tuberculosis of the lungs and of a child who had died from uraemia. In these cases there was not sufficient evidence to determine whether the doubly-refracting substance consisted entirely of cholesterol esters as the yield obtained was small. The-author calls attention to the pathological significance of the facts and the need for chemical identification of the doubly-refracting substances. Spontaneous Movements of Amphibian Muscle in Saline Solutions.GEORGE RALPH MINES ( J . Physiol. 1908 37 408-444). -The rhythmical periods in the contractions produced by exposing amphibian muscles to a 0.7% solution of sodium chloride vary from 6 to 0.06 sec. and the movements continue in the presence of curare; large doses of curare abolish them owing to the inorganic salts in the curare employed. The appearance of movements is accompanied by increased excitability t o galvanic currents. The addition of calcium chloride lessens the movements and the excitability. Potassium chloride first increases and then stops both phenomena. The move- ments are regarded as myogenic. S. B. S. W. D. H. Comparative Effect of Alcohol Ether a n d Chloroform on Striped Muscle. Effects of Muecarine and Atropine ou Striped Muscle.AUGUSTUS D. WALLER (Proc. physiol. Isoc. 1908 lxxi-lxxiv lxxxi-lxxxiv ; J. physiol. 3’7).-The comparative anaesthetic effect on the frog’s sartorius was tested by the con- tractions obtained by stimulation when subjected t o immersion in various strengths of alcohol ether and chloroform respectively in 0.6% sodium chloride solution. The strengths iV/alcohol N/10 ether and N/100 chloroform are very nearly physiologically equivalent. The action of muscarine and atropine was tested in a similar way. Both alkaloids act as paralysants the former more powerfully. The chief difference is that muscarine produces a temporary contracture not unlike that caused by nicotine and caffeine. The muscle recovers when placed in normal saline solution but this is less complete after atropine than after muscarine. The antagonism of the two drugs is best shown by mixing them together when the contracture is not observed.W. D. H. Action of Sodium Cyanide on Muscles and Nerves of Gold- blooded Animals. s. DONTAS (Arch. exp. Path. PI~arna. 1908 59 430-443).-111 frogs sodium cyanide acts not only on the central nervous system but also on peripheral nerves. Muscles will not con- tract on stimulation of their nerves when these are exposed to the action of a 0.005% solution of the salt. This is a reversible action and can be removed by washing with Ringer’s solution. I n the early stages of poisoning in the intact animal the toxic effects are removable by the injection of sodium tbiosulphate. W. D. H.76 ABSTRACTS OF CHEMICAL PAPERS.Chemical‘ Investigations of Placenta. S . HIGUCHI (Biochern. Zeitsch. 1908 15 95-104).-The mean percentage result of the analysis of six placenta water 84.91 ; dry substance 15.09 ; fat 0.846 ; unsaponifiable substance 0.283 ; glycogen 0.032 ; total S. 0.120; total P. 0-140 ; lecithin 0.899 ; total N. 2.266 ; albumin 14.16 ; aqueous extract 3.974 (containing N. 10.38% ; ash 0.38’7%) ; alcoholic extract 2.070 (containing N. 3.521% ; ash 0.492%) ; total asb 0.878. S. B. S. The Effect of Hydrochloric Acid on the Composition of the Subcutaneous Connective Tissue of Rabbits. J. PH. STAAL (Zeitsch. physiol. Chem. 1908 58 97-1 17. Compare Loghem Abstr. 1904 ii 751).-The following determinations have been made with the extract from the subcutaneous connective tissue of normal rabbits and of rabbits to which hydrochloric acid was administered freezing point electrical conductivity and percentage of sodium and of chlorine It is shown that the percentage of sodium increases rapidly (some 4 to 15 times) after the administration of 0.5% hydrochloric acid during two to seven days.The ratio Na/Cl also increases and thus Loghem’s view that by the administration of hydrochloric acid alkali is removed from the tissue is not correct. These new facts can only be brought into harmony with Loghem’s experimental data by concluding that although the percentage of sodium increases fhe sodium concentration decreases in the case of rabbits to which hydrochloric acid has been given Similar experiments were made on the blood of rabbits. J.J. S. Arsenic in the Animal Organism. W. H. BLOEMENDAL (Arch. Pharm. 1908 246 599-616).-The occurrence and distribution of arsenic in the animal organism both before and after the administra- tion of arsenical preparations have been investigated. Full details are given in the original as t o the methods used in preparing arsenic- free reagents. The method adopted of destroying the organic matter was that of Fresenius and von Babo involving the use of hydrochloric acid and potassium Ichlorate. For the detection of the arsenic an electrolytic form of Marsh’s apparatus was employed capable of revealing the presence of 0*0001 mg. of arsenic. The formation of an arsenic mirror was depended on for the detection of the poison and in quantitative work the mirrors formed were dissolved in a sulphuric acid solution of potassium dichromate of known strength and titrated back with N/lOOO or N/4000 sodium thiosulphate.After administration of arsenic the latter can be detected in all parts of the organism but the various parts can be arranged in the following descending order as regards their arsenic content nails hair spleen thyroid gland skin lungs liver kidneys heart sacrum muscle generative organs and brain (compare Scolosuboff t h i s Journ. 1876 i 93; Gautier Abstr. 1900 ii 152 168 226 ; 1902 ii 517; Besredka 1900 ii 156; Denigds 1905 ii 745). Arsenic commonly occurs in the hair even when absent from all other parts. Normally urine contains no arsenic or only traces. Soon after pdministration it can be detected in the urine aud disappears again inPBTSIOLOGIC AT CBEMISTRY.77 ten to twelve days after administration ceases (compare Carlson Abstr. 1907 ii 130). I n man a greater percentage of the arsenic is eliminated in the hair than is the case with rabbits goats or cows. Cacodylic acid is converted in %he organism into arsenious oxide but it is not certain that this is the case with atoxyl. The arsenic in sodium cacodylate is eliminated partly in a gaseous form but this does not appear to be the case with arsenious oxide No arsenic or only traces appears in the milk in the case of the cow goat cat or rabbit but a small amount appears in human milk. Both in man and ankals only traces of arsenic are found under normal conditions (compare Gautier Zoc. cit.) and this appears to have no physiological significance and to be absorbed merely in the form of impurities in food etc.No arsenic is passed from the parent to the foetus. The Relationships of Cycloses to the Animal Organism. EMIL STARKENBTEIN (Zeitsch. physiol. Chem. 1908 58 162-164).- Rosenberger’s conclusion that inosite is present in tissues partly as a mother substance (inositogen) is dissented from. The conclusion drawn from quantitative experiments is that the animal organism contains free inosite. W. D. H. T. A. H. Oxidation of Products of aholesterol in the Animal Organism. 111. ISAAC LIFSCH~TZ (Zeitsch. physiol. Chem. 1908,58 175-184. Compare Abstr. 1907 ii 899).-This paper deals with the methods for the detection of oxycholesterol and further proofs are given that this substance and its precursor exist preformed in blood and bone-marrow.The first oxidation product passes easily into the second. W. D. H. The Origin of Glycine from Uric Acid. L. HIRSCHSTEIN (Arch. exp. Path. Pharm. 1908,59 401-406).-Further proofs are advanced that glycine originates from uric acid both in the body and in uitro. It does not however appear t o be an end-product of uric acid break- down for in alkaline solutions it is destroyed in part as soon as it is €ormed and if the concentration of the alkali is sufficient it is difficult to detect any at all. Storage and Retention of Quinine in the Human Organ- ism. G. GIESMA (Chem. Zentr. 1908 ii 1053 ; from Arch. Schifs- Tropsn-hyg. 1908 12 78-81).-The observation of Schaumann that quinine can be found in the organs of a dog even when the urine is free from alkaloid applies also t o the case of man.The quantities found were however as a rule so small that they could not be estimated quantitatively. I n a kidney weighing 420 grams 6 mg. were found. The blood was free from quinine aiid this observation does not confirm the general opinion that the alkaloid circulates in the blood-stream. The hsmolysis of black-water fever probably occurs in the kidneys. The Extractives from Fish Flesh. A. SUWA (Chem. Zentr. 1908 ii,jlll2 ; from Zentr. Plqsiol. 1908,22 307-310).-The extract W. D. H. S. B. S.78 ABSTRACTS OF CHEMICAL PAPERS from the flesh of cod was treated with tannin barium hydroxide and lead salts. From the concentrated purified extract creatinine separ- ated.From the filtrate the bases were separated by phosphotungstic acid. From the carbonates t%e alloxuric bases were precipitated with 20% silver nitrate. Other bases were obtained by fractional precipita- tion with silver nitrate and barium hydroxide Creatinine and methylguanidine were obtained in these fractions. After separating excess of silver other bases were obtained by fractional precipitation of solutions of chlorides with mercuric chloride. S. B. S. Osmotic Cloncentration in Body-Fluids of Aquatic Animals. WILLIAM J. DAKIN (Bio-Chem. J. 1908 3 473-490).- Further experiments are recorded on fishes and invertebrates which shorn that changes in the water in which they live brings about sooner or later an alteration in the electrolytes and non-electrolytes of the body-fluids followed by an alteration in the chemical constitution of their cells.Whether the interchange occurs by the gills or the alimentary canal is left undecided. W. D. H. Gharacteristic ‘Principles of Sclerostomum equinum. Presence in this Parasite of an Intensely Hamolytic Crystal- line Alkaloid. TH. BONDOUY (Compt. rend. 1908 147 928-930). -This worm which occurs in the intestine of horses contains an oily base crystallising in prisms yielding precipitates with general alka- loidal reagents furnishing a crystalline picrate and reducing auric chloride in the cold; less than 0.0001 gram produces hsmolysis in seven to eight minutes. G. B. The Sensitising Action of Vegetable and Animal Pigments on Paramacia. WALTHER HAUSMANN and W.KOLMEB (Biochem. Zeitsch. 1908 15 12-18).-1t has been shown already that certain pigments on exposure to light bring about rapid haemolysis of red blood-corpuscles. I n a similar way they can kill paramoecia. The pigments investigated were chlorophyll animal bile from different sources and hsematoporphyrin. I n some cases the pigment was added i n alcoholic solutions it being determined by preliminary experiments that the alcohol had no deleterious influence in the strength used. S. B. S. Sugar from Colostrum. JOHN SEBELIEN and EINAR SUNDE (Zeitach. angew. Chem. 1908 81 2546-2550).-The authors reply t o Schiebe’s criticism (Abstr. 1901 ii 204). Independent evidence is given of the presence of lactose in colostrum and the results of esti- mating this substance by the optical method and by Kjeldahl’s method are compared.Differences are .found of about the same magnitude and in the same direction as was observed when lactose was estimated in milk the optical method giving higher values than the gravimetric method. It is suggested that some small quantity of arabinose causes this difference the amount being put at about 0.05% of the colostrum. J. V. E.PHYSIOLOGICAL CHEMISTRY. 79 Excretion of Iodine and Lithium by the Bile. E. FRICHEB (Biochern. Zeitsch. 1908 14 286-39Y).-After the administration of lithium iodate in doses of 1 gram by the mouth in man the excretion of iodine by the bile reaches its maximum in the third hour. Some also leaves the body by the urine but later. If lithium iodide is given 0.86% leaves the body by the bile within twenty-four hours.Lithium also appears in the bile and its excretion by this channel lasts seven hours. The excretion of the two elements does not run parallel. The observ- ations were made on a patient with a biliary fistula. W. D. H. Condition in which Iodine Occurs in the Urine after Inges- tion of Iodides and Iodates. ELI CRESPOLANI (Boll. chim. faym. 1908 47 679-685).-The author confirms the presence of organic iodo-compounds in the urine after ingestion of potassium iodide. Further when alkali iodates are administered the reduction which they undergo takes place only during the gastric digestion and is complete when the quantities of iodate taken are not too great ; this reduction is affected by the action of the peptones in a solution which is faintly acidified with hydrochloric acid.T. H. P. The Influence of Tolylenediamine on the Cholesterol Content of the Faeces. CHOSABUR~ KUSUMOTO (Biochem. Zeitsch. 1908 14 107-41O).-’L’olylenediamine has been stated to cause a destruction of the red blood-corpuscles to which fact has been ascribed the increased amount of cholesterol found by the author in the bile of a dog with a biliary fistula. Further experiments with a normal dog show that subcutaneous injection of the drug causes also an increased excretion of cholesterol in the faxes. The increase like that in the bile is only transitory. S. B. S. The Cholesterol Content of bogs’ Faxes with Ordinary Nutrition and after Administration of Cholesterol. CHOSABUR~ KUSUMOTO (Biochern. Zeitsch. 1908 14 41 1-415).-With a meat diet more cholesterol was ingested than excreted.Addition of cholesterol to the diet caused increased cholesterol excretion. The increase in the amount excreted was however less than the increase in the amount ingested part disappearing presumably either through resorption in the alimentary tract or through destruction by bacteria. S. B. S . The Content of Dogs’ Faxes in Cholesterol and Copro- sterol. CHOSABURO KUSUMOTO (Biochern. Zeitsch. 1908,14,416-418). The acetylation number of the cholesterol isolated from faeces indicated that the crude product contained only cholesterol and coprosterol. The relative amounts of these substances found in the faeces after different diets were determined by means of the iodine number. S. B. S. Uric Acid Hxcretion in Normal Man. PAUL J.HANZLIK and PHILIP B. HAWK (J. BioE Chem. 1908 5 366-366).-The average daily excretion of ten healthy students of ages from nineteen to80 ABSTRACTS OF CHEMICAL PAPERS. twenty-nine years on a normal mixed diet containing 91.2 grams of protein (or 1.33 grams per kilo. of body-weight) was 0.597 gram. The generally accepted average is 0-7 gram. Changes in the Circulation of Nitrogen Produced by Colloidal Silver Prepared by the Electrical Method. EDUABDO FILIPPI and LEONARDO RODOLICO (Chem. Zentr. 1908 ii 1052 ; from Arch. Furrn. sperim. 1908 7 313-328).-Quantities of 5 C.C. of a reddish-brown colloidal silver solution containing 0.025-0.035% of metal were injected for eight days partly subcutaneously and partly intravenously into rabbits.There was a decrease in the nitrogen ’ingested during this period but an increase in the iiitrogen excreted s. B. s. BENJAMIN ~IOORE (Bio.-Chem. J. 1908 3 449-161).-Althougli the lessening of free hydrochloric acid in the gastric contents of cases of cancer is not absolutely diagnostic the author holds that it occurs in the majority of cases in spite of the opposite results obtained by Copeman and Hake in mice. W. D. H. the latter being chiefly in the form of urea. Hydrochloric Acid in the Stomach in Cancer. H e replies to the criticisms of these authors. W. D. H. The Occurrence of Lmmlose in Diabetic Urines. WJLHELM VOIT (Zeitsch. physiol. Chem. 1908 58 122-1 33).-The unsatis- factory nature of both Rosin’s and Borchard’s tests for lsvulose in brine is pointed out ; they frequently give contradictory results and sometimes positive results with normal urine.I n no case of diabetic urine was the I~vulose osazone obtainable. Inhibiting Effect of Potassium Chloride on Sodium Chloride Glycosuris. THEO. C. BURNETT (J. Biol. Chem. 1908 5 351-355). -After glgcosuria has been produced in rabbits by the injection of sodium chloride solutions the injection of a mixture of that salt with potassium chloride (100 2.2) markedly lessens the amount of sugar excreted. W. D H. W. D. H. The Lipolytic Powers of Syphilitic Sera and the Diagnostic Value of Lipolysis by Sera. JULIUS CITRON and KARL REICHER (Chem. Zentr. 1908 ii 1197; from Berl. Klin. Woch. 1908 45j 1398-1400).-Syphilitic sera have a lipolytic power of 208-3.5 for monobutyrin and 0.7-1.4 for lecithin as compared with the values 1.25-2.5 and 0.05-0.5 for normal sera.In view of the fact that Heuberg and Reicher have shown that most immune sera have a high lipolytic capacity this high lipolytic power of syphilitic sera cannot Anzesthesia and Paralysis Caused by Magnesium Salts. SAMUEL J. MELTZER and JOHN AUER (Amer J. Pltysiol. 1908 23 141-147).-Ryan and Guthrie’s view that the symptoms caused by magnesium salts are due t o asphyxia (increase of carbon dioxide in the blood) is an incorrect conclusion they have drawn from a single experiment and is entirely unsupported by analytical evidence. The be considered specific. s. €3. s.PHYSIOLOCIICAL CHEMISTRY. 81 magnesium salts affect the respiratory centre without any preliminary excitation such as is caused by carbon dioxide poisoning.W. D. H. Antagonicam of Alcohol and Carbolic Acid. ALONZO Z. TAYLOR (J. Biol. Chem. 1908,5,319-322).-As tested by its behaviour towards yeast there is no chemical detoxication of carbolic acid by ethyl alcohol. The effect noted by surgeons that alcohol applied to carbolised wounds checks the internal action of the phenol must therefore depend a.; Sollman has suggested upon some physical basis. W. D. H. Beheviour of the Three Isomeric Phthalic Acids in the Dog’s Organism. CH. PORCHER (Biochem. Zeitsch. 1908 14 35 1-360).-Animals received doses of the three acids per 08 generally in small quantities at a time over periods of several days The urine excreted during these periods was collected and the amounts of the phthalic acids therein estimated.It was found that phthalic acid was almost completely burnt in the organism whereas the isophthalic and terephthalic acids were recovered unchanged to the extent of 76%. No glycine conjugated acids were isolated. S. B. S. Physiological Action of Products of Metabolism. 111. Action of Scatole on the Frog’s Heart. IV. Action of Indole on the Frog’e Heart B. DANILEWSKY (Pfliiger’s Archiv 1908 125 349-360 361-377).-The frog’s heart was perfused with Ringer’s solution containing scatole or indole. Both substances depress the activity and frequency of the heart-beat the action being on the cardiac muscle direct. These substances are also deleterious t o ciliated epithelium and low organisms. W. D. H. Physiological Effect of Alkaloids from Hemlock (Conium maculatum). JACQUES M. ALBAHARY and KARL LOFFLER (Compt. rend. 1908 147 996- 999).-Given hypodermically to intact guinea- pigs these bases produce a fall of body-temperature sometimes followed by convulsions and death. The action of d- and Lconiine is identical. The introduction of a hydroxyl group in conhydrine and in $-conhydrine lessens the toxicity which is on the other hand increased by the double linking in the coniceines derived from the conhydrines by elimination of water. The action of $-coniine (obtained by reduc- tion of q-coniceine) is not identical with that of coniine. W. EMERSON LEE (Quart. J. exp. Physiol. 1908 1 335-372).-Nicotine is the most important poison in tobacco smoke; pyridine bases in the quantities present are not injurious. The amount of nicotine inhaled does not depend on the amount in the tobacco but on the form in which it is smoked. The greater the condensation area between the point of combustion and the entrance into the mouth the more nicotine is distilled off from the hot area and will be inhaled Smoking raises the blood-pressure by vasoconstriction accelerates the heart and respiration and increases intestinal movements. In excess cerebral depression may occur and . G B. Action of Tobacco Smoke. VOL. XCVI. ii. 682 ABSTRACTS OF CHEMICAL PAPERS. blood-pressure may be lowered to the point of collapse. are chiefly seen in unpractised smokers. may induce arterial disease. These effects Prolonged tobacco smoking W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9099605066

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

77 Organic Chemistry. Density of Methane; Atomic Weight of Carbon. GEOBGES BAUME and F. LOUIS PERROT (Compt. rend. 1909 148 39-42).-The methane was prepared by the action of water on magnesium methyl iodide and after being passed through different reagents and then dried was purified by liquefaction and fractional distillation. The density determinations were carried out in tbree bulbs of different size in the usual way. As a mean of nine moderately concordant experiments the weight of a litre of the gas a t 0°/760 mm. is 0.7168 gram. From the results the atomic weight of carbon is calculated by the physico-chemical methods of Leduc D. Berthelot and Guye respectively; the mean value is C=12*004 (H=1*0077) in good agreement with the accepted value. G. S. Hydrocarbons C,H ; New Synthesis of Tetramethyl- methane [Dimethylpropane].ENOS FERRABIO and F. FAGETTI (Gazzetta 1908 38 ii 630-634).-Dimethylpropane may be prepared by the action of (1) methyl magnesium iodide on tert.-butyl iodide (15-20% yield) ; (2) tert.-butyl magnesium iodide on methyl iodide (15-20% yield) ; (3) methyl sulphate on tert.-butyl magnesium iodide (75% yield). The &t.-butyl alcohol required in the last of these syntheses may be obtained in 75% yield by the action of carbon dioxide on methyl magnesium iodide (compare Grignard Abstr. 1904 i 213). T. H. P. Synthesis of Ethylene from Carbon Monoxide and HydrQgen by Gontact with Nickel and Palladium. E. I. ORLOFF (J. Rust?. Phys. Chem. soc. 1908 40 1588-1590).-When a mixture of approximately equal volumes of carbon monoxide and hydrogen is passed over pieces of coke impregnated with reduced nickel and palladium and heated a t 95-lOO0 no formaldehyde is produced the gaseous mixture obtained consisting of carbon monoxide hydrogen and ethylene with a small proportion of air.In one experiment the gases contained 6.6% of ethylene and in another 8.3%. The first part of the reaction piobably consists in the reduction of the carbon monoxids to water and the methylene group CO + 2 8 = H,O + CH t g o methylene groups then combining to form ethylene. Attempts to absorb the ethylene in the mixture of gases formed by means of bromine or bromine water met with failure which the author accounts for by the great dilution of the ethylene with other gases. A concentrated solution of potassium mercuric iodide HgI,,BKI in sodium hydroxide constitutes a far more certain absorbent of ethylene than either bromine or bromine water.The formation of ethylene inbtead of methane which would bw espected from the results of Sabatier and Senderens and of Ipatieff is aot in accmd with the thermal chaagoe occurring during these VOL. XCVI. i. 918 ABSTRACTS OF CHEMICAL PAPBRS. reactions which would indicate the formation of methane rather than ethylene. When a mixture of carbon dioxide and hydpogm is passed over coke impregnated with nickel and palladium and heated at 95-looo the resultant gases do not contain either formaldehyde ethylene or methane. A t higher temperatures also no formation of formaldehyde is observable carbon dioxide and hydrogen yielding ethylene and methane ; this observation is not in accord with those of other investigators who state that only methane is formed by the reduction of carbon dioxide The carbon dioxide first undergoes rediiction in the presence of heated coke to carbon monoxide which is then reduced to ethylene and methane.T. H. I?. Preparation of Nitromethane. WILIXELM STEINKOPP (Ber. 1908 41 4457-4458).-A modification of the original Preibisch method (this Journ. 1874 462) which not only gives a much better yield of nitromethane but also avoids the evolution of hydrogen cyanide. A solution containing potassium chloroacetate ( = 200 grams of acid) and 300 grams of potassium nitrite in one litre of water is heated in a flask fitted t o a condenser until carbon dioxide begins to be evolved.Tne reaction then proceeds and the nitromethane distils in the steam. ’She yield is 49% of the theoretical. W. R. Ethylisoamylcarbinol and Methylisohexylcarbinol. ARMAND Compare Henry BUELENS (Bull. Acad. ?soy. Belg. 1908 921-929. Abstr. 1906 i 723).-E’tl~~ZisoanzyZca~binoZ CHMe2*CH2*CH2*CHEt*OH m. p. 61° b. p. 165-166” D 0.8084 n 1.42011 obtained by the action of magnesium isoamyl bromide on propaldehyde is IL liquid of pleasant odour and burning taste. The acetyl derirative ‘b. p. 184-185O D2O 0.8554 n 1.41602 is a colourless mobile pleasant-smelling liquid. Methylisohexylcarbinol CHMe,-CH,-CH,*CH2*CH~leeOH b. p. 171--172°/760 mm. D20 0-8128 n 1-42381 obtained by the interaction of magnesium isohexyl bromide with acetaldehyde is a liquid of agree- able odour and sharp taste.The ucetute b. p. 187-188O/768 mm. D20 0.8494 n 1-41 37 is a colourless mobile pleasant-smelling liquid. Methyl isol~xpl ketone b. p. 166’/770 mm. D20 0*8151 obtained by oxidising the alcohol with chromic acid is a colourless liquid and forms a sodium bisulphite compound. The methyl ethep CHRle,* CH2* CH2-CH,* CHMe* OMe b. p. 149-1 5 Oo/76O mm. D20 0-7945 obtained by the action of chloroethyl methyl ether MeCHCl-0 *Me on magno~iam isohexyl bromide i s a liquid of agreeable odour. /3-Jlethyll~eptaoze CHMe,*[CH,],*CH b. p. 1 ld0/760 mm. D2O 0.7134 m z 1.39807 was obtained by the action of metallic sodium on a mixture of propyl iodide and isoamyl iodide tho normal hexaiie and the decane simultaneously formed being eliminated by fractional distillation.It is a colourless very mobile pleasant-smelling liquid,ORGANIC CHEMISTRY. 79 The hohexgl alcohol b. p. 147-14S0 used in the research mas prepared by the action of trioxyrnethylene on magnesium isoamyl bromide in presence of zinc chloride. isoHezyZ bromide b.. p 146-147*/760 mm. D20 1.1683 n 1.44897 obtained by saturating the alcohol with hydrogen bromide and warming in a closed vessel is a colourlesq mobile liquid of slight not unpleasant odour. T. A. H. Direct Dehydration of Certain Tertiary Alcohols. LOUIS HENRY (Compt. rend. 1908 147 1260-1 262).-1n the production of fly-dimethyl-A"- bu tylene and Fi-dirne t h yl-As- but ylene by heating dimethyli8opropylcarbinol with acetic anhydride containing a small amount of sulphuric acid (Abstr.1907 i 374) it was originally considered that since only a very small proportion of sulphuric acid was present the acetic -anhydride acted as the dehydrating agent. Delacre however has shown (Abstr. 1907 i 459) that dimethyliso- propylcarbinol is transformed into its acetate by the action of acetic anhydride. Thus the sulphuric acid must be the active agent in the reaction which seems to be a curious instance of catalyeis. That the acetic anhjdride takes part in the reaction however is shown by the fact t h a t it is only iu the presence of a few drops of sulphuric acid that the decomposition of the acetate already formed takes place more easily and more ispidly than that of the alcohol as such. Contrary to the behaviour of dimethylisopropylcarbinol cyclopropyl- methylcarbinol (Abstr.1908 i 881) when heated with acetio anbydride containing a little sulphuric acid does not undergo dehydration but is completely transformed into its acetate. The con- clusion is drawn that the existence of a closed chain in the molecule confers stability on the alcohol. E. H. ~-DirnethylaJlylcarbinol. MAURICE VAN AERDE (Bull B a d . roy. Belg. 1908 929-939).-~-Chloro-/3-methyl-A~-amylene CUe, CH*CH,*CH,CI (Henry Abstr. 1907 i loti) yields a liquid dibromide D20 1.71 and is converted into the corresponding acetate (the dibronaide of this. has D20 1.551) by heating in c l o d tubes with potassium acetate and acetic acid and this on treatment with potassium carbonate yields yy-d.in~st?~:yZaZZylcarbinoZ CMe,:CH*CH,*CH,*OH b. p. 157-15S0/771 mm.D20 0.8615 n 1.44116 a colourless liquid with a slight terebinthinous odour and sharp acrid taste. On re-conversion into the acetate D20 0.9183 nD 1.4308 by the action of acetic anhydride the product obtained boiled a t 165-175O which would seem to indicate that the alcohol and chloride referred to above are mixtures in spite of their constant boiling points. Having regard to its method of foruation the hupposed chloride might consist of the two substances CMe,:CH*CH,*CH,Cl and C H 2:CMe*CH,.C d $C1 but it does not yield acetoiie on oxidation with chromic acid as t h e second suggested constituent should do. On adding acetic anhydride to the mixture resulting from the g z80 ABSTRACTS OF CHEMICAL PAPERS. action of magnesium methyl bromide on ethyl y-chlorobutyrate (Abstr.1907 i 106) adding water and extracting with ether a mixture of r-chloro-P-methylpentane-P-ol OH*CMe,*CH,*CH,.CH,Cl (Zoc. cit.) and dimethyltetramethylene oxide CMe,.y= wa8 o<CH,-CH,' Y * obtained in place of the expected chloroncetin T.A. H. Physico-chemical Properties of Ethylene Qlycol and of its Solutions in Water. F. SCHWERS (Bull. Acad. rog. Belg. 1908 814-854).-The author has determined the densities of ethylene glycol and of its mixtures with water at temperatures from 0-looo the specific heats of ethylene glycol and its mixtures with water and the heats developed when it is mixed with water in various proportions. From the results obtained which are given both in tabular and in graphic form the following conclusions are drawn (1) Ethylene glycol has D 1.12570 and its expansion by heat can be represented by the expression (2) A contraction in volume accompanied by a development of heat occurs when ethylene glycol is mixed with water in any proportion.At Oo the maximum contraction (1.545% of the initial volume) is observed with a concentration of 58% of glycol and 42% of water corresponding with the hydrate 2C,H,(OH)2,5H,0. The contraction decreases generally with increase in temperature but between 50' and 70° a slackening in the rate of this decrease is observed for all concentrations and is indicated by a flattening of the curves between these temperatures. This phenomenon which seems to be connected with the boiling points of the components of the mixture is also exhibited by mixtures of glycerol and water between 70° and 90°.Mixtures of the monohydric alcohols with water of certain concentra- tions undergo the same contraction a t all temperatures but a similar behaviour is not observed with aqueous solutions of the diols and triols. (3) The specific heat of ethylene glycol is 0.563 at 20' and 0.591 at 3.i0 whilst that of its aqueous solutions is always greater than that calculated additively from the specific heats of the glycol and of water (=l). (4) The heat developed by mixing glycol with water reaches a maximum for the concentration of 37% of glycol and 63% of water which corresponds with the hydrate C1H,(OH),,6H,0. It decreases with rise in temperature but the diminution is relatively small so that it is still positive a t the boiling point.The system ethylene glycol-water follows the thermodynamicrule that the difference between the calculated and observed specific heztts is equal to the coefficient of the heat of admixture. In all the above respects the properties of the diols are intermediate between those of the mono- and tri-hydric alcohols. Vt = Vo(l + 0.0005657t + 0*0000017074t2 + 0*00000000293t~). E. H. Expansion of Ethyl Ether and of Some Mixtures of the Ether and Ethyl Alcohol. WXLLY BEIN (Abhand. K b'ornabic?& rcngskom. 1908 7 reprint from author).-'l'he density a t 5 O loo,ORGANIC CHEMISTRY. 81 1 5 O 20° and 25* of the purest commercial ethyl ether (Kablbaum) Di5 = 0.7300 of a specimen of ordinary commercisl ether Dt6 = 0 7274 and of two mixtures obtained by mixing Kahlbaum’s ether with 5% and 10% of a commercial spirit containing 90% of alcohol by volume have been determined.The two latter specimens had Dis = 0.7280 and 0.7354 respectively. As the investigations were carried out mainly for revenue purposes no measurements were made with absolutely pure ethyl ether. The density determinations were made in a U-shaped dilatometer the upper parts of the two branches being long graduated capillary tubes; at the extreme ends the capillaries were so narrow that no appreciable error was caused by leaving them open. The density results are probably accurate to sonie units in the fifth decimal place and for convenience of reference they are also tabulated to 1 in 10,000. The mean expansion for lo ct = [( Vt/Yo) - l]t between 0’ and to is as follows allowance being made for the expansion of the glass Purest ether ..... . . . . . . . Ether of D = 0.7280 ... 0.001522 + 0.0000040t. 0.001480 + 0.0000042t. D = 0.7354. .. 0*001438 + 0*0000040t. The results are compared in detail with those obtained by previous observers. In an appendix the impurities which may be present in commercial ethyl ether and the methods of detecting and removing them are given. G. S. Alkylated Halohydrin and Vinyl Ethers. PAUL HORINGI (Bet-. 1908 41 4459-4460. Compare Abstr. 1908 i 497).- Polemical. A reply to Houben (Abstr. 1908 i 935). W. H. U. Action of Alkalis on Sodium Alkyl Thioaulphates. T. SLATER PRICE and DOUGLAS F. Twiss (Bev. 1908 41 4375-4378. Compare Trans. l908,93,1395).-The formation of disulphides by t h e action of alkalis on complex organic thiosulphates was observed originally 3y Bernthsen (Abstr.lbS9 775). The existence of Gut- mann’s thioethyl hydroperoxide (Abstr. 1908 i 497) is questioned. Fromm’s experiments (ibid 969) are also regarded as pointing to the non-existence of this compound. The authors’ previous view of the reaction between alkalis aud alkyl tbiosulphates is adhered to. J. J. S. Indirect Analysis by means of the Dilatometer. Lower Hydrate of Sodium Acetate. W. LASH MILLER (3. Physical C‘hem. 1908. 12 649-654).-When sodium acetate trihydrate is heated it partly melts at 58O with formation of a solution and separation of a new h a l t occurring in leaflets. The leaflets consist of a normal acetate of sodium but they cannot readily be separated from the solution for purposes of analysis. It is shown however on the basis of the phase rule that the com- position of the leaflets can be deduced by adding to a definite quantity82 ABSTRACTS OF CHEMICAL PAPERS.of the tribjdrate a known amoiint of the anhydrons acetnte and determining the proportion of trihydrate present in equilibrinm a t 58". The amount of trihydrate preseiit has been determined by dilntometer measurements. I n this way i t is shown t h a t the le~flets consist of the anhydrous salt a concluqion confirmcd by the direct experiments of Green (next abstract). G. S. The Melting Point of Hydrated Sodium Acetate. Solubility Curves. W. P. GREEN ( J . Physical Chem. 1908 12 655-660) - The leaflets separating when sodium acetate is heated to its apparent melting point at 5s' have been drained a t 9 5 O and shown by analysis and m.p. determination to be the anhydrous salt. The solubility of the anhydrous salt has heen determined from 0" t o 123" the boiling point of the saturated solution and t h a t of the trihydrate from its cryohydric point to 58'. The latter tempernture is a. transition point at which the reaction CH,-C02Na,3H,0= O*092CH3*C0,Na + solution (0 OS$CH,CO,Na + 3H,O) is in equi- librium. The lowest temperature a t which a clear solution can be obtained is 79" when the solution saturated with the anhydride has the same composition as the crystals of the trihydrate. G. S. Molecular Compounds of Magnesium Bromide and Iodide with Derivatives of Acetic and other Organio Acids. BORIS N. MENSCHUTKIN (Zeitsch.anorg. Chent. 1909 61 100-1 18. Corn- pare Abstr. 1907 i 19 395).-Magnesium iadide combines with methyl acetate forming the compound MgI,,6CH3*C02Me. Mixtures containing from 3.5% to 74.5% of the cornpound separate into two layers on melting. On the other hand the ethyl propyl and iso- butyl acetate compounds MgI,,GCH,*CO,Et MgI,,GCH,*CO,Pr~ and Mg1,,6CH,*C02*C,H9@ give regular freezing-point curves aud do not Eeparate into two liquid layers. Separation into two layers is brought about in the case of the ethyl acetate compound by the addition of a little water. Magnesiam bromide forms compounds containing 3 mols. of ester which however crystullise badly. Magnesium iodide and ethyl formate form a compound Mg12,6H*C0,Et which is less hygroscopic than the acetate compounds.The following compounds have been prepared but not further described M.gJJr2,2C,H,*C0,Et m. p. about 110"; RlgBr2,2C,H,.C0,*C4H9B m. p. about 130° ; Mg12,3C,H,*C0,Me m. p. 115-1 17" ; Mg12,3C,HS*C0,Etl m. p. 105". Ethyl mnlonate gives MgBr,,2CH,(COzEt)2 m. p 135' and Mg'l2,4CH,(CO,Et) m. p. about 115'. C. H. D. The Waxes of the Coniferze. A New Group of Natural Principles. J. ROUGAULT and LBON BOURDJER (Compb. rend. 1908 147 131 1-1 314).-By employing the method described by Bourquelot (J. Phurm. Chim. 1901 [vi] 14 481) the authors have isolated white,ORGANIC CHEMISTRY. 83 crystalline powders resembling certain known vegetable waxes in appearance from many of tho Conifers for example from Junipwue Sabina J. cornrntmi8 Picea excdsa Pinnus sytvestris and Thztyo occidsntaZis.Kawalier the only previous worker on these substances (J. p. Cl~m. 1F53 60 321 ; 1855 64 16) owing to the defective method used obtained erroncow results. The purified wax is not a simple substance that from J. Sabina having m. p. 73-78" and yield- ing on repeated recrystsllisation a series of substances having m. p.'s 65' to 84'. All the substances isolated however have the following properties they are acids with an acidity value varying from 25 t o 54 (indicating a molecular weight of 3OCO-1000 i f they are mono- basic acids) contain an alcohol group and are esters with saponification values of about 230. ,411 t heir snponificrrtion products are acids that is the waxes do not give any substances analogous t o glycerol or cetyl or melissyl alcobol.Thus the products of saponification are alccihol- acids and from the results obtained on acetylation seem to contain only a single alcohol and carbosyl group. So far only two of these acids have been isolated. The first has the compositioz CI6H3,O3 of a hydroxypalmitic acid i t has m. p. 9 5 O and is designated juniperic acid. The second sabinic acid m. p. 84O seems to be a hydroxylauric acid C12H2,0s. By connoting the results obtained the authors deduce the mheme R:CH( OH) [CR,],*CO* 0 CHR' [ CH21m-C0 O*CHR*[ CH,lp . . C0,H for the constitution of the waxes R R' R etc. and 72 mlp being either identical or different. The frequent appearance of juniperic acid suggests that they are generally identical. The name etholides is proposed for this group of natural substances whiuh probably differ by the number of acid-alcohol molecules associated in them rather than by differences in the acid-alcohol molecules themselves.They thus resemble the polypeptides more nearly than the polysaccharides. E. H. Eeteno XI. New Method of Formation of Carbon Suboxide. HERMAKN STAUDINGRB and ST. BEBEZA (Ber. 1908 41 4461-4465 Compare Staudinger and Ott Abstr. 1908 i 602).- In attempting to prepare malonic anhydride by acting on malonyl chloride in ether or ethyl acetato with silver lead or zinc oxide it was found that carbon suboxide was formed probably thus Carbon suboxide is also obtained when malonyl chloride is treated with either silver oxalah or malonate; however in none of these cases does the yield of aribon suboxide exceed 10%.Silver malonate inferacts with acid chlorides such as cinnamoyl chloride yielding gmdl quantities of carbon suboxide ; the latter must result from tihe decomposition of malonic anhydride or ft mixed anhydride ; consequantly malonic anhydride differs from its alkyl derivatives in that it yields carbon suboxide and not keten when it decomposes. Acetyl chloride forms with silver malonate a substance which is probably identical with that obtained by Diels and Lalin (Abstr. 1908 i 939) by acting on carbon suboxide with acetic a d . It is also probable that the analogous compound derived from carbon CH,(COCl) + Ag,O = C,O + %AgCl+ H,O.84 ABSTRACTS OF CHEMICAL PAPERS. suboxide and formic acid (loc. cit.) is a mixed anhydride of formic and malonic acid having the fmmula C&(CO*O*CHO) A compound having this constitution when heated would decompose yielding carbon monoxide carbon suboxide carbon dioxide acetic acid and formic acid.A 50-80% yield of carbon suboxide may be readily obtained by treating a solution of dibromomalonyl chloride in ether or ethyl acetate with zinc shavings. Dibrornomalonyl chlorzde CBr,( COCI) prepared by the action a€ phosphorus pentachloride on an ethereal solution of dibromomalonic acid is a colourless oil b. p. 75-7'i0/15 mm. which solidifies to a colourless crystalline mass a t the ordinary temperature. It reacts with aniline forming dibromoinalonanilide CBr,( CONHPh) compact crystals m. p. 143-144". Action of Zinc Dust at High Temperatures on Various Types of Aliphatic and Aromatic Acids. ALEXANDRE HEBERT (Bull.Soc. chim. 1909 [iv] 5 11-1 9).-A continuation of previous work (Abstr. 1901 i 251 ; 1003 i 396) on the products of the distillation of acids with zinc dust. The acids were mixed with from three t o four times their weight of zinc dust and heated at 350-400'. Succinic acid yielded carbon dioxide and inflammable gases composed principally of hydrogen water and liquid oletines. The residue in the flask contained some carbon and zinc Carbonate. Oxalic acid gave hydrogen carbon dioxide. carbon monoxide and water. Bonzoic acid furnished hydrogen carbon dioxide water benzene benzaldehyde some unchanged benzoic acid and a little naphthalene. The decom- position which ensued with cinnamic acid was very complicated. The gases evolved consisted of carbon dioxide hydrogen and some hydro- car bow.The liquid distillate included water benzene toluene xplene styrene diphenyl naphthalene and its homologues stilbene fluorene fluorauthrene homologues of anthracene and phenanthrene tolane and phenylmethanes ('l) with some tarry matters. The residue in the flask contained carbon and some zinc carbonate. Distillation of cinnamic acid with lime showed that styrene is not as is generally supposed practically the sole product of the reaction. The distillate resembled in composition that described above but contained more benzene and a little benzaldehyde. Phthalic acid gave carbon dioxide hydrogen gaseous hydrocarbons water benzene phthalic anhydride and tar. Action of Sulphuric Acid on Acetaldehyde and Paracet- aldehyde.Preparation of Grotonaldehyde. MABCEL DEL&PINE (Compt. rend. 1908 147 1316-1318 *).-The methed of preparing crotonaldehyde described previously (Abstr. 1902 i 133) has been improved by using pnracetaldehyde instead of acetaldehyde. Paracet- aldehyde (50 grams) is added in portions of 10-15 grams to ordinary concentrated d p h u r i c acid (250 c.c.) contained in a flask which is continually shaken and cooled by a stream of cold water. After fifteen minutes the product is diluted to 2 litres with water and * and Am. Chint. P7qs. 1909 [viii] 16 136-144. W. H. G. T. A. H.ORGANIC CHEMISTRY. 85 distilled. By rectification of the product 43% of the theoretical yield of crotonaldehyde is obtained. In tbe reaction tbere are also formed L cowound C,H,,O b.p. 92-98'/30 mm. which seems to be a bimolecular polymeride of crotonaldehyde and a considerable amount of resin. The new polymeride differs from those described by KekulB ( A r m a h 1872 163 105) Raper (Trans. 1907 91 1831) and Zeisel and Bit16 (Abetr. 1908 i 761) in t h a t it forms a gemicarbazone CgHl5O9N3 m. p. 191-194O and a stable o x i m m. p. 106O. The reains formed are fawn-coloured and on oxidation with nitric acid give oxalic acid and a yellow amorphous substance which dissolves in smmonia to an orange solution. E. H. Anodic Oxidation of Aldehydes. GEORGE W. HEIMROD and PHOEBUS A. LEVENE (Ber. 1908 41 4443-4448).-1t has already been shown that acetaldehyde is a good depolariser in acid solution (Dony-Hhault Abstr. 1900 ii 644) and in alkali solution (Baur Abstr.1902 i 77) and further Law (Trans. 1905 87 198) obtained quantities of carbon dioxide and monoxide as well as the corresponding fatty acid on electrolytic oxidation. Acetaldehyde in sodium sulphate or 0*85N-sulphuric acid solution at 4-5O with a current of 1 ampere using s spiral platinum electrode is oxidised almost quantitatively to acetic acid only small quantities of the oxides of carbon being liberated. I n 0-9N-sodium hydroxide solution however only 92% of the oxygen is absorbed by the aldehyde a large amount of carbon monoxide dioxide and oxygen being liberated in the anode gas. Formic acid is found i n the liquid and it is probable that acetic acid is only formed in small amount. Butaldehyde and isobutaldehyde in N-alkali solution give only small amounts of acid and a large volume of carbon dioxide; in the latter case acetone was found but formic acid could not be detected.W. R. Syntheses by means of Mixed Organo-metallic Zinc Derivatives @-Ketone Alcohols and &-Acyclic Uneaturated Ketones. EDMOND E. BLAISE and RI. MAIRE (Ann. Chim. Phyu. 1908 [viii] 15 556-576).-Mainly a resume of work already published (compare Abstr. 1907 i 749 ; 1908 i 79 248 318 596) ; the following compounds are described for the first time y-Hydroxy- y-ethylhcxnn-&one OH-C Et,*COEt b. p. 68'/11 mm. prepared by the action of magnesium ethyl iodide on ethyl semi-ortho-oxalate ; y-methyl- Ar-heyten-r-one CMeEt:CH*COEt b. p. 16Q0 forms a senzicurbazone m. p. 159' ; ethgl cacetoxy-sec.-butyZ htom [a-acetoxy-/3-ethylpsntan-y-m] OAc*CH,*CHEt*COEt b.p. 102'112 mm. ; y - r r a e t h y l m b n - b e CH,:CEt*COEt b. p. 137" ; p - acetoxy - y - ethylhexan- 8 - on.8 OAc*CHMe'CHEt=COEt b. p. l02"/ 12 mm. ; @-methyLA~-hexen-8-m CMe,:CH*COEt b. p. 145O forms a semicarbazooe m. p. 162'. Ethyl P-hydroxya-ethylisovalmate OH*CMe,*CEt*CO,Et b. p. 84O/ 9 mm.; the corresponding acid has m. p. 73'; ethyl PP-dimcthyl-a- ethytacrytate CMe,:CEt*Cc),Et b. p. 1 6 7 O obtained from the above ester by the action of phosphoric acid; the corresponding d has86 ABSTR&CTS OF CHEMICAL PAPERS. b. p. lOO"/lO nim. and the chloride b. p. 49'/13 mm. reacts with zinc ethyl to form P-methyl-y-ethyl-Ap-hexen-6 one CMe,:CEt*COEt b. p. 16P0 of which the semicarbaaone has m. p. 11Y. M. A. W.Formation of Hydrocellulosee by means of Sulphuric Acid. GEORG B~~TTNER and J. NEUMAN (Zeitsch. amgew. Chem. 1908 21 2609-2611. Compare Girard Abstr. 187'3 779 ; Bumke and Wolffenstein Abstr. 1899 852 ; Tauss Ding. Poly. J. 1889 286).- Arnyloid prepared by leaving cotton wool in contact with sulphuric acid (1.53) for several days then carefully precipitating and washing has the composition C 41-89! 42.00 and H 6.0 6.07%. An ideal hydrocellulose can be obtained by Ulzer's method (Wagnei's Jahresbe~*. 1905 192). The cotton is impregnated with 4% sulphuric acid pressed and kept a t the ordinary temperature for four days or until dry and then carefully heated at 7 5 O for eight hours. When touched the maw falls to a white powder and its suspensions in acid have a colloidal nature and do not clear wben kept.Analyses of the washed material dried at 100' gave C 43 S6 H 5.41% which agree with values required for the formula (C6H1005)6,HZ0. When this hydrocellulose is further treated with 50% sulphuric acid sometimes it does not undergo any further change sometimes it yields compounds of the types 3C,H,,O,,H,O and 2C6H,,0,,H,0. The hydrocelluloses are white powders with a gritty feel and are resistent t o acids and alkalis. With sulphuric acid and acetic anhydride they yield cellulose acetates which can be preoipitated by water. They are coloured blue by zinc chloriodide or a solution of iodine in potassium iodide solution and have reducing properties but are not turned black by the ovidising action of the atmosphere (compare Girard). J.J . S. Humin Substances in [Peat Wool ('( Quate de Tourbe"). L EOGER and E. VULQUIN (Compb. rend. 1908 147 1404-1406)- The humic acids extracted from peat wool by sodium hydroxide are derived from cellulose-like substances from which they differ in containing more carbon and nitrogen They contain neither pentosans nor hexosans; alcoholic hydroxyls still seem to be present for acetyl derivatives and thiocarbonates can be formed as in the case of celluloee. The benzene nucleus the grouping *CH,*CO and double linkings are also present. Example of Iaodimorphism. [Ethylamine Halides.] H. MAR AIS (Cmpt. ?*end 1909 148 45-47).-Ethyl:imine hydrochloride and the corresponding hydrobromide are monoclinic at the ordinary temperature. At 80° the hydrochloride changes t o a uniaxial modification which fuses at 10s'.A t 8 3 O the hydrobromide is also changed t o a uniaxial form which melts at 146". Puitlier i l l the superfused hydrobromide an anstable uniaxial f om1 appears which fuses at 118O but under ordinary conditions rapidly changes to the stable form. The monoclinic forms of the two compounds are miscible in all proportions tbe temperature of transformation remains betweea SOo G . B.ORGANIC CHEMISTRY. 57 and 83".. 'She forms obtained at higher temperatures are isodi- morphous the htable form of one being isomorphous with the unstable form of the other. Further as the composition approaches the point corresponding with 45% of the hydrobromide at loo' the unstable forms tend to become relatively stable. Valyl-leucine Anhydride.E. KRAUSE (Monatsh. 19OS 29 11 19-1 130).-The paper is mainly an account of unsuccessful ex- periments and of compounds already described-( Fischer A bstr. 1907 i 684). Vcilyl-leucine anhpdride m. p. 273-274O is formed by heating equal molecular quantities of valine and leucine ester8 at 180-190° or equal quantities of d i n e and leucine in an evacuated tube at 340'. Some Amides of Amino-acids. ERNST KOENIGS and BRUNO MYLO (L'er. 1908 41 4427-4443).-The amides of amino-monocarboxylic acids are not easily obtained in the pure state but i t is found that the ethyl esters are converted into the amides by liquid ammonia and as a rule they are unstable in the presence of water. When the ester of glycine is treated with three times its volume of liquid ammonia there is formed diketopiperazine glycylglycinarnide and glycinamide C2H,0N2 ; the latter compohnd cry stallises from chloroform in needles m.p. 65-67O (corr.). It is strongly alkaline and hygroscopic. The dina~htlulZe~sulp?~~ny~glycinumide from naphthalenesulphonyl chloride and amide crystallises in slender needles m. p. 201O (corr. decomp.) ; P-naphthalenesulphonamide is obtained on its hydrolyhis with N/lO-sodiurn hydroxide showing that the two naphthalenesulphonyl radicles are attached to the amido- nitrogen and not to the amino-group. Carbethoxyglycinamide (Fischer Abstr. 1903 i 609) may also be prepared from the amide by the action of ethyl chlorocarbonate in the presence of alkali and a 10% yield of bydnntoin is obtained from carbethoxyglycinamide by the action of N/Z-sodium bydroside during twenty-four hours at the ordinary temperature.d-AZaninamide C H ON crystallises from ohloroform in colourles~ slender prisms m. < $2' (corr,) [aID + 6' in 5.2% aqueous solution. The dl-alaninamide prepared by liquid ammonia agrees in all respects with that obtained by Franchimont and Friedmann in 1906. Carbethoxy-dl-alaninamide can be obtained in 86% yield from the amide (compare Fischer and Axhausen Abstr. 1905 i 689) and a-methyl bydantoin from the carbethoxycompound has m. pI 146.5' (corr.). p-Naprht~halene8u~p'phonyEdl-alani~amide C1,Hl,O,N,S has m. p. 220' (corr. decomp.). dl-a-Amino-n-butyramids C,H,oON crystallises in prisms II~. p 74-75' (corr.) and yields carbethoxy-dl-a-amino-n-butymmide which forms colourless needles m.p. 115-116O (corr.). u-EtrTryZ hydantoin C5H802N2 crystallises from chloroform in slender needles m. p. 11 8-1 20' (corr.) and p-nu~~trhalenesulphonyl-dl-amino~tyr~ am& Cl,H,,03N,S has m. p. 251O (corr. decomp.). dl-Yalinamide C,H,,ON only results after the ester and liquid G. S. c. s. C22HI SOP2S29 C7H1403N2,88 ABSTRACTS OF CHEMICAL PAPEHS ammonia have been in contact three mouths; it has m. p. 78-80° (corr.) and yields /3-nap/rthalenesulphonyZ-dl-ualinarnide C,,H,,O,N,S of m. p. 256-257O (aorr.) ; cnrbethoxy-dl-ualinamids,' C,H,,C),N slender needles m. p. 143-144' (corr.). dl-leucinumide C6Hl,0N2 has m. p. 106-107O (corr.) ; the P-nuphthabnesulphonyl derivative has m. p. 176-178' (corr.) ; cnrb- ethozy-dl-Zeucilzamide C,Hl,0,N2 m. p.1 OSO and 6-isobutylhydantoin (compare Pinner and Lifschutz Abstr. 1887 1055) is readily obtained from the preceding compound by shaking with sodium hydroxide. dl-~~enR/lalnninccmid~ C,H,,ON crystallises in prisms m. p. 138-1 40' (corr.) and yields the P-naphthalenesulphonyl compound of m. p. 164-166' (corr.) and the carbethoxy-dl-phenylataninamide C,,H,,0,N2 m. p. 141O (corr.). l-Y'yro~tznamride CgH,,O,N crystallises from alcohol in large flat prisms m. p. 153-154" [uE + 19.49' in water and its dicarbethoxy- derivative C,5H2006N2 forms needles m. p. 185' (corr.) ; the morio- carbethox y-1 -t yrosinamide OH*C,H,*CH,*CH( NH* C0,Et) *CO *NH has m. p. 155-157' (corr.). The dinaphthalaizesulphonyl compound C29H,,0,N2S has m. p. 204' (corr.). Carbethoxy-1-uspuragine C17H,205N2 crystallises from water and has m.p. 269-17 1' (COI r.) ; the p-nccphthaleneeul~~onyl-l-as~ragine C,,H,,O,N,S has m. p. 192-193' (corr,). C19H1803N2S'2~ W. R. Preparation of Glycocyamines or Guanino-acids. HENRIK RAMSAY (Ber. 1908 41 4385-4393. Compare Streckor Conzyt. rend. 1861 52 1212 ; Duvillier Abstr. 2880 895 ; 1887 850; Nencki and Sieber Abst r. 1879 70).-One of the simplest methods for the preparation of guanino-derivatives of fatty acids (glyco- cyamines) is warming tbe halogenated fatty acid with a large excess of guanidine (5-10 mols.) and a libtle water. With the simpler com- pounds up to bromoisohexoic acid a temperature of 60' for a few hours is su5cient. With the derivatives of higher fatty acids for example bromopalmitic acid or a-bromophenylacetic acid eight hours at loOD or ten hours at SOo are necessary.Guaninoacetic a-guanino- propionic a-guanino-n-butyric a-guaninoisovaleric a-guaninoisohexoic a-guaninopalmitic and a-guaninophenylacetic acids have been prepared by this method. a-Gunninopropionic acid (alacreatine) has m. p. 226' (corr.) when quickly heated whereas Baumann gives (Abstr. 1873 1024) m. p. lS0' ; the nit?-ate decomposes at 150" and the sulphate at 155-160°. a-Guanino-n-butyric acid (oxybutyrocyamine) crystallises from hot water in slender needles or rectangular prisms and has m. p. 243-245O (corr. decomp.). The nitrate decomposes at 162O and the sulphate at 165-168'. a-Guanino isovaleric acid (ox yvalerocyam in e) forms rectangular plates and has m. p. 842' (corr. decomp.).The nityate decomposes at 172-176' and the sdphute at 1T8-1S0°. a-Guaninoisohexoic acid (a-aminohexocyamine) crystallises in needles and decomposes at 242-243O (corr.). The nitrate decomposes at 177-180° and the szclphate a t 182-1S5O.ORGANIC CHEMISTRY. 89 a-Gzucninopalmitic acid CH,.[CH,Jl3.C(CH,N3).CO,H crystallises from methyl alcohol in octahedra has m. p. 173' (corr. decomp.) and dissolves in alkalis and in concentrated acids. crystallises in slender glistening needles and has m. p. 155-156' (corr. decomp.). The niti*ate (C,7H,,O,N,),,HNO The hydrochloride decomposes at 132-134O (corr.). Phenylguaninoscetic acid (glycol yl phen ylguanidine) CH,N,*CHPh-CO,H appears to be identical with the product obtained by Berger (Abstr. 1880 802) from phenylcyanamide and glgcine.decomposes at 220-226' and the hydrochlovide at 255-258' (corr.}. The nitrate (C,H,,O,N,) HNO,* J. J. S. Acetamide as a Solvent. BORIS N. MENSCHUTKIN (J. Russ. Phys. Chem. Xoc. 1908 40 1415-1434).-The author has determined the solubility curves of various salts in acetamide only salts being chosen for which the solu6ility curves in water have been worked out. The results show that acetamide closely resembles water both in the form of the solubility curves of salts in it and in other proper- ties for example the ionising power. It may indeed be expected that every salt which forms hydrates will give corresponding com- pounds with amides those formed with formamide and acetamide approximating in their properties most closely to those formed with water. No hydrate of potassium iodide is known yet Walker and John- eon (Trans.1905 87,1597) state that this salt forms with acetamide a stable cpmpound KI,GCOMe=NH m. p. 5 4 O . Besides th'e fact that compounds of such a type are usually formed by haloid salts of metals of the second and higher groups the low m. p. given argues against the existence of this compound. The author's investigation of the Byatem acetamide-potassium iodide characterises this system as one in which the components do not combine. The curve which has a form very closely recembling that of the water-potassium iodide curve con- sists of two branches (1) the curve OF lowering of the m. p. of acetamide by the addition of potassium iodide and (2) the curve of solubility of the iodide in acetamide.These two branches meet in a eutectic point about 53O the composition there corresponding approxi- mately with the formula KI,7*1COMe*NEC:,. Crystallisation from methyl alcohol of mixtures of potassium iodide and acetamide of the compositions KI,GCOMe*NH to KI,7COMe-NH2 yielded apparently homogeneous crystals which however the microscope showed were merely mixtures of crystals of potassium iodide and acetamide Hence the conclusion is drawn that Walker and Johnson's co,mpound KI,GCOMe-NH does not exist. The diagram for the system ncetamide-Podinm bromide indicates the existence of the compound NaBr,2COMe-NH2 which decomposes a+ 135-136O (compare Titherley Trans. 1901,79 413). Comparison of this diagram with that for the system water-sodium bromide Rhows that the three branches (1) curve of lowering of m.p. of scetamido OF wat,er by addition of mdiurn bromide (2) curve of solubility of90 ABSTRACTS OF CHEMICAL PMERS. NaBr,2H20 or NaBr,2COMe*NH2 and (3) curve of solubility of pure sodium bromide are practically identical in form in the two cases The diacetamide compound is less stable than the dihydrate a fact which may account for the noo-existence of a compound NaBr,SCOMe*NH corresponding with the pentahydrate. The curve representing the lowering of the m. p. of acetamide by sodium iodide ends in a eutectic point 41.5' corresponding -with NaI,5COMe*NH2 from which starts the curve of solubility ill acet- rtmide of the compound Na1,2COMe*NH2 which decomposes at 125O (compare Tithorley Trans. 1901 79 413). I n this case also no acetamide compound is formed corresponding with the pentahydrate.In the system acetamide-calcium chloride the eutectic point is very low namely 46' corresponding with CaC12,3COMe*NH,. Beyond this point comes the solubility curve of CaC12,6COMe*NH con- tinuing to the m. p. 64"; this compound crystallises from methyl alcohol in hygroscopic plates. At 64" begins the solubility curve of the compound CaC1,,3COMe*NH2 which crystallises in hygroscopic needles decomposing at l86" the solid phase beyond this temperature being probably CaCI,,COMe-NH,. Comparison of this diagram with that for the system water-calcium chloride shows that the solnbility curves for CaCl,,GCONe*NH and CaC12,6H20 are very similar ; with acetamide however no compounds are formed analogous to the a- and P-tetrahydrates and the dihydrate.Like the solubility curve of CaC12,3Me0H (compare Abstr. 1907 i 271) that of CaCl,,3COMe*NH2 also closely resembles that of CltC1,!2K,O. The triacetamide com- pound decomposes the trialcoholate with evolution of methyl alcohol the compounds CaC1,,3MeOH CaC1,,3COMe-NH2 and CaCl,,xH,O being in order of increasing stability. T. H. P. The Action of Chlorine on Garbamide whereby a Dichloro- carbamide is Produced. FHEDBRICK D. CHATTAWAY (Proc. Roy. Soc. 1908 A 81 381-3ss).-Diel~Zoroca;rbamicEe CO(NHCI) prepared by passing a very rapid stream of chlorine into a well- cooled solution of carbamide (%) grams) in water (40 c.c.) separates in thin colourless plst,es. The compound is endothermic and detonates when heated rapidly owing to the formation of nitrogen chloride; when heated cautiously it has m.p. about 83" (decomp.). It is readily hydrolysed by water and when kept in aqueous solution at the ordinary temperature cnrbon dioxide nitrogen nitrogen chloride and ammonium chloride are formed slowly. Acids and alkalis accelerate the hydrolysis and also alter the nature of the end products; thus in presence of dilute acids all the chlorine in the compound is liberated a s iiitrogen chloride but this compound is not formed when - hydrolysis takes place in alkaline solution. The addition of potassium hydroxide c:iuses violent evolution of nitrogen the reaction taking place qumtitatively in accordance with the following equation 3CH20N2C1 + 12KOH = 3K,CO + 2NH + ciKCl+ 2N2 + 6H,O.When carbamide is treated with excess of an alkaline hppobiomita,ORGANIC CHEMISTRY 91 it is probable that a dibromocarbamide is first formed; the manner in which this undergoes hydrolysis is supposed by the author t o furnish an explanation of the variable amount of nitrogen liberated during the decomposition. Dichlorocarbamide is an acidic substance and its aqueous solution reddens and then bleaches litmus; it shows all the reactions of a typical nitrogen chloride. w. 0. w. Dearnotropy and Merotropy. V. Gonstitution of Hydrogen Cyanide. ARTHUR MICHAEL and HAROLD HIBBERT (Annalen 1909 364 64-76).-1n continuation of previous work on the use of tertiary amines for distinguishing between enolic and ketonic deriv- atives (Michael and Smith Abstr. 1908 i 943) the authors have applied this method towards the elucidation of the constitution of hydrogen cyanide.When tertiary amines are brought into contact with anhydrous hydrogen cyanide at O" no salt is formed but only a very slight polymerisation takes place. The rapidity of the latter decreases according to the series triethyl- tripropyl- and triisoamyl-amine that is the capacity possessed by tertiary aminss of polymerising hydrogen cyanide changes in the same relation as their capacity of enolising desmotropic ketones. On the other hand primary and secondary amines unite with hydrogen cyanide forming unstable salts and polymerisation does not take place. This can only be explained by the assumption that hydrogen cyanide exhibits keto-merotropy and that primary and secondary amines can bring about merotropy in the substance whilst tertiary amines can not.The authors' experiments show that the dialkyl- are less dissociable than the trialkyl-ammonium cyanides that is by substituting a hydrogen atom i n NH,F,NC by a third alkyl radicle the affinity between hydrogen and nitrogen is lessened and hence mcondary amines can effect merotropy in hydrogen cyanide with the formation of salts whilst tertiary amines can not. The existence of trialkylammonium cyanide shows that if hydrogen cyanide were in the acidic form (HNC) salt formation with tertiary bases would be possible. The conclusion is drawn therefore that hydrogen cyanide possesses the nitrile constitution HCN. DipropgJ- and diisobuty2-ammonium cganides are white unstable salts; .the latter has m.p. 35". Diisoam$arnmoniitm cyanide is a white crystalline very unstable substance m. p. 68-70". Yiperido?kum cyunide is a white crystalline salt m. p. 47-48O; it is more stable than the other cyanides examined being decomposed only after twenty minutes on keeping i n a desiccator under diminished pressure. isoButyl- and isoamyl-ammonium cyanides remain on evaporation of their solutions in a vacuum partly as oils arid partly crystalline AL1.tJanzmoniuna cyanide is a viscid yellow oil. Aniline does not react with hydrogen cyanide. From the rise of temperature (15') observed on mixing 90% aqueous hydrocyanic acid and triettiylxmine at Oo the authors conclude that salt formation takes place. By treating the trialkylatnmonium chlorides with silver cyanide in methyl-alcoholic solution double salts are obtained.Thus trimethylammonium chloride92 ABSTRACTS OF CHEMICAL PAPERS. gives the salt NMe,HNC,AgNC a white crystalline substanm and triethylammonium chloride yields the salt NEt,HNC,AgNC in white felted needles. On adding hydrogen cyanide to an equimolecular mixture of triethylamine and water and evaporation of the solution in a vacuum an oil was obtained which gave the above double salt with silver cyanide and hence contained triethylammonium cyanide. Tripropylamine behaves similarly 'Dry ammonia combines i t &tautly with dry hydrogen cyanide or its ethereal solution to form am.nonium cyanide. J. C. C. Rewtion between Ferric SaJts and Thiocyanates. ARNALDO BBIONI (Gazxetta 1908 38 ii 638-640). -The author criticises Bongiovanni's views (Abstr.1908 i 770 859) on the interaction of a ferric salt and a thiocyanate. T. IT. P. Simple Preparation of Mercurio Oxycyanide Solution from its Components. ERWIN RUPP and F. LEHMANN (Chem Zentr. 1908 ii 1816; from Apoth. Zed. 1908 23 793-794. Compare Abstr. 1908 i 770).-The reaction indicated by the equation HgC1 + HgCy + 2KOH = HgCy,,HgO + 2KC1+ H,O is brought about by mixing aqueous solutions of molecular proportions of the com- ponents. For the preparation of a 1% solution the following details are given mercuric chloride 5 8 gram ; mercuric cyanide 5.4 grams dissolved in 800 grams of water a1 e add€ ;I slowly to potassium or sodium hydroxide 44.8 grams and water 1000 grams. This solution con- tains 0.25% sodium chloride or 0.32% potassium chloride.After keeping a bolution of mercuric oxycyanide prepued in this manner for three months the mercury mercuric cyanide and also the oxy-corn- ponent were estimated and the results were in good agreement wit4 kl gCy&W= J. V. E. Decomposition of Grtlcium Cyanamide. FELIX LOHLNIS and R. MOLL (Csntrr. Bakt. Par. 1908 ii 22 254-281. Compare Abstr. 1908 ii 230 and Kappen ibid. 414).-It is considered probable that in dissolving calcium cyanamide is converted into the compound Ca(NH*CN) which subbequently decomposes into calcium hydroxide and cyanamide. The latter when heated with lime or when subjected to the action of carbon dioxide yields fitst ammonium cyanate and then carbamide which is converted by bacteria into ammonium carbonate.h direct action of bacteria on cyanamide seems to be impossible. The bacteria flora found i n solutions of the substance consists of varieties which are able to resist the poisonous actiom of cyanamide and cyanates. Dicyanodiamide is not attacked by bacteria and there is no evidence that it exists in soils. N. H. J. M. Chemical Changes of Calcium Cyanamide in Manuring. HUBE~T RAPPEN (C'sntr. Bub. Par. 1908 ii 22,281-298. Cornpate Abstr. 1908 ii 728).-A criticism of Lohnis' results and oonclubions. When calcium cyanamide is digested for some time with distilledORGANIC CHEMISTRY. 93 water at 60° the filtered solution yields crystals of dicyanodiamide. The same change takes place a t the ordinary temperature when solutions are kept for L long time. In the case of concentrated solutions the sparingly soluble compound CN*N( Ca*OH)2,6H,0 and cyanamide are formed the latter changing gradually into dicyano- diamide under the influence of alkali.I n dilute solutions the calcium compound is not formed ; calcium hydroxide separates in crystals whilst the cyanamide all remains in solution and gradually polymerises. N. H. J. M. [Organo-mercury Compounds.] WALTER SCHRAUTE and WALTER SCHOELLER (Ber. 1908 41 4479-4480. Compare Abstr. 1908 i 617).-A reply to Biilmann (this vol. i 17). Action of Nitric Acid on Saturated Hydrocarbons. 11. S. S. NAMETKIN (J. Rust?. Phys. Chem. Soc. 1908 40 1570-1579. Compare Abstr. 1908 i 329).-Experiments on the action of nitric acid (D 1.2) on cycEohexnne show that the yield of nitro-products diminishes and that of acid oxidation products increases as the pro- portion of nitric acid used increases. Nitrocyclohexane C,H,,*N02 is a colourless liquid with a character- istic smell b.p. 109*5O/40 mm. 202'/742 mm. (decornp.) D! 1.0853 Dig 1.0680 nl,g1*4612. This nitro-derivative is not an intermediate product in the oxidation of cyclohexane t o ndipic acid as the latter is formed more readily from cyclohexane than from nitrocyclohexane. Such intermediate product is almost certainly unstable isonitrocycZohexane wbich immediately it is formed is transformed partly into the stable nitrocyclohexane and partly into aldehyde (or ketone according to the nature of the hydro- carbon) which undergoes further oxidation to the corresponding carboxylic acid. The process of formation of tertiary nitro-derivatives is essentially different from that of primary or secondary nitro-compounds the most striking difference lying in the mechanism of the formation of water in the two cases.In the first water is formed from the tertiary hydrogen and the hydroxyl group of the nitric acid R C:H + OHINO = R,C*NO + H20 whilst with primary or secondary hydrocarbons the oxygen atom only is taken from the nitric acid and the two hydrogen atoms from the hydrocarbon R 2 CiH--+-G;NO*OH ._._ 2 _.._____. = R2C:N02H + H20. ARNOLD F. HOLLEMAN (Rec. trau. chim. 1908 27 455-457).-This paper contains details for the preparation of 2-chloro-3-nitrotoluene from 3-nitro-o-boluidine by means of the Sandmeyer reaction. An 84% yield is obtained and the product has m.p. 215O (compare Wynne and Greeves Proc. Bromination of Toluene. 11. ARNOLD F. HOLLEMAN and J. J. POLAK with VAN DER LAAN and EUWES (Rec. trau. chim. 1908 27 435-454. Compare Abstr. 1906 i 154).-The authors continue W. H. G. ........_........ 3 L ...__.._ ~ _.__..__ T. H. P. Preparation of 2-Chloro-3-nitrotoluene. 1995 21 151). w. 0. w. VOL. XCVI. i. h94 ABSTRACTS OF CHEMICAL PAPERS. the studies on the bromination of toluene and in the present com- munication ciiscuss the influence of temperature and dilution and the action of catalysts on the ratio bromotoluenes benzyl bromide. Tables are given showing the percentages of benzyl bromide formed with various proportions of bromine and toluene at 25’ and 50°. The authors claim that their results are more accurate than those obtained by Bruner and Dluska (Bbstr.19OS i 146). On plotting in the form of a curve the values obtained by these authors in their experi- ments on the influence of temperature and comparing these with the data obtained by van der Laan certain discrepancies appear for which at present no explanation can be found. To explain the action of catalysts it has been supposed that these are capable of converting benzyl bromide into a mixture of bromo- toluenes no experimental evidence in support of this view could be obtained however since it was found that when benzyl bromide or chloride is boiled with toluene and ferric bromide the sole product is p-benzyltoluene. A similar experiment in which antimony tribromide was the catalyst resulted in the formation of a small quantity of a liquid containing 50.9% bromine (bromotoluene requires 46.78%).Bromine itself was found to be incapable of behaving as an au t ocatal ys t. Cohen Dawson and Crosland (Trans. 1905 87 1034) have recorded the production of chlorotoluene by the action of nascent chlorine generated by electrolysis on boiling toluene. The hypothesis put forward by Bruner and Dluska (Zoc. cit.) and by Bancroft (Abstr. 1908 ii 788) who suppose that the molecules of bromine attack the side-chain whilst the atoms bring about substitution in the benzene nucleus cannot however be sustained inasmuch as a repetition of Cohen’s experiments using toluorie and hydrogen bromide showed that benzyl bromide and bromotoluene were both formed but that the former underwent reduction by hydrogen produced in the electrolysis. The sugg6stion is made that the true explanation is to be found in the existence of compounds of the type HBrl that these attack the benzene nucleus whilst the molecules of bromine act only on the side-chain.This theory accounts satisfactorily for the influence of dilution for the increase in the amount of benzyl bromide a t higher temperatures and for the increase in the proportion of bromotoluenes brought about by substances such as acetic acid or nitrobenzene which act as solvents for hydrogen bromide. An explanation is also afforded of the specific action of the bromides of iron aluminium. and antimony wkch also promote substitution in the ring. w. 0. w. Properties of Diphenyleneiodonium Hydroxide and of some of its Derivatives.LUIGI MASCARELLI ( A t t i R. Accad. Lincei 1908 [v] 17 ii 580-583; Gaxxattcc 1908 38 ii 619-629. Compare Abstr. 1907 i 1021).-On treating diphenyleneiodonium iodide with moist silver oxide it yields the hydroxide ?6H4>I*OH which is a strong base and could not be isolated owing to the readi- ness with which it absorbs carbon dioxide from the air. I n aqueous (4%ORQANIC CHEMISTRY. 95 solution the hydroxide is reduced by sodium amalgam giving an almost quantitative yield of diphenyl C,,H,I*OH + 2H = C,,H + HI + H,O. This decorcposition indicates the slight stability of the heterocyclic ring containing carbon and iodine which is confirmed by the quantitative change of diphenyleneiodonium iodide into o o- di-iododiphenyl when it is heated for a short time at its melting point.Evidence has been obtained of the formation of a periodide P6HJ 2%- C6H4 DiphenyZeneiodonium bromide YGH4>I*Br separates from water as a white crystalline powder m. p. 245-250’ (decornp.). When heated a t its melting point it is converted into 2-bi*om0-2’-iododiphenyZ (?) m. p. 91*5O which is iinder investigation. T. H. P. Action of N-Amino-compounds on Dehydracetic Acid. CARL BULOW [with HANS FILCHNEB] (Ber. 1908,41 4161-4168)- Dehydracetic acid reacts with p-toluidine in alcoholic solution to form dehydracet ic-p- toluidide C H s < ~ ~ ~ ~ > C * C€€,*CMe N ‘C,H crystallising in colonrless needles m. p. 154’. Boiling with 10% sodium hydroxide resolves it into its components again. It reacts with phenylhydrazine p-toluidine being eliminated and de- hydracetic acid phenylhydrazone formed crystallising in golden- yellow plates m.p. 202O and identical with the compound obtained by the direct interaction of phenylhydrazine and dehy dracetic acid. It gives a characteristic blue coloration with concentrated sulphuric acid and a trace of ferric chloride and is resolved on boiling with 10% sodium hydroxide into its components. condenses with dehydracetic acid in a similar manner to p-toluidine. The condensation product Ethyl- 1 -amino-2 5 - dimethylpyrrole- 3 4 -dicarboxylate has m. p. 160’; it is of acid character and dissolves in &lute alkali whence it is precipitated by carbon dioxide. Dehydracetic acid formylhydraxona C,H,O,:NbNH*CHO crystallises in colourless needles m.p. 1 5 4 O and likewise possesses a faintly acid character. Dehydrucetic acid semicarbazone C,H,O,:N*NH*CO*NH crystallises in colourless needles m. p. 197-198O; it dissolves in weak alkali and is precipitated unchanged in crystalline form by weak acids. E. F. A. Chromophores without Double Linkings. HUGO KAUFFMANN and IMMANUEL FRITZ (Bey. 1908 41 4413-4422).-Ullmann and Loewenthal’s 2-iodo-1 4-dimethoxybenzene (Abstr. 1904 i 72ri) m. p. 2 3 O b. p. 157’/10 mm. is conveniently obtained in 90% yield by treating an alcoholic solution of quinol dimethyl ether with iodine and mercuric oxide. A small quantity of di-iodoqzcinol dimeth?/Z ether C,H,T,(OMe) m. p. 1 no is also obtained. Chloroiodoquinol dimethyl ether C6H2ClI(OMe)2 m. p. 115O in which the position of the chlorine h 296 ABSTRACTS OF CHEMICAL PAPERS.has not been ascertained is prepared by treating a chloroform solution of 2-iodo-1 4-dimethoxybenzene at 0' with chlorine digesting the red product with 10% sodium hydroxide and treating the resulting iodoso-compound with an acidified solution of potassium iodide ; it separates from alcohol in white needles C,H,Cl(OMe),* IC12 m. p. 45-50' (decomp.) is a brick-red crystalline powder? prepared by the action of chlorine on a chloroform solution of chloroiodoquinol dimethyl ether at 0'; by treatment with 10% sodium hydroxide it yields a white amorphous iodoso-compound C',H,Cl(OI\IIe),*IO m. p. 106' (decomp.). Dichloroiodoquinol dimethyl ether C6HC1,1(OMe) m. p. 81' is obtained when the preceding iododichloride is kept in a closed vessel for some days and separates from alcohol in white woolly crystals ; the iododichloride C,HCl,(OMe),*ICl m.p. 130° is a citron-yellow crystalline powder and the iodoso-compound m. p. 70' (decomp.) is a white amorphous substance. Trichloroiodoquinol dimethyl ether C,Cl,I(OMe) m. p. 135O crystallises in colourless needles and is prepared by leading chlorine into a chloroform solution of 2-iodo-1 4-dimethoxybenzene which is only slightly cooled so that the final temperature is about 30'. The iododichloride C,Cl,(OMe),*ICl m. p. 125-1 30' (decomp.) is a pale yellow crystalline powder and the iodoso-compound C,Cl,(OMe),*IO m. p. 120-125' prepared in the dark is white and amorphous. 1 4-Dimelhoxy~~heiz?/l di-iododichloride C,H,(ORle),(ICl,) m.p. 50-60° (decomp.) prepared by leading chlorine into a chloroform solution of di-iodoquinol dimethyl ether a t Oo is an orange crystalline powder which by keepinb for a few days in a closed vessel is converted into colourless dichlorodi-iodoquino2 dimethyl ether. The di-iocloso-com- Nitroquinol Dimethyl Ether. HUGO KAUFFMANN (Ber. 1908 41 4396-4412).-See this vol. ii 107. Fluorescence of Potassium Quinoldisulphonate. HUGO KAUFFMANN (Bey. 1908 41 4422-4423).-1~ reply to Hantzsch (Abstr. 1908 ii 446) the author states that the fluorescence of por;aasium~quinoldisulphonate so far from being slight is visible to the Derivatives of Ethyl Catechol. HERMANN PAULY and KARL NEUKAM (Ber. 1908 41 4151-4161. Compare Abstr. 1907 i 91 6).-The dibromide of 3 4-dihydroxystyrene (vinylcatechol) methyl- ene ether forms colourless matted needles m.p. 82' (compare Barger and Jowett Trans. 1905 87 967). When heated with bromine in carbon disulphide a tribromide m. p. 62" crystallising in colourless The iododichloride C,HCl,(OMe),~IO pound C,H,(OMe),( 10)2 is a yellow powder. c. s. naked eye in an ordinary test-tube. c'. s. needles is formed. The cyclic carbonate CO<O>C,H,*CH:CH 0 (Abstr. 1907 i 916) exists in two forms needles m. p. 195' (corr.) and needles m. p. 200' (corr.). CO<g>C,H,* CH Br*CH,Br The dibronzide,ORGANIC CHEMISTRY. 97 obtained by the action of bromine in carbon disulphide solution at - lo' crystallises in short obliquely-cut prisms m. p. 69-70'. Free vinylcatechol is best prepared by hydrolysis of the carbonate with aqueous pyridine. It is obtained as a deep yellow viscid oil which easily polymerises ; it dissolves in fuming hydrochloric acid with a rose-red coloration which disappears on dilution.The view formerly expressed that vinylcatechol exists in a quinonoid form is now held with all reserve. 3 ; 4-Dihydroxyphen yl-,B-chloro-a-ethanol methylene ether CH~<:>C,H,*CH(OH)*CH,CI prepared by the addition of hypochlorous acid to the styrene was ob- tained as a yellow oil which on purification by distillation in a vacuum formed a colourless odourless oil b. p. 157' (corr.)/9 mm. 163-164'1 13 mm. When kept the chlorine content increases and P-chloro- methylenedioxystyvene CH2<g>C6H3*CH:CHCl is formed with the elimination of water. This is also formed on slow distillation of the chlorohydrin; it is a transparent colourless oil with an anise or piperonaldehyde-like odour b.p. 1 38'/1 1 mm. 141-142'/13 mm. It forms an oily additive dibrornide. At the same time as the above chlorohydrin a substance containing an additional atom of chlorine is formed by the action of hypochlorous acid ; this crystallises in well- formed glistening colourless needles m. p. 197.5' (corr.). It shows no catechol reaction when heated with sodium carbonate. The corresponding chloroh3drin of the cyclic carbonate CO<E>C,H,* CK(0H) * CH2Cl prepared in a similar manner forms colourless crystals M. p. 95-96'. The bromohydrin prepared by the decomposition of the dibromide of vinylcatechol carbonate separates in small colourless prisms which melt at 100' to a red liquid and decompose to a greyish-violet dye m.slowly heated 96' or quickly heated 107'. These carbonate derivatives give yellowish-brown colorations with ferric chloride. The chlorohydrin of the catechol is obtained from the corresponding carbonate by heating with magnesium carbonate in acetone solution. The phenol is transferred t o warm benzene and quickly brought to crystallieation using special precautions to prevent the formation of dyes. It crystallises in thin colourless pointed plates m. p. lOa0 decomposing instantly into a greyish-violet dye. P-Methylamino-3 4-dihydroxyphenyl-a-ethanol methylene ether CH2<g>C6H,*CH( OHj*CH,*NHl\le prepared by double decomposition of the chlorohydrin with methyl- amine is a viscid colourless oil with a faint violet fluorescence b. p.170"/12-13 mm. It turns litmus blue and is perhaps identical with the methyIalkamine described by Barger and Jowett (Zoc. cit.). The picrate forms small yellow sandy crystals m. p 1 8 8 O (corr.) (Barger and Jowett give 178'). It unites with phenylcarbimide in alcoholic solution forming in the first place an easily soluble oil and sub- sequently a crystalline compound m. p. 155' probably a hydrothiazole.98 ABSTRACTS OF CHEMICAL PAPERS. The carbonate of the chlorohydrin forms an amorphous base with methylamine very similar to epinephrine (Abel Abstr. 1900 i 72). E. F. A. Resorcinolbenzein. MANS VON LIEBIG (J. p. Chern. 1908 [ii] '78 534-543. Compare Abstr. 1908 i 445; Kehrmann and Dengler Abstr.1908 i 1002 ; Doebner Abstr. 1883 861 ; Cohn Abstr. 1894 i 120).-Resorcinolbenzein is formed by fusing resorcinol with either benzil or benzoic anhydride. It is possible that in the latter case a reaction takes place similar to that which occurs in the synthesis of fluoresrein Ph*C:(C H *OH),:O P h C (C,H,* OH),:O H C6H:,(0H)212 -+ >06 >O + H E c,H,w),I Ph*C:O Ph*C:O Resorcinolbenzein forms a barium salt C76H42012Ba4 glistening bluish-red leaflets and a hydrochloride C7,H,,,O1,,4HC1 brownish- yellow leaflets. It is converted by an alcoholic solution of ammonia into anhydro~~esorcinolbenxein C7,H,,01,,EtOH (?) which crystallises in brownish-red leaflets with a blue shimmer. The latter compound and resorcinolbenzein when boiled with glacial acetic acid yield a substance C76H,,01,,Ac*OH obtained as brownish-red leaflets with a blue reflex.An alcoholic solution of potassium hydroxide converts resvrcinolbenzein into a substance CRSHSOOg almost colourless needles m. p. 147' and 2 4 2' 4'-tetrahydroxytritan-2 2'-ether Cl9Hl4O3 which crystallises with benzene of crystallisation in colourless leaflets or aggregates of prisms m. p. 170-171'. The latter substance is identical with Doebner's tetrahydroxytritan which however because it was crystallised from dilute spirit contained an additional H20. It yields an acetyl derivative C,gH120(OAc)2 m. p. 184" and a dimethyl derivative C,,H,,O(OMe) thin colourless leaflets m. p. 126". Resorcinolbenzein reacts with methyl sulphate forming a methyl derivative Cl~HiiO(OMe) colourless crystals m.p. 105O and with acetic anhydride yielding the ucetyl derivative CIgH,,O(OAc),,Et* OH colourless pointed prisms m. p. 147' ; when the acetylation is carried out in the presence of zinc dust the acatyl derivative C3,H2603(0Ac) is formed ; it crystallises in colourless glistening needles m. p. 1'79". W. H. G. The Structure of Guaiol. A. GANDURIN (Ber. 1908 41 4359-4363).-Guaiol (Wallach and Tuttle Abstr. 1894 i 538. Compare this vol. i 112) extracted from guaiacum-mood oil by means of ether crystallises from 70% alcohol in large colourless prisms [a]E - 26.64' ; it is triboluminescent. Dihydroguaiene prepared by the action of zinc dust on guaiol is a colourless almost odourless oil b. p. 122"/11 mm. [.IF5 - 2S.6S0 D 0.9089 D2p5 0.8914. ngz 1.49317.Guaiol methyl ether is a colourless almost odourless oil b. p. 141-143'/9 mm. [a] - 31*81' D 0.9513 Di5 0.9332 nZ5 1.48963. Guaiene prepared from guaiol through the xanthate (compare Wallach and Tuttle Zoc. cit.). is a colourless almost odourless oil b. p. 124'/11 mm.,ORGANIC CHEMISTRY. 99 [ C C ~ - 66.11° Di 0.9133 D',5 0.8954 ng 1.49468. The author draws the conclusion particularly from the mol. refraction of the above substances that guaicl is a tertiary dicyclic alcohol containing an ethylene linking. J. C. C. Triphenylcarbinols. Huao EAUFFMANN and IMMANUEL FRITZ (Ber. 1908 41 4423-4427. Compare Abstr. 1905 i 280 773).- 2-Iodo-1 4-dimethoxybenzene readily reacts with magnesium in dry ether and the reaction of the oily product with ethereal 2 5-dimeth- oxybenzophenone leads to the formation of 2 5 2' 5'-tetramethoxy- triphenylcavbinol OH*CPh[C,H,(OMe),] m.p. 1 ZOO which develops a dark green colour with concentrated sulphuric acid and is reduced by warm alcoholi. hydrogen chloride to 2 5 2' 5'-tetramethoxytripienyl- methane m. p. 74". The ethereal solution of the preceding organo- magnesium compound reacts with carbon dioxide yielding in the usual may a small amount of dimethylgentisic acid and as the main product Kauffmann and Grombach's 2 5 2' 5'-tetrsmethoxybenzophenone. The interaction of the latter and the organo-magnesium compound leads to the formation of 2 5 2' 5' 2'' 5"-hexamethoxytripJ~enyL carbiinol OH*C[C,LX,(OMe)2]3 m. p. 136" which gives an indigo-blue colorahion with Concentrated sulphuric acid a green coloration with concentrated hydrochloric acid and yields by reduction with alcoholic hydrogen chloride or with zinc and glacial acetic acid 2 5 2' 5' 2" 5"- hexamethoxytriphenylmethane m.p. 15 lo. c. s. Electrolytic Reduction of Benzoic and Salicylic Acids to the Corresponding Aldehydes. CARL METTLER (Bey. 1908 41 4148 -4150).-6enzoic acid i n presence of mineral acids is electro- lytically reduced to the corresponding alcohol (Abstr. 1905 i 436; 1906 i 851 ; 1907 i 315) and no trace of aldehyde is formed during the reaction. I n neutral or alkaline solution hydrogenated carboxy.lic acids are formed. On reduction however in presence of boric acid considerable quantities of aldehyde are formed (compare Weil Abstr. 1908 i 800). It is convenient to use an aqueous boric acid solution and sodium benzoate with a mercury cathode which gives rise to sodium amalgam on passing the current and this reduces the benzoic acid to aldehyde. It is necessary to ensure the continued presence of boric acid and to remove the aldehyde formed from further reducing action.To t b i s end benzene is added and the liquid stirred rapidly to keep it in a constant state of emulsion. Benzoic and salicylic acids and some of their derivatives can be reduced to aldehyde in this manner; the reaction t,akes place only with difficqlty in the case of the halogen benzoic acids and of hydroxynaphthoic acid. E. I?. A. Preparation of Benzoyl Cyanide. WILEELM WISLICENUS and ROBERT SCHAFER (Ber. 1908 41 4 169 -4l'il).-It has previously been shown (Abstr.1908 i 973; this vol. i 29) that the group :C(NO,)Br has a pronounced tendency t o eliminate bromine and nitric oxide and form the keto-group. Phenylacetonitrile is readily converted by meaas of ethyl nitrate and sodium ethoxide into the sodium100 ABSTRACTS OF CHEMICAL PAPERB. derivative of phenylisonitro-acetonitrile (Abstr. 1902 i 541) which Fliirscheim (Abstr. 1903 i 79) has converted into bromocyano- phenylnitromethane. Chlorine acts on the acetonitrile even more readily than bromine forming phenylchZoronitrocyanometham C,H,*CCl( NO,).CN a light yellow oil. This rapidly decomposes when warmed and affords almost the theoretical quantity of benzoyl cyanide crystallising in large plates m. p. 32-34'. Iodine is without action on phenyliso- nitro-ace toni trile.E. P. A. Z-Gampholic Acid. MARCEL GUERBET (Compt. rend. 1909 148 98-10t).-Z-Campholic acid can be prepared by the method described previously for the dextro-acid (Abstr. 190S i 661). When Lborneol identified with Z-camphol by Haller's method (Abstr. 1889 1206) is heated in sealed tubes with recently-fused potassium hydroxide it is oxidised thus C,H,<XE?OH + KOH = C,H1,<CH3 + H2. The resulting l-campholic acid forms colourless crystals m. p. 106-1 07' [a] - 49.1' (molecular solution in 95% alcohol). Its chemical properties are similar t o those of the d-acid (compare Guerbet Abstr. 1896 i 56). The ammonium salt readily dissociates evaporation of its aqueous solution leaving the acid. It cannot be esterified by the direct action of alcohol8 with or without the presence of hydrogen chloride. l-Campholic anhydride (C,,H,,O),O prepared by dehydrating the acid with acetic anhydride crystallihes from acetone in colourless square tablets m. p.57-58' which are not attacked by cold alcohol but give ethyl campholate on boiling with the latter. It is gradually hydrolysed by boiling aqueous potash. The chloride C,,H,,OCl obtained by treating the acid with a slight excess of phosphorus penta- chloride is a colourless liquid b. p. 222' (the same as the d-isomeride) which when heated with a trace of phosphoric oxide deconiposes into hydrogen chloride carbon monoxide and i-campholene C,H,,. Ethyl 1-campAoZate C,,H,,O,Et prepared by the action of alcohol on either the anhydride or the chloride is a colourless oily liquid b.p. 228'/765 mm. (corr.) having a strong odour of pears. It is not saponified by alkalis under ordinary conditions but is readily decomposed on heating with hydriodic acid. The sodium salt CloH170,Na,SH,0 crystallises in efflorescent nacreous lamellae whilst the copper salt (CloH,~02),Cu,0Et crystal- ises from ether in large green prisms containing ether of crystal- lisation. l-Cumpholamide obtained by the action of ammonia on an ethereal solution of the chloride forms eolourless needles m. p. 77-78" which are ditficultly hydrolysed by alkalis but readily by acids. Syntheses in the Camphor Group. I. isoLaurolene and isoLauronolic Acid (@-Campholytic Acid). GUSTAVE BLANC (Bull. SOC. chim. 1909 [iv] 5 24-3l).-A r6sum6 in greater detail of results already published (Abstr.1906 i 523) dealing with the syntheses of these two substances from a=-dimethyladiplc acid as a starting point. C0,K E. H.ORUANIC CHEMISTRY. 101 The product of the condensation of isolaurolene- with acetyl chloride in presence of aluminium chloride (Abstr. 1899 i 630 ; 1906 i 524) contains a substance which is probably tetrahydro-p- xylyl methyl ketone b. p. 210'. This is liquid and yields an oxim m. p. 106' crystallising in small prisms and sparingly soluble in light petroleum. The principal product of the condensation is the ketone I >C,H*COMe (Zoc. cit.) which yields a n o x h e m. p. 65" readily soluble in light petroleum and with care can be oxidised directly by sodium hypobromite to isolauronolic acid or the ketone may be reduced by sodium in alcohol to the secondary alcohol CMe2*CMe CH,-CH yMe,*CH Me CH,-CH >CH*CHMe*OH (loc.cit.) which on oxidation with chrGmic acid is converted into 3-acetyl-1 1 2-trimethylcyc3opentane b. p. 195O a mobile liquid with a faint odour; its semicarbazone m. p. 213' is sparingly soluble in alcolbl and the oxime m. p. 47O b. p. 137'/20 mm. forms large scales and is readily soluble in most organic solvents. This ketone is oxidised by nitric acid or better by sodium hypobromite solution to dihydroisolauronolic acid and this on bromination and treatment with potassium hydroxide in alcohol yields isolauronolic acid as described h e a d y (Abitr. 1906 i 524). T. A. H. Xylenolglycollic [Dimethylphenoxyacetic] Acids and their Derivatives. GIOVANNI JANDOLO (Rend.Accad. Sci. Pis. Mut. Napoli 1908 [iii] 14 149-155).-These acids may be obtained in good yield by melting the xylenols with chloroacetic acid and adding a quantity of sodium hydroxide solution (1.3) three times as great as that of the xylenol used. 2 ; 4-0imethyl~henoxyacetic acid (m-xylenolglycollic acid) C,H,Me,*O*CH,*CO,H crystallises from all the ordinary solvents in flat white needles m. p. 141'. I t s silver C,,H,,O,Ag and barium (C,,Hl,0,),Ba,2H,0 salts were prepared. The corresponding anilide C,H,Me2*O* CH,*CO*N HPh crystallises from alcohol in a silky mass of slender needles m. p. 104'. The anhydride ( C,,H,102),0 crystallises from alcohol in yellow needles m. p. 94-95'. a-2 4-Dimethy~phenox~ciizrzamic acid (m-xylenolcinnamic acid) C6H ,Me,*O C( CO,B) CHPh crys tallises from alcohol in transparent white prisms m.p. 1'71'. The barium and silver salts were prepared. 2 ; 5-Dirmethylphe~tox~acetic ucid (p-xylenolglycollic acid) C,H,Me,*O*CH:,*CO,H crystallises from water in transparent white needles m. p. 119'. The silver and barium ( + 2H,O) salts were prepared. The anilide C,H,Me,*O*CH,*CO*NHPh crystallises from alcohol in groups of white silky needles m. p. 90'. 3 ; 4-DimethyZphenoxyacetic acid (o-xylenolglycollic acid) C1,H,,O crysfiallises in sbining white scales m. p. 162". The silwer and102 ABSTRACTS OF CHEMICAL PAPERS. bavium ( 2H,O) salts were prepared. colourless rectangular monoclinic lamins m. p. 80'. The anilide CI6Hl1O2N forms a-3 4-Dimetl~ylphenoxycinna~ic acid (0-xylenolcinnarnic acid) -~ C17H1603 forms white prisms m.p. 180'. Attempts t^o prepare a-3 5-dimethyl phenoxycinnamic acid (p-xylenol- cinnamic acid) did not result in a pure product owing to the difficulty of crystallising it. T. H. P. Benzoylacrylic Acid. J. BOUGAULT (Ann. Chim. Phys. 1908 [viii] 15 491-515).-A detailed account of the preparation and properties of benzoylacrylic acid and its derivatives part of which has been already published (Abstr. 1908 i 179 269 422 537 791). Benzoylacrylic acid more conveniently prepared from /3- bromo- benzoylpropionic acid by the action of sodium acetate and acetic acid (Wolff Abstr. 1891 1185) combines with bromine to form the dibromo-derivative m. p. 148O (Pechmann Abstr. 1883 1074 gives 135'). When treated with ammonia benzoylacrylic acid yields the ammonium salt m.p. 197' of an amino-acid which probably has the constitution COPh*CH,*CH(NH,)*CO,H whilst with aniline it combines directly t o form an acid xn. p. 138' probably COPh*CH,-CH( NHPh)* CO,H which condenses with phenylhydrazine to form the acid C,,H,,O,N m. p. 151'. The compound obtained by Gabriel and Colman (Abstr. 1899 i 390) by the inheraction of hydrazine an'd benzoylacrylic acid is probably not the hydrdzoiie as described but 3-phenyZpyraxoline-5-carb- which yields the crystalline bromo- oxylic acid CO,H*CH< m p. 251'. The oxime and semi- derivative CO,H* C H< curbnzone of benzoylacrylic acid have m. p. 168' and 190' respectively. p-Methoxy- and methylenedioxy-benzoylacrylic acids (Abstr. 1908 i 269) can also be prepared by the action of sodium acetate and acetic acid on the broruo-derivative of p-methoxybenzoylpropionic acid and methylenedioxy benzoj lpropionic acid respectively.1'-Xethoxy- benzoylpropionic acid (anisoyipropionic acid) has m. p. 147' (Poppcnberg Abstr. 1902 i 60 gives 140-141') ; the bronzo- derivative OMe*CGK,*CO*CHBr*CH,*CO,H has m. p. 114' ; methyZeizedioxyberLzoylyro~~onic acid CH,O, C H;CO*CH,* CH,* CO,H m. p. 1 3 6 O yields a ~TOWO-derivative CH20,:C,H3*CO*CHBr*CH2-C0,H m. p. 147'. NH 'q CH,-C Ph' NH-N CHBr-8 Ph' M. A. W. The Colours of Indoneacetic Acids and their Carb- &zones. HANS STOBBE and OTTO HORN (Rer. 1908 41 4381-4384). -The colours of indoneacetic acid (this vol. i 31) 3-methyl-l- indone-2-acetic acid (Abbtr. 1904 i 503) and 3-phenyl-l-indone-2- acetic acid (ibid.1902 i 542) and of their semicarbazones have been examined and their ul tra-violet absorption spectra photographed.ORGANIC CHEMISTRY. 103 The substitution of methyl for hydrogen in either the acid or its semicarbazone has no effect on the colour whereas introduction of phenyl increases the depth of the colour the absorption limit of the phenylated acid being 34 wave-lengths nearer the red end of the spectrum. The relationships are much the same in the case of the semicarbazones (compare Abstr. 1906 i 960). All three semicarbazones are paler in colour than the corresponding acids. J. J. S. Mode of Oxidation of Phenyl Derivatives of Fatty Acids in the Animal Organism. 111. Synthesis of some Derivatives of Phenylpropionic Acid. HENRY D.DAKIN (J. BioZ. Chem. 1908 5 303-309. Compare Abstr. 1908 ii 720 964).-In the organism P-hydroxy-P-phenylpropionic acid is oxidised with much greater difficulty than P-phenylpropionic acid and is mostly excreted un- changed. I n order to test the hypothesis that combination with glycine it a necessary preliminary to combustion P-hydroxy-/3- phenylpropionylglycine OH°CHPh*CH,*CO*NH-CO,H was prepared. Cmnamoylglyciue CllH,,O,N obtained by the Schotten-Baumann reaction mas found to be identical with that previously obtained from urine (Zoc. cit.) and yielded successively ap-dibromo-6-phenylpropionyl- glycine C,,H110,NBr2 prisms m. p. 190-191' a-bromo-P-hydroxy-P- phenylpropionylglllcine C1 H,,O,N Br needles m. p. 87-88" and ~-hydroxy-~~henylp~o~ionyZglycine CIlI3,,O4N needles m.p. 146-1 47'. The last substance but one yields with warm concentrated hydro- chloric acid P-chloro-a-bronzo- P- phenylpropionylgZycine C,,H O,NClBr m. p. 203-204'. G. B. isoPhthalacene Group Structure of Phthalacene. 11. GIORGIO ERRERA (Gazzetta 1908 38 ii 588-598. Compare Abstr. 1908 i 183).-The author has investigated the structure of the acids obtained by the actionrof concentrated sulphuric acid on 3 B-diphenyl- toluene-2 2' 2"-tricarboxylic acid (Zoc. cit.). It is found that this action yields the following three isomeric monobasic acids which were separated by means of their ethyl esters (1) the original phthalacone- carboxylic acid which yields 3 5-diphenyltoluene-2 2' 2"-tricarboxylic acid when fused with potassium hydroxide ; (2) isophthalaconecarb- oxylic acid which when reduced with hydriodic acid and phosphorus yields (a) an isomeride of phthalacene to which the name iso- phthalacene is given and (P) isophthalacenecarboxylic acid ; (3) phthalacoiieisocarboxylic acid.The oxidation of isoph thalacene yields the oxide of isophthalacene and isophthalacone which are analogous with the corresponding oxidation products of phthalacene. crys- tallises from acetic acid in shining golden-yellow needles m. p. 316" and dissolves sparingly in alcohol o r befizene and readily in xylene. The corresponding acid C,,K,,O separates from xylene or acetic acid in minute irregular brownish-yellow cry.tals m. p. 370' (decornp.) and dissolves sparingly in the ordinary solvents. qO--$XCMe*8*FO C H,* C CH-C C A,* CO,E t' Ethyl ~so~htha~aconecarbox~~c6te,104 ABSTRACTS OF CHEMICAL PAPERS.is deposited from xylene in shining golden-yellow crystals m. p. isoPhthalacenecar6oxylic m i d crystal- lises from acetic acid in faintly yellow leaflets or needles m. p. 286-287' and dissolves sparingly in alcohol benzene or xylene. The ethyl rester C2,H2,02 separating from acetic acid as a dirty yellow crystalline powder m. p. 172-173O and the sodium salt C2,H,,02Na,4&H20 were DreDared. $?6H4*Q CH- CMe Q*QO CO-C~-=C*C,H,*CO,Et' Ethyl phthakaco~isocarboxytate 3 29-330'. QH2-Q CMe*s*QH C,H,* C:CH-C*C6H3*C02H' 1 . 1 . isoPhthakacene F!H2-?:CMe'g*?H2 crystallises from benzene in C,H,* C:CH-C* C6Hl faintlv vellow laminae m. D. 222'. . r w isoPhthalacene oxide ' CO'-YCM~*E*FH~ I acid in golden-yellow leaflets m.p. 216-218'. is0 Phthalacone ~o-F:cMe*Eo(?o crystallises from acetic C6H4*C:CH-C*CsH4' crystallises from aniline in C,H,*C:CH-C*C,H shining golden-yellow needles m. p. 355-356'. Hydrophthalic Acids ; Velocity of Addition of Bromine to the Tetrahydrophthalic Anhydrides. VI. GINO ABATI [with MAURO SOLIMENE] (Gaxxettcc 1908 38 ii 577-587. Compare Abstr. 1907 i 419 420).-The author has investigated the rate of addition of bromine (0.01 mol. solution) to each of the five tetrahydrophthalic anhydrides dissolved in chloroform (0.01 mol. solution) at 25'. Bauer (Abstr. 1905 i 729 ; 1907 i 307) finds that the accumula- tion of negative substituent groups at two carbon atoms connected by an ethylene linking diminishes or annuls the capacity of the compound to unite with bromine.This is in accord with the author's observation that the A1-tetrahydrophtbalic anhydride requires thirty-four days to complete the addition of bromine whilst with the cis-Abanhydride less than three days is required ; with the other anhydrides examined no such relation is observed. There appears to be a close connexion between the time occupied by the anhydride in absorbing bromine and the dissociation constant of the corresponding acid as is seen from the following table T. H. P. Time of Dissociation absorption of bromine. constant of acid. Al-Anhydride ............. 33-34 days 0-0590 A3-Anhvd ride .............. 25-26 0.0581 trans-A4-Anhydride ...... 20-21 0'0118-0 0130 A2-Anhydride ............... 24-15 0.0074 cis- A4-Anh ydrid e ...........2-3 9' 0.0062 The conclusion is drawn from these and other rewlts that the unsaturated carbon atoms constituting the ethylene linking are of such a nature that the influences tending to lower the capacity of the linking to take up a negative element tend to increase the capacity of additiou of a positive element and vice versa. T. H. P.ORGANIC CHEMISTRY. 105 Action of isoPhthalic and Terephthalic Acids on p-Amino- phenols. DOMENICO PUULIESE and GIAMBATTISTA SELVAGUI (Rend. Accad. Xci. Xiis. Mat. Napoli 2908 [iii] 14 141-146).-1n alcoholic solution isophthalic acid (1 mol.) and p-aminophenol or its ether8 (1 mol.) react giving the corresponding acid salt CO2H~C,H,*CO2H,NH2~CBH4*OR. With terephthalic acid however no reaction takes place probably owing to the slight solubility and feeble acid properties of the acid.When however isophthalic or terephthalic acid (1 mol.) and a p-aminophenol ether (1 or 2 mols.) are heated together in the absence of a solvent they react giving only the corresponding diamide I n some instances however further changes went on to such an extent even when the compounds were heated together in a stream of carbon dioxide that the diamide could not be separated in quantity sufficient for analysis. pAnisidine hydrogen isophthulute CO,H* C,H4*CO2*NH,*C,H4*O~e separates in shining white fragments and begins to turn brown without melting at above ZOO'. p-Phenetidine hydrogen isophthalate CO,H*C,H,* CO,*NH,*C,H,*OEt is deposited in tufts of white needles and decomposes at slightly above 100'. is0 Phthulodi-p-anisidide C,H,(CO*NH*C,H,*OMe) prepared by the interaction of isophthalic acid (1 mol.) and p-anisidine (2 mols.) crystallises from alcohol in slender neiitral white needles m.p. 268'. (rerepl,t?~aZodi-panisidide C,H,(CO*NH*C,H,*OMe) crystallises from alcohol in neutral nacreous scales m. p. 246-248'. Terephthulo~i- p-pheizetidicle C,H,( CO-NH-C,H,*OEt) prepared from terephthalic acid and p-phenetidine was obtained mixed with terephthalic acid which could not be removed by crystallisation. C,H,(CO,H) + 2NH,*C,H4*OR = C,H,(CO*N H*C,H,*OR) + 2H20. T. H. P. Phenylitaconic Acid. HANS STOBBE (Ber. 1908,41 4350-4357). -The author has made a further study of the reaction between ethyl succinate and benzaldehyde (Stobbe and Kloppel Abstr.1894 i 594) with the object of obtaining an increased yield of phenylitaconic acid (compare Hecht Abstr. 1903 i 700). The anhydride and the two mono-esters have also been investigated. [With OTTO Hoa~.]-Phenylitaconic acid is obtained in a 35% yield by adding slowly a mixture of ethyl succinate and benzaldehyde to finely-divided sodium ethoxide suspended in boiling ether and boil- ing the whole for three hours. The sodium salts of dibenzylidene- succinic phenylitaconic and phenylaticonic acids are separated by crystallisation and extraction with water. Phenylitaconic anhydride is readily obtained by treating the acid with cold acetyl chloride. The @ethyl ester GHPh:C( CH,*CO,H)*CO,Et ( Fittig and Leoni Abstr. 1890 894) crystallises in needles or tablets m.p. 72'. The bai-ium calcium and silver salts are described. [With PHOKION N~ori~.]-The a-ethyl ester (Fittig and Leoni loc. cit.) forms hairy woolly needles m. p. 76-79'. J. 0. C.106 ABSTRACTS OF CHEMICAL PAPERS. Iminodicarboxylio Acids. GEORGE STADNIKOFF (Ber. 1908 41 4364-4373 ; J . Buss. Phys. Chem. Soc. 1908 40 1638-1649).- The author finds that the rate of formation of derivatives of imino- acids decreases with increase of the molecular weight of the hydroxy- nitrile but has no relation to the molecular weight of the amino-ester. Both in the synthesis of the imino-acids previously described (Abstr. 1907 i 393 1015 1016) and in the interaction of hydroxypropio- nitrile and ethyl aminocycloheptanecarboxylate or phenylaminoacetic acid the reaction is at an end in five hours whilst the interaction of msndelonitrile and ethyl aminoacetate or phenylaminoacetate requires ten days for completion; it is however quicker in the sunlight than in t h e dark. C-Phenyliminodiacetic acid CO,H*CHPh*NH*CH,=CO,H prepared by condensing the hydrochloride of glycine ethyl ester with benzalde- hyde and potassium cyanide and hydrolysing the resulting nitrile hydrochlmide (m.p. 82O decomp.) crystallises in starry aggregates of small needles m. p. 220° (decomp.) ; the hpdrochloride forms leaflets m. p. 220' (decomp.); the copper salt (3H20) is described. The diethyl ester is a colourless oil with a faint odour b. p. 195-196'/17 mm.; the nitroso-derivative of the latter is a yellow viscid oil b. p. 220-221'/ 17 mm. The dzmethyl ester is a viscid oil b.p. 188-189'/17 mm. and yields a nitroso-derivative which is a viscid yellow oil b. p. 301-203'/16 mm. sym.-C-Phenyl-C-i,zetfiylinai~odiacetic acid CO H C H P h N H - C H &I e C 0 H prepared by the interaction of ethyl phenylaminoacetate hydrochloride acetaldehyde and potassium cyanide and hydr olysis of the resulting nitrile hydrochloride (m. p. 160-161° decomp.) crystsllises in starry aggregates of slender needles decomp. 210-21 3' ; the hydrochloride has m. p. 210-212' (decomp.) and the diethylester forms a viscid oil b. p. 182-183'/13 mm. By the condensation of ethyl phenylaminoacetate hydrochloiide benzaldehyde and potassium cyanide the hydrochloride of the nitrile ester CO Et*CHPh*NH*CHPh*CN,HCI is formed in slender needles m. p. 156-157O; with water it gives the nitrile ester a crystalline mass m.p. 43-45'. 011 boiling this with 20% hydrochloric acid it is decomposed into phenylaminoacetic acid benzsldehyde and hydrogen cyanide. J. C. C. Synthesis and Reactions of Ethyl Phloroglucinoldicarb- oxylate. Condensation of Esters containing Nitrogen and the Preparation of Sodium Cyanate. HERMANN LEUCHS and ARTHUR GESERICK (Ber. 1908,41 4171-4186).-The supposed ethyl phloroglucinoltricarboxylate synthesised by Baeyer by the sodium condensation of ethyl malonate mas shown by Moore (Trans. 1904 85,165) to be in reality ethyl phloroglucinoldicarboxylate. Willstatter (Bbstr. 1S99 i 576) isolated ethyl acetonetricarboxylate as an intermediate product and observed the formation of ethyl acetate which he attributed to the action of sodium ethoxide on ethyl malonate CH,(CO,Et) + EtOH = CH,*CO,Et + C0,Et2.He was unable to confirm the presence of ethyl carbonate but this theORUANIC CHEMISTRY. 107 authors have succeeded in doing. The Baeyer synthesis is explained thus two molecules of ethyl malonate unite to form ethyl acetone- tricarboxylate which in turn reacts with ethyl acetate. Ethyl malonate in cold ethereal solution is half converted into the sodium salt the ether distilled off and the residue heated at 130-140° any liquid which distils being collected. A yellow semi-solid mass is obtained which after purification yields colourless needles of ethyl phlnroglucinoldicarboxylate m. p. 107-108*5' (corr.). Ethyl carbonate was obtained in quan tity on fractionating the distilled liquid.Ethyl malonate dissolve? in light petroleum reacts with aluminium chloride forming colourless crystals of ethyl aluminomalonate m. p. 97-98' (Tistshenko gives 94-95' Abstr. 1900 i 270). This is decomposed by neither alkalis nor acids. By the action of nitric acid on ethyl phloroglucinoldicarboxylate three products are obtained. A very characteristic bluish-violet colora- tion is at first produced. &~'thyZ nitrop fLlorogZucinoEdicarboxylate N02*C6(OH),(C0,Et)2 crystallises in colourless six-sided plates or massive prisms m. p. 120-121' (corr.). It is conveniently prepared by heating equal weights of carbamide and the pbloroglucinol compound with concentrated nitric acid at 80'. EthyZ 5-nitro-2 4 6-trincetoxy- benzene-1 3-dicccrboxyZate forms colourless prismatic crystals m.p. 94-95'. NitrophZorogZucinoZ C,H,(OH),*NO prepared by heating the ester at 130-135' with potassium hydroxide crystallises in long sealing wax-red prisms which become yellowish-red on heating m. p. 186-1S7° (corr.). Ethyl ccminophlorogZzcci~toldicccrbox~Zate is obtained by reducing the nitro-compound with zinc and hydrogen chloride in the form of the hydrochloride crystallising in colourless needles m. p. 209' (corr. decomp.). The base separates in minute needles m. p. 96-97'. When left during several days in dilute methyl-alcoholic solution crystals separate and the alcohol assumes a deep red colour. The other products of the action of nitric acid on ethyl phloro- glucinoldicarboxylate are citron-yellow and dark red in colour ; they are isomeric and are formed from two molecules of ester united by an imino-group.The red substance C,H,O,N is regarded as a quinone derived from ethyl hexahydroxydiphenylaminetetracarboxylate ; it has m. p. 164-165O. By the action of acetic anbydride a mixture of substances is produced one of which has m. p. 138-152' and crystal- lises in orange-yellow needles. The quinone is reduced on prolonged boiling with alcohol or by means of sulphurous acid to a brown com- pound C,,H,,O,,N which on heating becomes bright red at 130' and dark brown again near the melting point 196-197' (corr.). The acetate crystallises in orange-yellow needles m. p. 175 -1 77'. The lactone from ethyl hexahydroxydiphenylaminetetracarboxylate crystallises in citron-yellow needles m.p. 220' (corr.) ; it forms a faintly yellow acetate m. p. 160-1 7 lo crystallising in needles. The condensation of ethyl sodio-N-carbethoxyglycine yields an ester CloHl,O,N crystallising in long needles m. p. 144- 145' (cow.). This hasan acid reactioninaqueoussolution,and may beethyldiketopiperazine- 1-carboxylate or ethyl aminocyclobutan-2 4-dione-1 3-dicarboxylate.108 ABSTRACTS OF CHEMICAL PAPERS. Attempts to condense sodium urethane showed that reaction takes place between several molecules but the intermolecular elimination of alcohol results in the quan titative formation of sodiiim cyanate. Similarly the action of sodium on urethane in boiling benzene results in the formation of sodium cyanate alone. This is a convenient method for preparing salts of cyanic acid.Sodium Benzaldehydesulphoxylate. A Correction. EMIL FROMM (Ber. 1908 41 4385. Compare Abstr. 1908 i 970).-When sodium benzaldehydesulphoxylate is heated with benzyl chloride and sodium hydroxide solution the product is not the unaltered sulph- oxylate as previously stated but sodium benzylsulphonate. J. BOUVEAULT and GUSTAV BLANC (Compt. rend. 1908 147 1314-1315).-From previous work the conclusion has been drawn (Abstr. 1908 i 134) that the amide formed by the action of sodamide on camphenilone E. F. A. J. J. S. Syntheses of Derivatives of Camphenilone. is isopropylcyc2opentan e- 3-carboxylarnide C H,* F HPrp NII,.C02*CH<(7*,.cH This conclusion is now verified by di;ect sinthesis. isoPropylcyclo- pentan-3-one is obtained by the decomposition of P-isopropyladipic anhydride and is shown t o beidentical with the ketone obtained from camphenilone by preparation of its semicarbazone and its dibenzyl- idene derivative. On reduction with sodium and boiling alcohol it gives a secondary alcohol identical with that obtained from 3-amino- 1-isopropylcyclopentane by the action of nitrous acid.This alcohol when heated a t 100’ with hvdrobromic acid is transformed into CH2* $JHPr@ CH;CH 3-bromo-1 -isopropyZcyclopentane CHBr< a heavy colour- I c 1 less liquid b. p. 82’/16 mm. The latter reacts with G rignard’s reagents giving magnesium derivatives which when saturated with dry carbon dioxide give 3-is0 propylcyclopen tanecar boxylic acid iden tical with that derived from camphenilone. The acid on treatment with phosphorus penta- chloride and then with gaseous ammonia readily furnishes the amide.E. H. A General Method of Preparing Mono- Di- and Tri-alkyl- acetophenones. ALBIN HALLER and ED. BAUER (Compt. rend. 1909 148 70-74).-1t has been shown previously (Abstr. 1908 i 987) that aromatic ketones of the type of benzophenone when heated with sodamide in benzene solution give either additive or decomposition products. The authors attempting to apply this reaction t o mixed fatty-aromatic ketones fiud that only those of the type in which R R’ and R are alkyl groups undergo the decomposition observed with diary1 ketones that is they break down into benzene and trislkylacetamides. 01 the ketones employed aaa-trimethylaceto- phenone COPh-CMe has been described by Nef (Abstr.1900 i 349) ; the others were prepared by alkylating acetophenone in the presence COP h- CRR’R”,ORGANIC CBEMISTTCY 109 of sodamide as in the method adopted with cyclic ketones (Haller Abstr. 1904 i 600 ; 1905 i 214 602) and by Claisen (Abstr 1905 i 256). aa-D imet hyl-a-eth$lacetophenone COPh* CMe,@t obtained by twice methylating propiopheaone or by ethylating phenyl isopropyl ketone is a mobile agreeably suielling liquid b. p. 112.5'/10 mm. ; the o~inrz forms needles m. p. 139' ; aa-dimethyl-a-p~*opylacetophenom COPh*CMe,Pra prepared by propylating phenyl isopropyl ketone is a liquid with z i penetrating odour b. p. 121-123°/10 mm. ; its oz:imet prepared by means of Crismer's reagent crystallises in needles m. p. 13%-133'; a-methyl-aa-d iethylacet ophenone COPh' CMeEt an nromdt ic smell i n g Iiquid b.p. 125-126c/l 1 mm. results on twice ethylating phenyl ethyl ketone ; the oxime has m. p. 12 1'1; aaa-triet~~?/laCeto~~~nan~ COPh-CEt obtained by successively ethylating acetophenone or by ethylating phenyl propyl ketone is an agreeably smelling liquid b. p. 146-1467' 16 mm. ; the ozirne prepared with Crismer's reagent forms needles m. p. 160-1 6 1' ; a-mathyl-cx-etrTryl-a-prop,uEcc~tophenone COPh*CMeEtPra prepared by successively methylating and propylating propiophenone is a liquid b. p. 135-136'/11 mm. which forms an oxime m p. 9 9- 1 0 Oo ; aa-d imet hyl- a- cclt y lace tophenone CO Ph* C Ale C,H a pleasant-smelling liquid b. p. 121"/11 mm. is formed by the actionof allyl iodide on phenyl isopropyl ketone; its oxime could not be obtained.By the action of propyl or allyl iodide on the additive product of sodamide and acetophenone not substituted ketones but condensation products of very high boiling point are formed ; the,higher homologues of acetophenone however undergo the normal reaction with these iodides. E. H Quinh ydrones. WILHELM Sr EGMUND (Xonatsh. 1 90 8 29 1087-1 109. Compare Urban Abstr. 1907 i 539).-By the addition of light petroleum to a benzene solution of p-benzoquinone and catechol a quinhydrone C1,Hl,O6 m. p. 90" (decomp.) DZo 1.359 is obtained which forms red needloa IS stable in boiling benzene and is decomposed by distillation with steam yielding p-benzoquinone and catechol t h e weight of the latter estimated as the lead derivative indicating that the quinnydrone contains 1 mol.C,H402 and 2 mols. Quinol and P-naphthaquinone do not react in water alcohol ether or benzene. In warm benzene p-benzoquinone and 1 2-dihydroxy- ]naphthalene yield in the molecular proportion 1 1 quinol and (/3-naphthaquinone ; in proportion 2 1 P-naphthsquinone and ordinary ,quinhydrone and in the proportion 1 2 quinol and R bluish-black ~substance C2,,H1204 m. p. 120° which seems to be identical with Stenhouse and Grove's dinaphthyldiquinhydrone (Trans. 1878 33 4 1 7). Xhe addition of light petroleum to a benzene solution of p-benzo- t quinone and 3 3-dihydroxynaphthalene produces tufts of blackish-red meedles of the mixed quinhydrone CI6Hl2O4' C,H*(W,. VOL. XCVL i. i110 ABSTRACTS OF CHEMICAL PAPERS. The formulae of the preceding quinhydrones are expressed in accord- Complete Synthesis of Camphor.GUSTAV KoMPPA (Ber. 1908,41 4470-4474).-The synthesis of camphor from a compound containing n smaller number of carbon atoms described by Wallach recently (Abstr. 1908 i 997) is not the first synthesis of camphor to be recorded since the author had previously synthesised racemic camphoric acid (Abstr. 1901 i 668; 1904 i l 4 l ) which he was subsequently able to convert into racemic camphor (Chem. Zeit. 1905 28 1202). It has since been found possible to obtain pure I-cam- phoric acid but not pure d-camphoric acid from the racemic acid by crystallisation of the quinine salts. Attempts are being made to resolve the racemic camphor into its components through the corre- sponding borneols.r-Cawpholide C,0H1602 prepared by the reduction of r-camphoric anhydride in alcoholic solution with sodium or better still by means of nickel and hydrogen crystallises in short thick needles m. p. 211°5-2120 (corr,). It combines with hydrogen bromide forming r-bromocampholic acid CloH170213r rhombic pldtes m. p. 178-179" and when heated with potassium cyanide at 230-240" yields r-cyanocampholic acid which is converted on hydrolysis into r-hornocamphoric acid C,H1&CO,B)2 obtained as feathery crystals m. p. 231-232' (corr.). The calcium salt C11H1,0,Ca,5H20 is a crystalline powder which when distilled with calcium hydroxide yields r-camphor m. p. 178-1 78.5' (corr.). Constituents of Ethereal Oils. Carvenene CI0Hl6 and Pure " Terpinene. FRIEDRICH W. SENMLER (Bey.1908 41 4474-4479).-Emphasis is laid ou the great differences in the physical properties of the (' pure " terpinenes obtained by various methods by the author (Abstr. 1907 i 714) Wallach (Abstr. 1907 i 64 ; 1908 i 813) and Harries and Majima (Abstr. 1908 i 733). I n order to throw some light therefore on the constitution of terpineine the author has prepared pure carvenene by reducing chloro- carvenene and finds that the hydrocarbon so obtained which must have the formula CPrB<C,2.CH2 CH-CH>CMe exhibits an exaltation of 1.5 units (compare Bruhl Abstr. 1908 ii 1002). It is thus definitely shown that two cyclic conjugate ethylene linkings produce a marked exaltation consequently the two terpenes A' 3- and -dihydro- cymene must differ considerably in their physical constants.The identity of carvenene with terpinene has not yet been definitely settled. The chlorocarvenene described by Klages and Kraith (Abstr. 1900 i 42) was impure. The pure substance has b. p. 95-98'/10 mm. -D$ 0.994 n 1.51700 and mol. ref. 51-90; that is it exhibits an exaltation of 1-71 units. It is readily reduced by sodium and alcohol to carvenene a colourless liquid b. p. 61-63'/10 mm. 179m5-180.50/735 mm. D 0.844 and n 1.49100 (compare Harries and Majima loc. cit.). The carvenene 60 prepared reacts slowly with nitrous acid yielding terpinene nitrosite. ance with Thiele'rs theory of partial valencies. c. s. W. H G. W. H. G .ORGANIC CHEMISTRY. 111 Aliphatic Terpenes and their Derivatives. 111. C . J ENKLAAR (Rec. trav. chim. 1908 27 422-434.Compare Ahgtr. 1908 i 664).-ln the present communication the author describes the preparation and properties of the ozonides of ocimene (van Romburgh Abstr. 1901 i 220) allo-ocimene and dihydro-ocimene. These ozonides are of somewhat variable composition the amount of oxygen depending on the time during which the hydrocarbons are exposed to ozone. Ocimeite ozonide C,,H,,O occurs as a pale yellow viscous oil. which explodes when heated or when brought into contact with concentrated sulphuric acid. When treated with water decomposition occurs with formation of acetone acetic acid malonic acid methyl- glyoxal and possibly malonaldehyde. allo-Ocimcne ozonide C,,H,,Og is an explosive oil rapidly decomposed by water with formation of acetone pyruvic acid and probably malonaldebyde. Dihydro-ocirnene ozonide under the same conditions gives acetone acetic acid lawulic acid and probably laevulinaldehyde and malon- aldehyde.An insoluble yellow resin was also obtained .in the decomposition of these ozonides by water ; further treatment with ozone converts this into an ozonide. A table is given showing the specific refractions for the a- and y-hydrogen lines and the D-sodium line and also the molecular refractions for the different rays of these three hydrocarbons. Tbe molecular dispersions between the a- and y-lines diverge considerably from the values calculated from Conrady's data. w. 0. w. Ethereal Oils. HEINRJCH HAENSEL (IImr~.prl)s HalJ-Yeurly Rep& October 1908. Compare Abstr. 1908 i 665).-dngeZica oil when free from terpene has D15 0.9508 aD - 3*16O acid number 0 ester number 87.3 after acetylation 168.1.Oil of Mugwort from t h e fresh plant Artemisia uulgcvm's (yield 0.0263%) is dark brown and smells strongly aromatic; D20 0.9279. The addition of 90% alcohol causes separation of small colourless plates which give a decided aldehyde reaction with ammoniacal silver solution. Birch-bark oil from Betula albcl has D20 0.9003 aD - 12-08' acid number 9.1 ester number 11 '4 after acetylatiou 36.5. The sesquiterpene isolated from this was colourless and nearly odourless ; it has b. p. 255-256'/744 mm. D20 0.8844 aD - 0.5' ; in glacial acetic acid it gives a cherry-red coloration with bromine and combines with 1 mol. hydrogen chloride when in absolute ethereal solution. The resulting dark-coloured hydrochloride D20 0,9753 when boiled with anhydrous sodiiim acetate and acetic acid yields a hydrocarbon b.p. 258-260"/747 mm. D2* 0.8898. Coriandlrr oil (Zoc. cit.) is for the most part d-linalool accompanied by small quantities of esters of this alcohol. Gym- gloesum oil prepared horn the leaves of Cynoglosmrn oflcimle (yield 0*107%) is dark brown with powerful camomile-like odour ; i t partly solidifies when cooled is solnble in all proportions of 90% alcohol and has D20 0.9412. Siberian pira needle oil from Bbies stbirica,has D20 0.9767 aD - 38.30° soluble 1 14.2 in 63% alcohol. Guaiacum-wood oil from BuZmia Sarm&mti,-Only about one- half of the guaiol contained in this oil is found by acetylation; it i 2112 ABSTRACTS OF CHEMICAL PAPERS.appears to be a ertiary alcohol in agreement with its behaviour towards phthalic anhydride. The guaiene obtained by warming the oil for an hour with three times its weight of anhydrous formic acid has b. p. 136-138°/14 mm. D20 0*9182 and is most probably a mixture of sesquiterpenev (compare Cl mdurin this vol. i 98). Oil of Lavender when free from teipene has D*'' 0.8898 an - 6-44' and is soluble 1 :Om95 in 80% alcohol. Oil of Lovrcye from Leoivticum oflcinale becomes slightly chaoged when kept ; it then contains myristic acid small quantities of an aldehyde possessing an odour resembling that of octaldehyde and also larger quantities of a brown resin which decomposes when warmed under reduced pressure Ginger-pass oil from Andropogon Schoenanthus is optically inactive has D20 0.8851 and dissolves in 3 5 parts of 60% alcohol.Italian Peppermint oil crude and purified has respectively D20 0.9035 and 0.9032 aD - 19.80' and - 18*10° ester number 11.2 and 9.1 after acetylation 154.4 and 145.9 content of esterified menthol 3% and 2*54% content of free menthol 45016% and 42.66%. Hungarian oil oJ~ Juniper.-D20 0.8672 aD - 1Z0 saponification value 5.9 after acetylation 20.9 and contains according to the phthalic anhydride test about 5% of a primary alcohol CloH,,O. The Italian oil bas D20 0.8658 aD - 9.82' saponification value 6-1 ; after acetyl- stion D20 0.8732 aD - 7-21' saponification value 21.3; after saponifica- tion and repeated acetylstion a reversal of optical rotation appears to take place. I n the higher boiling fractions phthalic anhydride indicates the presence of small quantities of a primary alcohol C,oH!,O ; the terpeue fractious do not contain nopinene.Olibanol from otl of Frankincense (Zoc. cit.) has b. p. 217'/20 mm. 333-3344751 mm. D20 0.9596 aD-71.50'; when warmed with an equal weight of molten zinc chloride a dark green oil is obtained b. p. 315-31S0/749 mm. D20 0.9400. Olibanol is only slightly oxidised by potassium permanganate in alkaline solution but in glacial acetic acid solution it is completely oxidised by chromic acid. J. V. E. Essential Oils. SCHIMMEL st Co. (Semi-Annual Report ATov. 1908 5-232. Compare Abstr. 1908 i 666).-A rBsum6 of informa- tion regarding essential oils accumulated during the period April t o November 1908. Much of the matter recorded has appeared in other journals and has been abstracted already.Cinnamon-bark oil.-Four samples from Mah6 Islands Seychelles had D15 0.9464-0.9670 [alD - 2'30' to - bolo' n 1*52843-1.53271 and contained from 35 to 35% of cinnamaldehyde and 6 to 15% '' phenols.') All the usual constituents of cinnamon-bark oil were present and in addition a small amount of camphor (compare Bull. Imp. Inst. 1908 6 111). Clove-leaf oil.-Clove leaves from the Seychelles yielded 4*55)! of oil (Zoc. cit.) ; this had D15 1.0489 [a) - 1°35' eugenol 87%. African Copaiba buham (oleo-resin) had D15 0.9919 [.ID - 2315' acid number 61.4 saponification number 68.5 and was not completely soluble in 98% alcohol. It contained 46.5% of volatile oil having DI5 0.9215 [a]D + 23'26' and acid number 2.2.Dalbergia cumingiann oil obtained to the extent of 0.5% from the wood had DZ6 0.891 [a] - 4'31' ester number 5 acetyl ester numberORGANIC CHEMISTRY 113 115. No aldehydes were present (Jaarboek Bept. Landb. Ncd. Id. 1906 45). DiZl herb oil from Spanish herb was greenish-blue had D15 0.9062 91 1.49185 and was dextrorotatory. It contained d-a-phellandrene terpinene carvone dillapiol (? dillisoapiol) and dipentene or limonene (P). Lemon &.-The chief constants of oils from different distriets in Sicily are recorded; they had D15 0*8569-0.8610 [ulg +56”50‘ to + 62’40’ left from 2.2 to 3.6% residue on evaporation and contained 4.3 to 7.1% citral. All these oils contained traces of pinene which is a natural constituent of lemon oil. Eucalyptus Rudderi leaves and twigs furnished 00309% of reddish-brown oil having D15 0.942 [a] - 8*5O and 9% 1.4898.The oil contained cineol and aromadendral but no pinene or phellandrene (Baker and Smith Proc. Linn. Xoc. N.S.W. 1906 31 ‘7 14). E Z C T O ~ U ~ Wormseed oil contains a-pinene terpinene terpineol and terpinenol and a sesquiterpene (b. p. 250’ approx.) (compare Schindel-Meioer Apoth. Zed. 1907 22 876). B’oeniculurn oficinale stalks and leaves grown in Java yielded an oil having DZG 0.950 [a]” +4’50’ b. p. 227-235” m. p. 12.8’. A second sample of oil had D15 0.9837 [a]D +b034‘ m. p. 16.2’. Both oils probably contain much aaethole (Janrboek Dept. Landb. Ned. Ind. 1906 45). Hyptis auaveolens oil from Java had [a] -1O56’ and saponification number 17. The yield was 1% and no aldehydes were present (Zoc.cit. p. 46). Andropogon cilrcctus oil is contained in largest quantity in the leave% and diminishes as the leaves age becoming at the same time richer in citral. The leaf sheaths contain a little oil and the thick roots 0.35 to 0.5%. A sample of “Cochin China lemon grass” oil produced in Barbados had D15 0.900 [u] - lo aldehydes 85.5 (neutral sulphite method). The ‘‘ acid sulphite ” and ‘‘ neutral sulphite ” processes for estimation of citral in lemon grass oil give results differing by from 2 to 5% so that the process of estimation should always be stated. Methylheptenol has been detected in Zinrtloe oil. Monarda dayma oil from the half-faded petals was pale yellow and had D15 0.8665 [ u ] ~ - 7’30’ ng 1.46892 and acid numbor 2.4 the yield was 0.32%.The dry leaves and stems furnisbed 0.096% of a lemon-yellow more soluble oil having D15 0.8855 [.ID -32‘38‘ n2,0 1.46898 and acid number 5.5. NutmegJEowers grown in Java yielded ’7.6% of oil having DZb 0.942 [a]% + 7’ and b. p. 155-285’. Fresh nutmegs furnished 3.8% of oil having D% 0.940 [u] + 10°20’ and b. p. 155-285’ (de Jong ‘‘ Teysmunnicl ’’ 1907 8). Condensed water from the distillatian of orris root oil contained acetaldehyde methyl alcohol diacetyl and furfuraldehyde. Pastinnca oil was found to coiitain heptoic and hexoic acids ( A p t h . Zeit. 1907 22 144). The physical constants of a number of Singapore and Java patchouli oils are recorded. ltaliun peppermint oiE distilled from plants grown trom Mitcham seed had 0.9090 [a]D - 21’12’ n 1-46248 and contained ‘‘ total ” menthol 50*5% and menthone 1702%.Java “peppermint ” oil had Dee 0-974 [a]? 12’28’ and ‘‘ total menthol ” 44.9% (Jaurboek Dept. h n d b . Ned. Ind. 1906 45) but doubt is expressed as to the validity of the above composition. Both oils had the odour of lavender.114 ABSTRACTS OF CHEMICAL PAPERS. Popbr bud oil.-Two samples had D15 0.8957 to 0.8991 5O16' to +5O45' acid number 2.8-6.4 and ester number 8.2-8.9. Acetylation experiments showed that the oil contained but little '* alcohols." East African sandalwood oil from Osyris ti3nu~oli.a 1- The yield from the wood was 4.86%. The oil had D15 0.9477 [aID- 42'50' ng 1.52191 ester number 11.1 acetyl ester number 72.8. The odour recalled those of vetiver and gurjun balsam oils.Thuja pZicatct.-The leaves and twigs yielded 0% to 1.4% of bright yellow oil which possessed a camphoraceous odour and had D25 0.9305 [a] - 6*9O acid number 0418 saponification number 5-7 and acetyl ester number 6-2. It contained pinene thujone fencbone and esters of borneol. Ylang-ybung oil from Madagascar had Dl5 0.9577 [a],,- 49'55' nz 1.51254 acid number 1.8 ester number 113.2 acetyl ester number 160.2. Samples from Mahd Island Seychelles had D15 0.924-0.958 and [aID - 18O46' to 45'27' (compare Bull. Imp. Inst. 1908 6 110). Arternisia arborescens yielded 0.62% of a dark blue oil possessing an odour like that of French wormwood oil and having D*5 0.9458 and acid number 9.8. " Mumuta " grass tubers (Andropogon sp.) from Samoa gave 1.05% of an oil with an odour like that of vetiver oil and having 1)15 0.9845 [a]D + 41°50' ng 1.5 1505 acid number 0-9 ester number 13.3 and acetyl ester number 65.2.From I' Nuanua " leaves (Nelitris sp.) from Samoa 0.63% of oil was obtained. This had an odour like that of ambergris and had DI6 0.9025 [aID+9O30' rnE 1.48490 acid number 2.2 and ester number 7.4 "Usi" leaves (Evodiu hortensis) from Samoa yielded 0.09% of a brown oil with a quinone-like odour and had D15 0.9450 [aID - loo and lzg 1.49685. '' Maali " resin from Samoa resembled elemi and gave 16.08% of a bright green solid oil with a faintly balsamic odour. It had m. p. 65-80° [.ID + 7'15' saponification number 3.3 and acetyl ester number 46.6. It contained m d y t ulcohot C15H260 m. p. 105O [a] + 1 8 * 3 3 O b. p. 260' (approx.) which crystallised from alcohol in silky needles often several inches in length and formed with resorcinol A complex condensation product m.p. 62O and with chromic anhydride a red additive product (C,,H,,O),,CrO,,. m. p. 1 1 1 O . On treatment with acetic anhydride or better formic acid maalyl alcohol is converted into a sesquite?*pone Cl,H2+ D15 0.9190 l a ] D + 12lo20' nD 1.52252 b. p. 270*5-271"/754 mm. which gives an indigo-blue coloration with sulphuric acid in acetic acid. No derivatives of the sesquiterpene could be prepared. The residue of the oil appears to consist of a solution of maalyl alcohol in a laevo- rotatory sesquiterpene. hlern%a indim(?) of Java yielded 0.28% of a bright brown oil having DZ6 0.949 [a] + 57'2' saponification number 99 acetyl ester number 228 (corresponding with 75.6% of thujyl alcohol).N o thujone could be detected (Jaarboek Bept. Landb. Ned. Id. 1906 44). Lantana odoratn from Jamaica gave 0.16% of lemon-yellow oil having an odour of hyssop and ambergris and having D15 0.9149 [aID - 1"36' w2,a 1,49630 ester number 4.7 acetyl ester number 51.0. Tagetes patula flowers from Mexico yielded 0.1% of a golden-yellow oil having D15 0-8856 [a]D - lio35' ng 1.49714 acid numDer 2.0 ester number 18.7 aoetyl Bster 4qmber 7493.ORGANIC CHEMISTRY. 11 5 The report concludes with a critical r6sumB of descriptions of essential oils in various pharmacopeias notes on recent chemical biological and physical research work on terpenes and their deriv- atives and a memoir on the history botany preparation and composition of Japanese peppermint oil by N.Inouye. T. A. H. Oxidation Products of Artemisin. ENRICO RIMINI (Atti R. Accad. Lincei 1908 [v] 17 ii 590-597).-The arteminic acid decribed by Horst (Abstr. 1902 i 387) as an oxidation product of artemisin is in reality a mixture of santonin and arternisin its formation being due to the use of impure artemisin. When artemisin is oxidised by alkaline permanganate (about 5 atoms of oxygen) in presence of ice it yields a ketonic acid C,,€€?,O in the form of a pale yellow syrup which reduces ammoniacal silver nitrate solution and Fehling's solution in the cold and yields iodoform with potassium hydroxide and iodine. The dipknyl- I~ydraxone of this acid C,,H2206(N213:Ph)2 forms chrome-yellow crystals m. p. 116-1 1 8 O (decomp.).If a large excess of permanganate is employed the oxidation of artemisin (1 mol.) yields oxalic acid (I mol.). T. H. P. Rhein. OTTO A. OESTERLE and ED. Trsza (Chena. Zentr. 1908 ii 1929-1930; from Schweiz Woch. Chem. Pharm. 1908 46 701-703. Compare Hesse Abstr. 1900 i 41).-When crystalhed about twenty times from pyridine and sublimed in a cathode ray vacuum this substance was obtained in small yellow needles or compact dark-coloured crystals m. p. 382-32 1.5' which gave on analysis 63.98 63 71% C and 2.88 2 81% H corresponding with C,,H,O the formul i suggested by Tschirch and Heuberger (Abstr. 1903 1 108). When acetylated in pyridine solution no higher acetyl derivative was obtained than the diacetate. When heated with propionic anhydride a pyridine solution of rhein yields a lemon-yellow crystalline propionate m.p. 223-224' ; analysis gave 68.21% C and 4.43% H. Benzoylation of rhein appears to result in the formation of at least two products which have not yet been separated. Methylation with methyl sulphate gives several metlqd ethers of which one insoluble in hot potassium hydroxide crystallices i n long pale yellow needles m. p. 2889 The conclusion is drawn that rhein is not a simple substance but a mixture. J. V. E. The Green Pigment of Bile. MAURTCE PIETTBE (Compt. rend. 1908 147 1492-1 495).-Bilirubin crystallises from benzyl chloride in long prisms often arranged in bundles ; it crystallises still better from a mixture of chloroform and carbon tetrachloride. The form- ation of biliverdin is not simply an oxidation f o r a green coloration is also produced when the halogens the halogen acids in glacial acetic acid trichloroacetic acid chloral bromal etc act on bilirubin.G. B.116 ABSTRACTS OF CHEMICAL PAPERS. Eetablishment of the Oxonium Theory. HERMAN DECKER and THEODOR VON FELLENBERG (Annulen 1909 364 1-44).-The salts of benzopyronium naphthapyronium and dibenzopyronium can only be regarded as compounds containing quadrivalent oxygen and the authors consider that the existence of quadrivalent basic oxygen is thereby established on as firm a basis as that of quinquevalent nitrogen quadrivalent sulphur and tervalent iodine The compounds regarded by Collie and Tickle Baeyer and Villiger Hewitt and Werner Fosse etc. as oxonium salts in spite of doubts which have been expressed as to this formulation are correctly so constituted and this also applies to Kehrmann's azoxonium compounds.The authors are in entire agreemenf with the views of Archibald and McIntosh (Trans 1904 85 919) on t h i s subject and they discufis at length the general resemblance between oxonium and ammonium compounds It is pointed out that the secondary valencies of oxygen are usually brought into play at a lower temperature than in the case of nitrogen ; thus oxonium compounds often decompose or even cannot exist at a temperature at which ammonium compounds are quite stable. I n this respect quadrivalent sulphur occupies a position intermediate between nitrogen and oxygen. The formation of a1 kylammonium salts as in the expression HI +- NH,Me ZZ NH,MeI NH + Me& whereby i the quaternary compound may decompose in two directions (to which phenomenon the term (' heterospasis " is applied) has its counterpart in the case of oxygen compounds and the formation of oxonium intermediate compounds with their possibility of hetero- spasis in many cases throws light on hitherto incompletely explained reactions.The syuthesis of benzopyronium derivatives is effected conveniently by condensing salicylaldehyde and its derivatives i n presence of sulphuric or hydrochloric acid with an aliphatic or aromatic aldehyde or ketone containing an acidic methylene group next to the carbinol group. Solutions of such oxonium salts in l0-15% hydrochloric acid are mostly yellow and on dilution or by partial neutralisation become colourless and deposit the corresponding colourless carbinol.Bonzo- pyronium ferrichloride is best prepared by shaking salicylaldehyde (2 mols.) and acetaldehyde (1 mol.) with 70% sulphuric acid and warming the mixture for three-quarters of an hour on the water-bath. After precipitating tar with hydrochloric acid solid ferric chloride is added. I n moist air it becomes black loses hydrogen chloride and coumarin is formed. 2-Methylbenzopyronium salts (Abstr. 1907 i 1064) are similarly prepared by the condensation of salicylaldehyde and acetone. The condensation of methyl ethyl ketone and salicyl- aldehyde in presence of sodium hydroxide lends to the formation of o-hydroxystyryl ethyl ketone OH*C,H,*CH:CH*COEt in small yellow crystals m. p. 101O (corr.) and a small amount of a compound C2.3H2203 in yellow leaflets m.p. 246-247" (corr.). Tho former on warming with fuming hydrochloric acid and adding ferric c h lor id e yield s 2 -e th ylbenaop yronium fewichlor ide C,,H ,OC1 FeC I in flesh-coloured crusts m. p. 68-70° (corr.) after sintering at 6 5 O . The salt becomes green on'exposure to light and decomposes under the influence of mcisture. When salicylaldehyde and methyl ethylORGANIC CHEMISTRY. 117 ketone are subjected to the action of hydrogen chloride and ferric Chloride added t o the purified product 2 3-dimethylbe~uopponium fmkhlorids C,,H,,OCl,FeCI,,. is formed in long yellow needles m. p. 117-118O (corr.) after sintering at 1129 On dissolving this in acetone and pouring into water the base probably dimetiiylbenzo- pyranol is precipitated.2-isoPropyZbsnmp yronium ferrichloridc C,2Hi,0Cl,FeCI prepared by condensing salicylaldehyde and valer- aldehyde in presence ol hydrogen chloride and subsequently adding ferric chloride forms long yellow needles m. p. 75-5-76.5O (con-.). 3-Itiethyl-2-ell~ylbeizzopyronium ferrhhloride Ci2H,,0C1 FeCl similarly prepned from salicylaldehyde and diethgl ketone forms golden leaflets m. p. 86.5-87.5' (corr.). With water it yields 3-rnethyt- 2-cthylbencopyrnnul Cl2Hl4O2 in small colourless needles m. p. 70-75" (corr. ). 'l'he condensation of salicylaldehyde and dipropyl ketone results in the production of a compound C2,H200 colourless glibtening leaflets m. p. 106-107° (corr.) and on adding ferric chloride t o the filtrate from this 3-eth y I- 2-prop ylbenxopyronium f eir-ichloride C14H,70CI,FeCI in yellow glistening leaflets m.p. 5 5 O which with water gives 3-ethyl-2 propylbenzopyrand in colourless needles m. p. 74-76O. 2-Phenylbenzopyronium ferrichloride is obtained in a 70% yield by condensing salicylaldehyde and acetophenone. 2 3-Dip?ien?/l- benzopyroniurn ferrichloride C2,H,,0Cl,FeCl similarly obtained froiri salicylaldehyde and deoxybenzoin crystallises i n long yellow needles m. p. 123-124' (corr.). With water this yields 2 3-diphnyZben:o- pymno7 C,,H,,O ic colourless needles m. p. 221-122' (corr.). On boiling this with methyl or ethyl alcohol the corresponding et?m is formed. 7-Hydroxy-2-phenylbenzopyronium chloride has the formiiln C,,HI,04Cl (Perkin Robinson and Turner Trans.1898 93 109Y give. C,,Hl,03C1). On heating at 140' in a current of bydrogen chloride the compound C,,Hl,02CI is formed. The picrate of t b e pyronium base turns brown at 19Uo and begins to sinter ; it is not cwnpletely melted a t 270° (Bulow and Sicherer Abstr. 1902 i 113 give m. p. 232-233'). The ferrichloride forms small yellow needles containing lC2H40 (from acetic acid) m. r. /\/'\ 165-163" (corr.) after previous sintering. I 11 I As a consequence of their work on benzopyronium OD\/\/ salts the authors consider that salts of phenacetein I 9 resacetein gallacetein quioacetein isobrasilein isohaema- tein fluorescein and coerulein are to be looked on as benzopyronium salts and suggest that the free bases contain the annexed chromogen. f2-P~en~lriaplithupyronium ferrichloride (annexed formuia) prepared by condensing /3-naphthaldehyde and acetophenone /\ and precipitating with ferric chloride forms small It I dark yellow needles m p.187.5" (corr.). On pour- \/\/'\ ing into water the colourless carbinol separates. I ' Ph 2 ; 3-Dip~enyZnaphtl,apyronium firrichloride \/\fl C?,H,@CJ,FeCJ3 9 similarly prepared from 6-naphthaldchyde and deoxy- cl FeCJs benzoin crystallises in small slender yellow needles rn. p. 205-206' (corr,); the carbinol base forms two picrcates that118 ABSTRACTS OF CHEMICAL PAPERS. with two mols. of picric 'acid forms dark-coloured crystals m. p. 118-1 ZOO and that with 1 mol. of picric acid gives smaller crystals m. p. 161O (decomp.) aftergintering at 145'. J. C. C. C heiroline the Alkaloid containing Sulphur obtained from wallflower Seeds.WILHELM SCHNEIDER(&W.,1908,41,4466-4470). -The formula assigned by Wagner to cheiroline (Abstr. 1908 i 202) is incorrect ; it should be C,H,,O,N,S,. Cheiroline is practically a neutral substance and is optically inactive ; it gives a white precipi- tate with mercuric chloride and when warmed with an alkaline solution of lead oxide yields lead sulphide and with an ammoniacal Rilver solution forms a mirror and silver sulphide. When the solution obtained by boiling the alkaloid (1 mol.) with dilute aqueous sodium hydroxide is acidified it evolves hydrogen sulphide (1 mol.) and carbon dioxide (about 1.4 mols.). The solution then contains a base,C,HIIO,NS which is obtained as an exceedingly deliquescent crystalline mass ; the hydrochloride C,H1,O,NS,HCl crystallises in almost colourless deliquescent prismatic needles m.p. 145-146'. The base when treated with sodium ethoxide and methyl iodide yields a quaternary methiodide C,H,,O,NIS obtained as glistening silky scales m. p. 183O; it is therefore probable that the base is a primary base. Since cheiroline readily parts with a carbon atom and a sulphur atom yielding a strong base it is probable that these atoms are connected to the two nitrogen atoms as in thiocarbamide. W. H. G. Ergot of Rye. ERNST VAHLEN (Archiu exp. Path. Pharm. 1908. 60 42-75).-The author controverts the statement of Barger and Dale (Abstr. 1908 i 204) that the crystalline product clavin previously isolated from ergot is a mixture of leucine and aspartic acid.H e shows that by means of cupric acetate or hydroxide it can be resolved into two constituents one of which gives an insoluble copper salt whereas the other gives a soluble salt. The latter is a weakly basic substance of the formula C,H,,O,N m. p. 258-260° and does not give precipitates with the ordinary alkaloidal reagents ; the former is Lleucine. For these reasons the formula C,,H240,N is assigned to clavin. Clavin leucine and the clavin base are all very similar to one another in their crystalline form solubility in solvents and capacity for subliming and the clavin is regarded as the leucine salt of the base. The author also criticises Dale's experiment on the physiological action and maintains in opposition to Dale that clavin has a specific action on the uterus.Experiments were also carried out t o determine the physiological action of the alkaloids ergotinine and hydroergotinine which were isolated and described by Kraft. The latter has been assumed to be identical with the so-called ergotoxine the water-sollible amorphous alkaloid isolated by Barger and Carr (Trans. 1907 91 337). It was found that more than 16 decigrams per kilo was the toxic dose of hydroergotinine for cats whereas according to Dale (Abstr. 1907 i 791 1-5 mg. of ergotoxine phosphate was a toxic dose for the sameORGANIC CmMLSTRY. 119 animals. For these reasons the chemical identity of hydroer otine and ergotoxine cannot be regarded as proved. It is suggestef that both might be contaminated with varying quantities of a highly toxic substance. Ergotinine is relatively non-toxic when compared with hydroergotinine. An' experiment was made with the crystalline secalaminosulphonic acid which was isolated by Kraft.It was found when injected into a frog to be physiologically inert. It is not therefore the active principle in the; preparations described as sclerotic and ergotic acide. S. B. S. apoMorphine Hydrochloride. DAVID B. DOTT (Pharm. J. 1908 [iv] 27 8Ol).-Experiments have been made which indicate that apomorphine hydrochloride has the composition represented by the tormula C,4H,,0,N2,2HCI,2H20 in which i t is assumed that apo- morphine is formed by the condensation of 2 mols. of moEphine with elimination of 1 mol. of water. E. G. Action of Acids on Di-iodo-a-methylsparteine. AMAND VALEUR (Cornpt.rend. 19OS 147 1318-1319. Compare Abstr. 1908 i lOO6).- When iodoisosparteine methiodide is heated with either dilute sulphuric hydrochloric or acetic acid and the solution cooled the product is invariably iodoiso8pa?*teins methiodide hydriodida C1,H2,N2Me 12,H I m. p. 1 9So which regenerates iodoisosparteine methiodide when treated with sodium carbonate. The reaction is probably to be explained by the eeparation of hydrogen iodide from part of the methiodide thus CH ___ CE[(CH,IJ+M~I = /CH(C,H,,N)*CH b H - CHZ /CH(C8HJ4N)eCH2\ HI + CH- CkI( .UH,) -NMel and the subsequent action of the liberated hydrogen iodide on the unchanged methiodide. This view is supported by the fact that tho mother liquors from the action of dilute acetic acid on the methiodide contain a small quantity of a substance containing approximately the proportion of iodine required by the above formula.Moreover when iodoisosparteine methiodide is heated in a sealed tube with diluta sodium hydroxide solution at 125-1 30° a-methylsparteine is formed probably according to the reaction C,,H,,N2MeI + 2NaOEl= CIgH2,N,Me + 2NaI + 0 + H,O the oxygen hberated serving to oxidae part of the a-methylsparteine produced. Relation between a-Methylsparteine and isosparteine. Reciprocal Transformation of these Bases. 11. isosparteine- methosulphste and Some Salts of this Base. 111. Action of Alkalis on i8oSpar teinemethoaulphate. Methylisosparteinium Hydroxide. AMAND VALEUR (BULL SOC. china. 1909 [iv] 5 31-37 37-40 40-42).-The first paper is theoretical and gives an inter- pretation of results recorded in 44e second qnd third papers and other \CH2- OH,/ E.H.120 ABSTRACTS OF CHEMICAL PAPERS. work (Abstr. 1908 i 1006) on the basis of the formula? previously assigned to sparteine a-methylsparteine and isosparteine (Abstr. 1905 i 659 717; 1908 i 206). Most of this work hag been published already (Zoc. cit. and 1908 i 736). isosparteine methosulphate (Zoc. cit.) dissolves in 1 *5 parts of water and the solution is slightly bitter neutral to litmus and does not reduce potassium permanganate. The anhydrous salt has m. p. 140-1 40.5O. isoSparteine methochloride hydrochloride m p. 192-193" (decomp.) [a] - 19*75" obtained by adding barium chloride to the solution of the methosulphate separates from alcohol on addition of acetone in transparent deliquescent crystals.isoSpar- tsine methobrowde hydrobromide m. p. 193' (decomp.) [aID - 15*3S0 similarly obtained is crybtalline and verv soluble in water. Its solution on addition of sodium hydroxide deposits an oil which goon crystallises and is probably isosparteine methobromide. isosparteine methiodide hydriodide (Abstr. 19OS i 44) has [a] - 11.80' and crystallises from alcohol with 1 H,O. Spa?-teine methosulphate Cl,H2,N,Me,HS0,,7 H,O [.ID - 24*54O obtained by the addition of the necessary quantity of sulphuric acid to a-methylsparteinium hydroxide crystallises from water on addition of alcohol and acetone. The solution is slightly acid to litmus and does not reduce permanganate. The transformution of isosparteine into a-methylsparteine described previously (AbGtr.1908 i 736) may be used for the recovery of a-methylsparteine from the mixture of bases obtained in methylating sparteine (Abstr. 1908 i 44). The mixture is treated with sulphuric acid whereby the u-methylsparteine is converted into isosparteine methosulphate the other bases remaining unchanged. The latter are washed out with ether and the residual methosulphate converted into a-methylisosparteinium hydroxide by the action of baryta and this into a-methylspsrteine. T. A. H. Stryohnos Alkaloids. 11. New Method for the Preparation of Sulphonic Acids. HERMANN LEUCHS and WILHELM SCHNEIDER (Ber. 1908 41 4393-4396. Compare Abstr. 1908 i 563).-It is extremely difficult to obtain strychninesulphonic acids by the direct action of sulphuric acid on the alkaloid but strychninesulphonic acid C,,H,,O,N,S is readily formed when sulphur dioxide is passed into warm water (60') in which finely-divided strychnine and manganese dioxide are suspended. The acid crystallises from hot water in colourless needles containing water of crystallisatiou which is given up at 105".The dried acid is extremely hygroscopic ?and has m. p. 350-360" (decomp.). It dissolves readily in dilute alkalis but not in 20% hydrochloric acid. The solution in sodium hydroxide has [u] - 233'. A hoG solution of the sodium salt deposits the free acid when cooled. EMILE BAUD (Compt. rend. 1909 148 96-98).-From determinations of the electro-capillary maxima of mixtures of water and pyridine Gouy (Abstr. 1906 ii 725) deduced the existence of a compound of these substances.To C,,H,,N,( CH$l) HC] J. J. S. Aqueous Solutions of Pyridine.ORGANIC CHEMISTRY. 121 tbe Fame end the author has studied the freezing temperatures con- tractions in volume refractive indices and heats of dissolution of similar mixtures. The curve obtained by plotting the solidification temperatures of mixtures of pyridine and water against their percentage composition consists rjensibly of four straight lines the first extending from 0 to 55% of pyridine representing the separation of ica ; the second from 55 to 77% of pyridine that of a hydrate ; the third from 77 to 83%*of pyridine of another hydrate whilst the fourth represents the separation of pure pyridine. The temperature reaches a minimum for 83% of pyridine (C,H,N + 0*9H20) which is accordingly the composition of a eutectic mixture.As the crystal- lisation curves of the hydrates intersect before the maximum tht3 composition of these hydrates cannot be deduced ; all that can be con- cluded is that one contains more than S*6H20 and the other mom than 1.3H20 per molecule of pyridine. The curve drawn with percentages of pyridine by weight as abscissae and the contractions in vtdume at' these mixtures as ortlinates exhibits a maximum for the mixture of the composition C,K,N,2H20. The index of refraction curve has a maximum also at the mixture of this composition. Tbe heat of dissolution of pure pyridine in a large excess of water diminishes with rise in temperature according t o the expression Q = 2.800 - 0904.4 (t - 19.5).Determination of the heats of dissolution of the mixtures of w'tter and pyridine permits of the calculation of the heats of formation of the latter. By calcdating the rebults with reference to the addition of increasing quantities of water t o a molecule of pyridine a smooth curve is obtained exhibiting a change of direction a t 2H,O and GH,O whilst calculation of the heats for the same volume of mixture gives a curve showing a maximum for C,H,N,2 W ,O. The conclusion is drawn that aqueous pyridine solutions contain a t l e ~ s t two hydrates C,H5N,2H,0 and C5€I,N,6H,0 dissociated at the ordinary temperature the more complex being the more dissociated. E. H. Alkaline Reduction of o-Nitrodiphenylmethane. PAUL CARRE (Compt. Tend. 1909 148 101-103*).-When o-nitrodiphenylmethane (Geigy and Kanigs Abstr.1885 1236) is reduced by gradually adding zinc dust to its boiling solution in alcoholic soda only 15-20% of o-llydrnzodiphenylmethane is formed the main product being o-aminodipheDylmetliane. o-~~d?.axodi~henylmet?~ane N,H,(C,H,-CH,Ph) crystallises in white lamella m. p. 148-149O. It i.; oxidised by mercuric oxide to o-azodiphenylmethane N,( C,H;CH,Ph) which exists in two forms. The a-modification crystallises from acetic acid in red needles m. p. 116-117" which on melting are transformed into the P-modification m. p. 124-125". The latter when recrystal- lised from acetic acid regenerates the a-compound whilst crystal- lisation of either from alcohol gives a mixture of the two forms. When o-hydrazodiphenylmethane is treated with dilute acids it under- goes the benzidine transformation giving 2 2'-dibenz&4 4'diamino- dipheizp? C,,H,(CH2Ph)2(NH,) which crystallises in long white * and Bull.SOC. chim. 1909 [iv] 5 119-121.122 ABSTRACTS OF CHEMICAL PAPERS. needleR m. p. 136q and forms a s u l p k t e C,6H24N,,H2S0 also crystallising in long white needles m. p 255" (decomp.) rapidly diesociated by boiling water and a hydrochloride C26H24N2 2 HCI,H,O crystallising in white needles m. p. 214' (decomp.) hydrolysed by water. o-Aminodiphenylmethane NH2*C,H,*CH2Ph prepared by Fischer and Schutte (Abstr. 1894 i ZOO) b u t not obtained by them in a crystalline form crystallises from ether in large light yellow prisms m. p. 5 2 O b. p. 19O-19lo/22 mm. 172-173O/12 mm. Its hydro- chZol*ide C,,H,,N,HCl crystallises in white needles m.p. 137' (decomp.) which are dissociated by boiliilg water. The amine when heated with phen y 1 t hiocar bi mide gives a-phen y l-fl-o-diphen ylmethane- thwcarbamide N HPh-CS*NH*C,H,*CH,Pb a white crystalline powder m. p. 138'. E. H. Reaction of Phenylhydraaine and a-Halogen Aryl Derivativee. GUIDO GOLDSCHMIEDT (G'cczxetta 1908 38 ii 634-638).-The results obtained by Ponzio and Valente (Abstr. 1908 i 458) had been published previously by Ofner (Abstr. 1904 i 818) and Flnschner (Abstr. '1905 i 936). FEANCESCO ANGELICO ( A tti R. Accad. Lincei 1908 [XI 17 ii 655-662).-Castellana and D'Angelo (Abstr. 1905 i 646) found that prolonged boiling of diazophenylindole with dilute sulphuric acid converts it into the corresponding azo-derivative. The author finds that diazotriphenylpyrrole does not undergo a similar transformation under the same conditions but that i t is con- verted into an isomeric compound which acts both as an acid and as a base dissolves readily in alcoholic potassium hydroxide solution giving a violet solution and separates in cinnabar-red scales ; with strong acids it gives insoluble blue salts.When treated with ethyl iodide in presence of sodium ethoxide it is converted into the ethyl derivative U,,HI,N,Et which crystallises from alcohol in shining indigo-blue needles m. p. 1 8 1 O . By the action of nitric acid on an acetic acid solution of the compound C,2H,5N3 the latter is converted into a diketone I which separates from alcohol in brownish-yellow crystals ni.p. 163O dissolves in concentrated sulphuric acid giving a blue solution and is converted by hydrazine into the correBponding axine C,2H14N4 crystallising from alcohol in golden-yellow needles m. p. 240° and subliming undecomposed. Reduction of the diketone bv means of zinc dust and acetic acid T. H. P. Transformations of Diazopyrroles. >NR yH:CH.s*N :N*y:CPh CH:CH*C-C:C'Ph CH:CH-E*N==T CH C H*C*CBz C Bz ' CH:CH R O N N*C:CPh CH:CH*C- yields the compound I ),:cph>O which crystallises from acetic acid in shining red needles m. p. 195' and is oxidiaed to the diketone by the action of nitric acid. T. H. P.ORGANIC CHEMISTRY. 123 Gonversion of Hydrazing Derivatives into Heterocyclic Compounds. XXV. N-Amino-osotriazoles. ROBERT STOLLE (J. p. Chem. 1908 [ii] '78 544-546.Compare Abstr. 1907 i 654).-The author now draws the conclusion that the compound obtained by the complete hydrolysis of 2 3-dibenzoyl-5 6-diphenyl- 2 3-dihydro-1 2 3 4-tetrazine which was thought previously to be 5 6-diphengl-2 3-dihydro-1 2 3 4-tetrazine (Abstr. 1905 i 97) is 1-amino-3 4-diphenyl-1 2 5-triazole 8ZiS>N*NH2 &ce when it is benzoylated it yields a compound isomeric with the dibenzoyl derivative j u s t mentioned but hiving m. p. 151"; this compound -is l-d&banxoylamino-3 4-diphnyl-1 2 6-t&axole is also formed when 2 3-dibenzoyl-5 6-diphenyl-2 3-dihydro- 1 2 3 4-tetrazine is heated at about 190° and by the benzoylation of the compound obtained by eliminating one of the benzoyl groups from the above dibenzoyltetrazine ; the latter compound must be therefore 1-benzoplamino-3 4-diphenyl-1 2 5-triazole It has also been shown that 2 3-dibenzoyl-5 6-dimethyl-2 3- dihydro-1 2 3 4-tetrazine when heated at about 150' passes into 1-dibenzoylarnino-3 4-dimethyl-1 2 5-triaxoZe YMeiN>N*NBz CJne.N m.p. 1 149 W. H. G. Addition of Hydrogen Chloride to Organic Bases and Aso-compounds. ANTONI KORCZY~SHI (Ber. 1908 41 4379 -438 I. Compare Abstr. 1908 i 977; Scholl and Escales ibid. 1898 i 18a).-Tbe absorption of hydrogen chloride by organic amines and azo-derivatives has been examined at various temperatures and in an apparatus similar to that used by Ley and Wiegner. The maximum number of molecules of hydrogen chloride absorbed is not a function of the strength of the base.At -75' aniline p-toluidine and 0- and m-nitroanilines form salts with 3HC1 and dibromo-p-toluidine End p-nitroaniline with 2HCl. At the ordinary temperature azo benzene p-hydroxyazo benzene p-me thoxyazobenzene and aminoazobenzene absorb 2HC1 and dimethylsminoazobenzene 3HC1. J. J. S. The Corntination of Iodine in Iodothyreoglobulin and aome Observations on Iodothyrin. ADOLF OSWALD (Arch. exp. Path. Pharm. Y.908 60 115-130).-The degradation of iodo- thyreoglobulin by pancreatin and barium hydroxide solution was studied. By means of the former a small amount of a substance was obtained which deposited from the digest and was goluble in alkalis but insoluble in acids ; it contained 3-4*5% iodine and was in many respects similar to Baumann's iodothyrin ; t h e greater part of the iodine found in the digest was not in combination with organic substances.By scission with barium hydroxide also only a small124 ABSTRACTS OF CHEMICAL PAPERS. amount of an organic iodine compound was obtained which was soluble in acids and was probably unchanged thyreoglobulin. S. €5. S. The Mono-amino-acids of Paramucin. FRITZ PREQL (Zeitsch. phpiol. Chern. 1908 58 229-232).-After acid hydrolysis paramucin yields glucosamine diamino-acids in traces leucine alanine proline phenyl-alanine as partic acid,.glutamic acid tyrosine and tryptophan. Quantitative data are not given. W. D. H. Hydrolysis of Glutokyrin. MAX SIEGFRIED and 0. PILZ (ZeitscA. plqsiol. Chem. 1908 58 215-228).-Glutokyrin P-sulphate was prepared from gelatin ; the phosphotungstic acid precipitate from it cwtains 80% of its nitrogen Arginine lysine and glutamic acid were found in the cleavage products after hydrolysis. Histidine and glycine were not obtained. W. D. H. Molecular Analysis of Proteins. ALEXANDRE ETARD and ANTONY VILA (Compt. rend.,. 1908 147 1323-1324. Compare Abstr. 1908 i 584).-The use of anhydrous methyl alcohol is advocated for separating and drying the mixtures of amino-acids formed in protein hydrolysis. A solution of barium hydroxide in anhydrous methyl alcohol is employed for precipitating the acidic substances thus obtained. G. B. The Influence of Acids Alkalis Neutral Salts and Carbo- hydrates on Trypsin. T. KUDO (Biochem. Zeitsch. 1909 15 473-500).-Tryptic digestion with ‘‘ pancreatin Rhenania ” proceeds best in a neutral medium. It is inhibited by alkalis and acids especially organic acids. Sodium carbonate has a very small destructive influence on the ferment acetic acid is indifferent other organic acids destroy it and mineral acids are rather more powerful in this direction. The destructive action is independent of their valency or concentration. Various salts have an inbibitory action but in most cases a slight one. Starch is also inhibitory but the sugars have little or no effect. W. D. H. The Adsorption of Diastase and Gatalase by Colloidal Protein and by Normal Lead’ Phosphate. AMOS W. PETERS (J. Biol. Chem. 1908 5 367-380).-A method of concentratioxi of enzymes is described in which the enzyme is adsorbed from solution by the addition of lead phosphate suspended in water or by peptone ,suspended in 50% acetone. Almost the whole of the enzyme is adsorbed and remains active in spite of the presence of the adsorbed precipitate from which it can only be separated to a slight extent by washing with water. The diastase employed mas obtained from germinating wheat from autolysed liver and from liquid bacterial cultures. The action of diastase is accelerated by the presence of lead phosphate but not for instance by that of zinc phosphate; the reason for the acceleration is unknown. G. U.

ISSN:0368-1769    

DOI:10.1039/CA9099600077

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

82 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Action of Oidium lactis and Vibrio choler= on Choline Hydrochloride. A. RUCKERT (Arch. Pha~m. 1908 246 676-69 1). -Brieger has stated (Die Ptomaine Berlin 1888) that certain bacteria have the property of removing a molecule of water from choline thereby forming the toxic substance neurine and this observ- ation has been confirmed to a certain extent by E. Schmidt (Abstr. 1892 219). With a view t o further confirmation the author has grown pure cultures of Oidium lactis and Vibrio cholerae in solutions of choline hydrochloride with bouillon as a nutritive medium and finds that these decompose choline forming ammonia and carbon dioxide but he was unable to detect any neurine in the reaction products.T. A. H. The Formation by Microbial Activity from Starch of Crystalline Substances which do not reduce Fehling’s Solution. FRANZ SCHARDINGER (Centr. Bakt. Par 1908 ii 22 98-103).-The substances i n question were obtained by the growth of Bacillus rnacerans in a medium two litres of which contained 100 grams of starch 2 grams of ammonium phosphate 0.5 gram of magnesium sulphate and sodium chloride. The mixture was filtered after four days’ incubation and the filtrate which smelt strongly of acetone and was acid in reaction was neutralised and evaporated. On cooling a crystalline product separated which was extracted with 50% alcohol. To the concentrated cooled alcoholic extract ether was added. A precipitate was thereby obtained which consisted chiefly of regular hexagonal plates ; intermixed with these were aggregates of needles.The substances do not reduce Fehling’s solution and give reactions with iodine solutions. Reduction of Nitrates during Alcoholic Fermentation. GIULO PARIS and T. MARSIGLIA (Chem. Zentr. 1908 ii 966; from Slax. sperim. agrar. ital. 1908 41 223-232).-During the process of alcoholic fermentation the nitrates present are found to be reduced in varying quantity to oxides of nitrogen. The action is sufficiently vigorous to reduce completely all the nitrates naturally present in the must ; in some cases the reducing action is so vigorous t h a t a relatively large amount of added nitrate may also be reduced whilst in other cases the greater part remains unchanged. I n these circumstances of varying intensity of reduction during fermentation little value is t o be attached to the amount of nitrate present in a wine as affording an indication of its dilution. S.B. S. J. V. E.VEGETABLE PHYSIOLOCIY AND AGRICULTURE. 83 Nitrification of Calcium Cyanamide in Various Types of Soil. SANTE DE GRAZIA (Chew. Zentr. 1908 ii 1060; from Xtaz. sperim. ugrar. itwl. 1907 41 241-257. Gompare Miintz and Nottin this vol. ii 88).-The nitrification of calcium cyauamide differs mainly from that of ammonium sulphate in that the former substance acts injuriously on the soil micro-organisms so long as it remaina undecomposed. The rate of nitrification is not particularly 'slow although in comparison with that of ammonium sulphate there is some retardation ; it is much quicker in clay soils and in those rich in organic matter but not acid than in sar,dy or chalky soils. The chief factors seem to be the water capacity and the absorptive power of the soils; the fermenting power is also important.E. J. R. The Influence of Oxygen on the Decomposition of Plants (Contribution to the Study of Humus Formation). DOMENICO CARBONE and RENATO MAHINCOLA-CATTANEO (Chenz. Zentr. 1908 ii 1049; from Arch. Farm. sperirn. 1908 7 265-301).-The decom- position of plants is mainly brought about by Eumycetes which break down the dead tissues chiefly in presence of oxygen but also in its absence. They not only attack the intracellular pectic substances but also the cellulose of the cell malls and in many cases even the starch. E. J. R. The Amounts of Caloium and Magnesium in Plant Seeds.ERNST SCHULZE and CH. GODET (Zeitsch. physiol. Ghem. 1908 58 156-161).-Analyses of the ashes of the husks and kernels of various seeds show that the husks contain relatively more calcium than magnesium but that the kernels are richer i n magnesium. The following numbers axe given 100 parts of ash contained Percent. A- of ash. K,O. CaO. BlgO. P205. Pinus Cemhra ............ Kernel ... 2.90 29.4 6.7 9'9 42.8 Husk ... - 44.9 12-6 11'0 3-2 Li~~nz6sangu:tifo lius... Iieruel ... 3.78 31.4 5.0 10.6 40.5 Husk ... - 27.5 38.7 9.4 6.1 Ctieurbita Pep0 ......... Kernel ... 3'67 18'5 1.1 19 0 85.8 Husk ... - 35.0 8.5 7'6 6'4 Ricinus cominunis ...... Kernel ... 3.64 - 4.0 19'8 31 9 Husk ... - 23.7 43'9 4.3 0.6 Helinntlzzrs annus ......Kernel ... 3.66 - 5'0 17'9 - Corglus nvcllnna ...... Kernel ... 3'09 - 9.6 15.5 - Amygdalis commzinis.. . Kernel ... 2 *86 - 12.8 13'4 - J. J. S. Juglnns regia ............ Kerncl ... 2.40 - 3.0 11.5 - The Nutritive Effect of Amides on the Germinating Seed the Detached Embryo and the Green Plant. JULES LEFBVRE (Compt. rend. 19OS 147 935-937).-The author has shown already (Abstr. 1905 ii 648) that green plants can develop perfectly and construct all their organic matter from tyrosine leucine oxamide alanine or glycine without being supplied with any carbon dioxide whatever. H e now shows that maize seeds will germinate and the 6-284 ABSTRACTS OF CEEMICAL PAPERS. young plant grow and increase in weight under the same conditions whilst the detached embryos of Pinus pinea will not; the latter however develop in a solution of sucrose.E. J. R. Transformation of Cyanogenetio Glucosides during Germination. LSON GUIGNARD (Compt. rend. 1908 147 1023-1028).-Etiolated seedlings of Phaseolus Zunutus lose in the first fortnight one-third of the phaseolunatin contained in the seed ; in seedlings grown in the light the disappearance of the glucoside is compensated for from the tenth day onwards by that which is synthesised in the leaves. Free hydrogen cyanide could not b0 detected at any stage ; it appears to be used up as soon as it is set free. G. B. The Relation between Plant Respiration and Alcoholio Fermentation. S. KOSTYTSCHEFF (Ber. deut. bot. Ges. 1908 26 a 565-573).-The reactions taking place during the normal respiration of plants have not yet been worked out experimentally although several schemes have been suggested.The author deals particularly with those hypotheses in which tho production of alcohol is supposed to be an intermediate stage namely (1) the plant sugar gives rise to alcohol which is then oxidised by enzymes t o carbon dioxide and water ; (2) the alcohol formed is not oxidised but is assimilated by the plant ; (3) the plant sugar decomposes in the same way as in alcoholic fermentation but the reaction does not go so far as alcohol production and the intermediate substances are oxidised. The author’s experiments were made with peas and in his view they confirm the last of these hypotheses. E. J. R. Correlations in Vegetable Metabolism. BARTHOLD HANSTEEN (Bied. Zentr.1908 37 7SS; from Landw. Jchb. 1908 262)- Under normal conditions every plant assimilates potassium mag- nesium and phosphoric acid in such a manner that each organ of the plant contains at all times the optimum amounts the amounts varying with different plants and different organs and according t o the period of growth. The single specific optima show certain variations ; exclusive addition of one of the substances modifies the process of nutrition which however again becomes normal when the usual conditions are restored. N. H. J. M. Glycogen of Ascomycetes and its Relaton to Trehalose. VLADIMIR A. TICHOMIROFF (Arch. Yhurna. 1908 246,582-59 l).-The investigations of Clautriau Errera and others having shown that glycogen probably serves as a reserve material and for this purpose is first hydrolysed into sugars it becomes of interest to investigate the relationship in the fungi of glycogen and trehalose the latter being the characteristic sugar of this class of plants.In all cases the distribution of glycogen mas determined mainly by staining microscopic preparations with iodine and the distribution and nature of the sugars by Senft’s micro-chemical method with phenylbydrazine in glycerol (Abstr. 1904 ii 595).VEGETABLE PEYSIOLOCTY AND AGRICULTURE. 85 The young asci of Terfeexia transcaucasica show much glycogen and the fully ripe ones scarcely any. With Senft's reagent yellow spherulites of trehalosephenylosazone are iformed. Similarly F. Boudieri gave minute spherulites of osazone after two months and a preparation kept in Fehling's solution showed slight reduction in the neighbourhood of some of the cell contents.T. Leonis was found to be rich in glycogen especially the fructification and in this case osazone crystals appeared after a month. Choiromyces nteandr~mmis Hydnotricl carnea Tuber mdanosporum T. brumale 2'. rufum 2'. Borchii F. maculatum 2'. magnatum 2'. aestivum and 2'. excavatum were also examined. The first second and seventh were found to contain glycogen and also yielded spherulitea of osazone after about one month especially in the stalks and contents of the young asci. The other species mentioned had all developed ripe spores and con- tained no glycogen but they formed small amounts of osazone crystals after two or three months' treatment with Senft's reagent A preparation of T.meZclnospo~*um showed no reduction when warmed in Fehling's solution. The alga Nostoc prungorrne and Fucus platycarpus were also examined and yielded after two months crystals of tbe same phenyl- osazone which may be that of dextrose galactose or fucose. T. A. H. Occurrence of Glycyrrhizic Acid in Plants. ALEXANDER TSCHIRCH and S. GAUCHUANN (Arch. Pharm. 1908 246 558-565. Compare Abstr. 1908 i 898).-In extension of previous work on the isolation and characterisation of the glycyrrhizic acid of liquorice root the authors have investigated the sweet root of Periandra dulcis and the bark of Pradosia Zuctescens and find that these also contain glycyrrhizic acid although from the second of these products it was ob- tained in the form of a dihydrate. The method of preparing the acid described by Tschirch and Cederberg (Abstr.1907 i 545) is not applicable in the case of the bark of Pradosia Zactescens or in those of the root of A6rus precatorius and the rhizome of Polypodium vulgare in which glycyrrhizic acid also occurs. T. A. H. Physiological Mechanism of the Coloration of Red Grapes and of Autumn Leaves. J. LABORDE (Compt. rend. 1908 147 993-995. Compare Abstr. 1908 ii 774).-Certain tannins such as gallotannin which are not transformed into a red colouring matter by heating with hydrochloric acid (Zoc. cit.) nevertheless yield such a pigment by exposure to light in hydrochloric acid solution in the presence of formaldehyde. The latter substance often assumed to occur in plants is compared to a ferment; the hydrochloric acid merely produces a favourable medium and the absence of pigmenta- tion in white grapes is regarded as due to an unfavourable medium.G. B. Alkaloids of the Tubers of Corydalis cam. ERNST SCHMIUT (Arch. Pharm. 1908 246 575-582).-The isolation of protopine and dehydrocorydaline from the tubers of CorydaZis clmbigzla (Abstr.,86 ABSTRACTS OF CHEMICAL PAPERS. 1908 i 825) and C. Vernyi (ibid. 908) has led the authors t o re- examine the tubers of C. cavu for these alkaloids (compare Abstr. 1897 i 174; 1898 i 604). Haars has already shown that the stem and leaves of C. cava do not contain protopine (Abstr. 1905 i 462). Dehydrocorydaline was obtained and identified by means of the aurichloride and by its reduction to i-corydaline. An alkaloid which may be protopine was obtained mixed with bulbocapnine from which it could not be separated.No protopine could be obtained from the seeds of C. nobilis or C . lutea. T. A. H. Analysis of the Tubercule of Dioscorea macabiha from Madagascar. EMILE BOURQUELOT and BRIDEL (J. Pharm. Chim. 1908 Liv] 28 494-500).-The tubercules of this plant which are reputed to be poisonous contain no alkaloid or glucoside hydrolysable by emulsin. Starch sucrose a reducing sugar and three enzymes invertase amylase and an anzeroxy dase were detected. The toxicity may be due to a toxin. T. A. H. Oils from Lycopodium Ergot Areca Nut and Aleuritse cordata Seed ARNOLD RATHJE (Arch. PImrm. 1908,246 692-709). -Authentic specimens of these oils have been examined with the view of establishing their chief constants and their composition.The methods of investigation employed are given in detail in the original. Lycopodium contains 49.2% of a greenish-yellow oil which is acid in reaction and has D 0.93617 nD 1.4671 saponification number 195.0 acid number 18.6 iodine number 81.0 Hehner number 88.0 Reichert-Meissl number 7.3 and true acetyl value 44.1. The mixed fatty acids have m. p. 39-40' neutralisation value 202.0 and iodine number 91%. The percentage composition of the oil is lycopodoleic acid 81 lycopodic acid (dihydroxystearic acid) 3.2 stearic acid 1.13 palmitic acid 0.85 myristic acid 2.0 glycerol 7.8 unsaponifiable matter 0.43 and inorganic matter 0.03 (compare Langer Abstr. 1889 741 1059). Ergot oil is dark brown in colour with a slightly irritant taste.Its constants in the order given above for lycopodium oil are D 0 9250 4ZD 1.4685 179.3 11.38 74.0 96.25 0.63 27-44 and for the mixed fatty acids m. p. 38-39' 183-0 77*2. The percentage composition of the oil is oleic acid 68 hydroxyoleic acid 22 palmitic acid 5 un- saponifiable matter 0.35 inorganic matter 0.2 alkaloid 0.6 and glycerol 7.5 (compare Mjoen Abstr. 1896 ii 506). Two samples of areca nut fat were examined the first having been extracted by ether ( A ) and the second by light petroleum (B). The constants in the order given under lycopodium oil are as follows; those for sample A are given first in each case. Oil D = 0.884 0.973 ; 91.45 ; 0*2,4*2 ; I1 '2 9-81; mixed fatty acids m. p. 39O 39-40'; 229 6 235.5 ; 25.95 13.6. The percentage composition of the mixed fatty acids in the two cases was lauric 43.6 53.3; myristic 21.0 24.7; palmitic 3.1 24.7; stearic 2.25 3.3 ; oleic 29.0 14.5 ; decoic 1.0 1.0.Sample B also yielded traces of hexoic and octoic agida. The other 3. p. 36-37' 37-38'; 227.4 234.6 ; 91.1 97.2 ; 24.3 12.3 ; 92.76,VEGETABLE PHYSIOLOGY AND AGRICULTURE. 87 constituents of the two fats in percentages were unsaponifiable matter 1-0 glycerol 5.0 and inorganic matter 0*02-0*03 and ~ o m e phytosterol. Two samples of oil from the kernels of Aleurites cordata (T'ung oil) were examined the one of Chinese (No. I) and the other of Japanese (11) origin. The constants in the usual order and with those of No. I first in each case were oil D 0.9383 0,9393 ; n 1.503 1.504 ; 191.5 189.9 ; 10.4 2.1 ; 156.2 153.2 ; 96.05 96.48; 1.04 0.55 ; 105 13.42 ; mixed fatty acids m.p. 39-40' 40-41O; 189.4 188.0; 163.4 160-3. The percentage composition of the oils was fatty acids 95.6 96.0; glycerol 9.5 8.7; unsaponifiable matter 0.45 0.48 and inorganic matter 0*001 and nil. I n both cases the fatty acids con- sisted of elmmargaric acid 75% and oleic acid 25% (compare Abstr. 1898 i 628; 1899 i S64). JULIA T. EMERSON and WILLIAM H. WELKER (J. Biol. Chern. 1908 5 339-350).-The tuber of this plant contains proteins carbohydrates (woody fibre with small amounts of sugar and starch) fat cholesterol lecithin and salts. It is used as a cathartic and in large doses is stated to be poisonous. No alkaloid was found and the substance responsible for its action was not discovered.Soils of Acid Reaction. YOSHINAO KOZA (Chrn. Zed. 1908 32 1187).-The author cites an instance of a peculiar acid-reacting soil in Nischigahara near Tokio. It contains hydrated silicates more especially clays and when a sample quite free from humus is washed with water the acidity of the soil remains unchanged and no soluble acid is dissolved out but after the addition of a soluble neutral salt such as potassium chloride or ammonium sulphate a soluble acid is at once detected. The potassium or ammonium appears to be absorbed by the clay causing liberation of hydrochloric or sulphuric acid and consequently after dressing such a soil with potassium or ammonium manures! worse results are obtained than previously. Fixation of Ammonia by Zeolites in Soils.THEODOR PFEIFFEH ALBE~T HEPNER and L. FRANK (Bied. Zentr. 1908 37 722-723 ; from Mitt. Iandw. Inst. I%. U%v. Breslau 1908 4)- Barley followed by oats were grown in pots in sand manured with blood meal ammonium sulphate and minerals and in similarly prepared pots with different amounts of calcium carbonate and calcium zeolite (prepared by treating apophyllite with calcium chloride) respectively. It was found as in previous experiments (Bied. Zentr. 1905 510) that the absorbed ammonia was held so firmly by the calcium zeolite T. A. H. Composition and Toxicity of Ibervillea sonorae. W. D. H. J. V. E. that it was only partly available for the second period of vegetation. N. H. J M. Sodium Chloride Experiments with Mangolds. HERMANN BRIEM (Bied. Zentr. 1908 37 73 1-732 ; from Deut.Iandw. Presse 1907 89).-Application of sodium chloride (2 cwt. per hectare)88 ABSTRACTS OF CHEMICAL PAPERS. in addition to superphosphate and sodium nitrate increased the yields of three varieties of mangolds (roots) and also the amount of sugar as compared with superphosphate and nitrate only. The amount of leaf was considerably increased in the case of the more leafv varietv. but slightly reduced in the case of the less leafy roots (Ecklndorferj.' N. H. J. M. The Impurities of Uhili Saltpetre. The Possibility of Using a Less-reflned Saltpetre. SANTE DE GRAXIA (Chem Zen& 1908 ii 1199; from Stax. sperim. agrar. itcd. 1907 41 258-269).-The author finds that the common impurities of Chili saltpetre (sodium chloride and magnesium sulphate) are beneficial t o vegetation whether applied alone or in conjunction with the pure nitrate.Potassium iodide is without effect. A less-refined saltpetre (not containing potassium perchlorate however) might therefore be used for manure. E. J. B Manurial Experiments with Two Commercial Forms of Calcium Cyanamide Sodium Nitrate and Ammonium Sulphate applied to Mangolds. RICHARD OTTO (Bied. Zentr. 1908 37 787; from Deut. Zandw. Presse 1908 35 No. I).-Ammonium sulphate and '' stickstoffkalk '* gave the highest results (991 and 984 cwt.) then " kalkstickstoff " (891 cwt.) and lastly sodium nitrate (864 cwt.). The yield without nitrogen was 553 cwt. per hectare. N. H. J. M. The Employment of Calcium Cyanamide in Agriculture. ACHILLE MUNTZ and P. NOTTIN (Compt. rend 1908 147 902-906 ; compare Sante de Grazia this vol.ii 83).-The authors have studied the nitrification of calcium cyanamide in the soil and find that the process varies somewhat with the amount present but is in the main Suf- 2 cient of each of these substances was mixed with soil to add 0.25 gram of N per kilo. and the quantity of nitrate produced per kilo. after definite intervals was found to be uite comparable with the nitrification of ammonium sulphate. Relative amounts of nitrate at 2 39 theend of 8 days. 15 days. 33 days. months. months. 5months. Calcium-cyanamide.. - 0.003 - 0.011 0'030 0.068 0.204 100 Ammonium sulphate 0'039 0.149 - - 0.247 88 Dried blood ............ 0'048 0.111 - - 0.154 66 Torrified leather. ..... 0.003 0.024 - - 0.037 26 The large amount of cyanamide used in this experiment (10 to 20 times the quantity customary in practice) at first inhibited nitrifica- tion and even caused some denitrification but later on exercised no disturbing effect. Smaller amounts had no inhibiting effect ; indeed by successively adding small quantities to the soil it is possible for large amounts to become nitrified especially in soils where nitrification is vigorous. These show that (1) calcium cyanamide gives substantially the same crop increases as ammonium Numerous field trials are recorded.ANALYTICAL CHEMISTRY. 89 sulphate; (2) it does not in practice have the injurious effect on germination that would be expected from laboratory experiments and can without any bad results be applied to the soil on the same day a8 the seed is sown; (3) it can be used as a top-dressing and the slight resulting injury to the plant is only temporary E. J. R.

ISSN:0368-1769    

DOI:10.1039/CA9099605082

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 89 An a1 y tic a1 Chemistry I A New Electrical Method for the Continuous Analysis of Gas Mixtures and its Application to the Measurement of the Velocity of Gas Currents. ADOLF KOEPSEL (Ber. deut. physikal. Ges. 1908 6 814-827).-The method depends on the variation of the thermal conductivity of a gas mixture with its composition. In its application the resistance of a wire suspended in the gas to be analysed is compared with that of a second wire contained in air or a gas mixture of constant composition. Both wires are traversed by a constant current but the difference between the thermal conductivi- ties of the surrounding gases results in temperature differences and consequently in differences in the resistances of the two wires which are measured. In the apparatus which has been constructed for the continuous electrical analysis two wires are suspended in the gas to be analysed and two in the standard gas and these are arranged so as to form the arms of a Wheatstone bridge. The method is recom- mended for the analysis of generator gas flue gases and mine gases.In the actual apparatus elaborate precautions are taken to avoid disturbances resulting from the action of the gas currents on the heated wires. The heated wires are so sensitive to the movements of gases that the arrangement may be utilised for the measurement of very slowly moving air-currents. Some observations relating t o the sensitiveness of the electrically- heated wires for different loads are communicated. For the wires used by the author all the gases and gas mixtures examined mere found to exhibit maximum sensitiveness when currents ranging from 0.30 to 0.34 ampere were passed through them.This variation in the current corresponded with a temperature range of 180' to 320'. H. M. D. The Mercury Bath a Too-little Known Useful Expedient in Gas-analytical Work. ALFRED STOCK (Ber. 1908 41 3834-3849).-The original contains a detailed illustrated descrip tion of a mercury-bath specially adapted for gas analysis together with directions for working with it. Gasometric Work by means of V. Meyer's Vapour Density Principle. JULIUS MAI (Ber. 1908 41 3897-3904. Compare Abstr. 1903 ii 98).-The method has now been simplified and the W. H. G.90 ABSTRACTS OF CHEMICAL PAPERS. sources of error reduced so that it may be employed in actual practice.The bulb is placed near the outlet tube and the constant temperature maintained by boiling xylene toluene aniline or water The asbestos cartridge has been displaced in favour of a glass tube 27-35 mm. x 6 mm. provided with one to two holes 4 to 6 mm. from the jop. The results obtained from calcium strontium and barium carbonates are in accordance with the theoretical ; magnesium carbonate gives low results. W. R. BERNIIARD TOLMACZ (Zeitsch. angew. Chem. 1908 21 2551).-The pipette is surmounted by a tap so bored that the interior of the pipette may be in communication with the outside air or with the suction tube or with neither according as it is turned. Tap pipettes with more than one bulb are found advantageous where several small quantities of the same liquid are to be measured out ; thus the contents of the upper bulb between two graduations on the stem may be accurately measured out and then the contents of the second bulb.J. V. E. Tap Pipettes. Burette for Calibrating Measuring Flasks. A. MULDER (Chem. Weebblad 1908 5 830-S31).-The burette consists of a fairly narrow tube with a large bulb and below it a smaller bulb a aide-tube being sealed on below the smaller bulb and a glass stopcock below the side-tube. Above the larger bulb is a zero mark between the two bulbs a 100 C.C. mark and below the smaller bulb a 110 C.C. mark. Above and below the last two marks there are a number of divisions corresponding t o tenths of a C.C. The portion of the tube below the stopcock is capillary to admit of the introduction of the water into the flask without wetting the neck of the latter. Water is introduced into the burette from a bottle at a higher level through the side-tube and a tube fitted with a pinchcock.The apparatus is suitable for the calibration of measuring flasks intended to contain any multiple of 100 or 10 C.C. An Indicator Highly Sensitive towards Alkali and Suitable for Titrations with Centinormal Solutions. ERWIN RUPP and R. LOOSE (Ber. 1908 41 3905-3908).-The authors find that p dimetlq Zaminoaao benzene-o - car boxv Z ic acid C02H*C,H;N N*C,H,*EMe surpasses other indicators and especially haematoxylin and iodoeosin when used in the titration of very dilute solutions (up to N/lOO) of weak bases (especially vegetable alkaloids).The indicator to which is given the name " methyl-red,'' is prepared by combining a diazotised solution of o-aminobenzoic acid with dimethylaniline in alcoholic solu- tion and crystallises from acetic acid in glistening violet needles. I t F colour in alkaline or neutral solution is pale yellow and in acid solution violet-red. J. C. C. Burette for the Analysis of High-Grade Oxygen. H. MURSCH- HAUSER (Zeitsch. angew. Chem. 1908,21 2503-2504).-A combination of two gas burettes of the Zuntz-Geppert type surrounded by a water jacket; one serves as a thermobarometer whilst into the other is A. J. W.ANALYTICAL CHEMISTRY. 91 introduced in the usual manner about 100 C.C. of the sample which may be measured to 1/50 C.C. By means of Hempel pipettes containing aqueous potassium hydroxide and alkaline sodium hyposulphite the carbon dioxide and oxygen are absorbed and the remaining gas consists of nitrogen.L. DE K. Detection of Hydrogen Peroxide Formaldehyde and Persulphates. S. ROTEIENFUSSER (Zeitsch. Nahr. Genussrn. 1908 16 589-591).-Hydrogen peroxide may be detected in milk by adding about 10 drops of 2% alcoholic benzidine solution and a few drops of acetic acid to 10 C.C. of the milk; a blue coloration is obtained if hydrogen peroxide is present. For the detection of hydrogen peroxide in liquids other than milk it is necessary t o add a little milk serum as well as the reagents as the coloration is obtained only in the presence of the protein. Persulphates give a blue coloration with the benzidine solution alone and 1 part of persulphate in 1,000,000 may be detected by this means.Formaldehyde may be detected in milk by warming a portion of the milk with twice its volume of concen- trated hydrochloric acid to which has been added 3 drops of a 2% solution of a molybdenum uranium cobalt silver mercury or copper salt; a violet coloration being produced in the presence of form- aldehyde. w. P. s. Analysis of a Solution containing a Mixture of Sulphides Hydrogen Sulphides Polysulphides and Hyposulphites. F. DHUIQUE-MAYER (Chem. Zent?'. 1908 ii 1124-1125 ; from Rev. gen. Chim. pure. appl. 1908 11 273-274).-Ten C.C. of the solution are diluted to 100 c.c. and 10 C.C. of this again diluted to 200 C.C. and titrated with N/lO sulphuric acid using phenolphthalein as indicator (A). The liquid is next titrated with A'/lO iodine using starch as indicator (I).After decolorising the liquid with a small drop of the solution it is again titrated with N,/lO sodium hydroxide until pink (R). Another 10 C.C. of the solution are diluted and shaken with 2 grams of lead carbonate and the filtrate is titrated with N/10 iodine which now only gives hyposulphite (23). A = sulphides R = total sodium hydrogen sulphide R - A =true sodium hydrogen sulphide I - 2 R == polysulphide and hyposulphite H = hyposulphite ( I - 2R) - H = polysulphide. The coefficients used in the calculation are the tenth- part of the molecular weights; in the case of polysulphides the titre is divided by 2 and the result is expressed as sodium disulphide. L. DE I(. Estimation of [ Ammoniacal] Nitrogen.FRITZ TAURKE (Chem. Zeil. 1908 32 1176).-The usual plan is to distil 50 C.C. of the usual solution (=1 gram of the sample) with magnesia; the distillate is collected in a receiver containing 50 C.C. of N/2 acid and the excess of this is titrated with N/4 alkali. The amount of nitrogen is then calculated from the formula (50 - a)/2 x 0.007 x 100 = percentage. I n order to facilitate the operation the author starts with 35 C.C. of the solution ( = O T gram of the sample) and titrates from a burette graduated ti0 0.1 C.C. from 25' at the top t o 0' at the bottom. The92 ABSTRACTS OF CHEMICAL PAPERS. number read off then at once gives the percentage of ammoniacal C.*ALBERTE GARCIA (Bull. SOC. chim. 1908 [iv] 3 111 1-1114).-The point for which novelty is claimed in this apparatus is the device for eliminating all the air from the burette before the reaction is started.The nitrometer consists of a burette provided with a stopcock A communicating with a cylindrical reservoir of the usual pattern at the upper end and terminating below in a cylindrical bulb of 40 C.C. capacity which communicates laterally at its upper end with a glass funnel serving as a water reservoir and at its lower end with a reservoir of mercury. The water and mercury reservoirs connect with the burette by flexible tubing and can be used for levelling purposes and their connexions with the burette are controlled by stopcocks B and C respectively. I n using the apparatus the water reservoir and its connexion are filled with boiled distilled water of which a little is allowed to run into the burette.The stopcock B is then closed and the burette filled with mercury by opening stopcocks A and C. Stopcock A is then closed. By lowering the mercury reservoir a reduced pressure space is created in the burette so that solutions of reacting ingredients can be sucked in through A . A t the termination of the reaction water can be added through B and the resulting gas saturated with water vapour measured in the burette in the usual manner. nitrogen. L. DE K. New Mercury Nitrometer. T. A. H. Volumetric Estimation of Water-Soluble Phosphoric Acid in Superphosphates. LUDWIG SCHUCHT (Chem. Zeit. 1908 32 1201-1202).-Five hundred C.C. of the aqueous solution of the super- phosphate (20 grams t o 1 litre) are mixed with N/-potassium oxalate in order to remove the calcium but'as an excess must be strictly avoided it is best t o ascertain by a special experiment how much oxalnte is really required.After heating at 70' and subsequent cooling the solution is diluted to 550 c.c. and 110 C.C. of the filtrate (= 2 grams) are titrated in presence of methyl-orange with N,/2 alkali. Another 110 C.C. are mixed with 25 C.C. of the oxalate solution and then titrated in presence of phenolphthalein. The following example is given. I n the analysis of a superphosphate the first titration required 2.7 C.C. alkali; the second 11.2 c.c.; 11.2-2.7 C.C. = 8.5 C.C. x 0.0358 x 100/2 = 15.1% soluble P,O,. The amount of free acid = 2.7 C.C. x 0.0355 x 100/2 = 4.8% of P,O,. L. DE K. Estimation of Boric Acid in Insoluble Silicates.EDGAR T. WHERRY and WILLIAM H. CHAPIN (J. Amer. Chem. Soc. 1908 30 1687-1704). -Volumetric Method (WHERRY). - 0.5 Gram of the sample is fused with 3 grams of sodium carbonate for fifteen minutes. The mass is treated with 20-30 C.C. of dilute hydrochloric acid and a few drops of nitric acid and heated nearly to boiling in a 250 C.C. round-bottomed flask. After adding a moderate excess of pure calcium carbonate a refiux condenser is attached and the contents are boiled vigorously for ten minutes. The precipitate is collected on a BiichnerANALYTICAL CHEMISTRY. 93 funnel and washed with hot water. The filtrate :is then returned to the flask and after adding a pinch of calcium carbonate it is freed from carbon dioxide by boiling under reduced pressure j in this manner there is no fear of loss of boric acid by volatilisation. The liquid is filtered and rendered decidedly alkaline t o phenol- phthalein when 1 gram of mannitol is added.The solution is now titrated for boric acid with standard sodium hydroxide until pink when another gram of mannitol is added and the titration continued if necessary. The aodirim hydroxide must be titrated accurately as to its true hydroxide content; in that case it matters not i f a little carbonate should be present as this is neutralised by the calcium chloride present. Distillation Method [CHAPIN].-T~~S method is briefly as follows 0.5 gram of the borosilicate is fused with 3 grams of potass- ium sodium carbonate. The mass is decomposed by 12 C.C. of dilute hydrochloric acid (1 l) and the solution put into a distilling flask together with 12 grams of dry calcium chloride.The flask is connected with a generating flask in which methyl alcohol is being boiled and when 25 C.C. of this have collected heat is applied and the vapours (methyl alcohol and methyl borate) are passed through a short condenser and collected in an Erlenmayer flask to which a water trap is attached. When 100 C.C. of distillate have collected another 100 C.C. are collected in a second receiver. The methyl alcohol is distilled off after addition of an amount OF sodium hydroxide sufficient t o retainall the boric acid The resulting solution is then titrated for boric acid as usual using either glycerol or mannitol as a medium. L. DE K. Combustion Analysis.JAMES WALKER and THOMAS BLACKADDER (Proc. Roy. Soc. Eldim 1908 28 708-?12).-The dimensions of the tube used for copper oxide combustions have been reduced so as to secure the advantages of the Dennstedt furnace and to make this method of analysis more suitable for students working at an ordinary labopatory bench A furnace of the Dennstedt pattern but only 60 cm. in length and a Jena glass combustion tube 66 cm. long and not more than 8 mm. internal diameter are employed. Tho tube is charged with coarsely- powdered copper oxide and the substance to be analysed also mixed mlth copper oxide is burnt in a moderately rapid current of oxygen at a dull red heat. Details are given for carrying out combustions of compounds containing nitrogen and also volatile substances such as benzene the results obtained in each case being very good.A combustion tube of the same dimensions may also be used for estimating nitrogen by the direct method with equally satisfactory results. J. V. E. The Use of Sodium Peroxide for the Quantitative Analysis of Organic Compounds. 111. HANS PRINGSHEIM (Ber. 1908 41 4267-4271. Compare Abstr. 1904 ii 447; 1905 ii 609).-A modification of the older method is described. Substances containing 75% or more of C + H + S require eighteen times their weight of peroxide and those with 50-75% C + H + S,94 ABSTRACTS OF CHEMICAL PAPERS. sixteen times. Substances containing 25450% C + H + S are mixed with half theirweight of acompound rich in C and H(for example,sugar); those with less than 25% C+H+S with their own weight of the compound rich in C and H.The first of these mixtures is used with pixteen times its weight of peroxide and the second with eighteen times its weight. The admixing is carried out in an iran crucible by means of an iron nail The lid is placed on the crucible which is introduced into a dish containing cold water. The iron nail is raised t o a red heat and introduced through the hole in the lid of tho crucible. If the mixture is in the right proportions the whole mass becomes molten and after cooling for a few minutes is dissolved in cold water and sulphur halogens arsenic or phosphorus estimated as already described. Excellent results can be obtained. Estimation of Potassium as Phosphomolybdate. A. SCHLICHT (Chem. Zeit. 1908 32 1125-1126 1138-1140.Compare Abstr. 1907 ii 130).-About 0.1 gram of potassium sulphate free from ammonium salts is mixed with 10 C.C. of the author's reagent and evaporated to dryness. The residue is taken up with 10 C.C. of hot 5% solution of magnesium sulphate and when cold the precipitate is collected on a weighed asbestos filter and washed first with 10 C.C. and then with 5 C.C. of 5% magnesium sulphate then again three times with 5 C.C. of 5% ammonium nitrate and finally with alcohol and ether. 0.1 Gram of pure potassium sulphate thus treated yields 0.8071 gram of dry and 0.7860 gram of ignited residue. The reagent is prepared as follows 100 grams of molybdic acid are dissolved in water with addition of 250 grams of crystallised sodium carbonate the whole is evaporated to dryness and the residue heated for two hours at 150'.It is then dissolved in water up to 500 C.C. Meanwhile 6 grams of magnesium pyrophosphate are dissolved in boiling nitrohydrochloric acid and then evaporated repeatedly with nitric acid to expel the chlorine. The residue is dissolved in a little water and nitric acid D 1.36 and diluted to 500 C.C. with acid of the same strength. To this is then added gradually and with stirring the molybdate solution also another 500 C.C. of water and after standingLfor two hours the liquid is J. J. S. filtei ed. L. DE I(. Volumetric Estimation of Potassium in Animal Fluids. W. A. DRUSHEL (Anzer. J . Xci. 1908 [iv] 26 555-662*).-The process has been described previously (Abstr. 1908 ii 66). The only modification is that the " cobalt-yellow " is washed with weak brine (1 1) instead of with water ; this permits the use of a coarser asbestos felt without danger of loss.It is then titrated with N/10 permanganate 8s usual. Potassium in Urine.-Ten to fifty C.C. of the sample are evaporated to dryness in a small platinum dish and the residue is heated with 6-10 C.C. of a mixture of nitric and sulphuric acids (9 1); when the first violent action is over the acid is expelled and the residue * and Zeztsch. nnorg. Chern. 1909 61 137-146.ANALYTICAL CHEMISTRY. 95 ignited. The residue is then dissolved in a little water and a few drops of acetic acid and without previous filtration the liquid is treated with the sodium cobalt nitrite reagent as directed. Potassium in Circulatory flhids.-In this case the mass (blood serum lymph) is oxidised with nitric acid alone and the residue is heated but not strongly enough to cause an explosive decomposition.The mass is then heated with sulphuric acid and finally ignited. In the case of defibrinated blood this may be treated with about 2 C.C. of bromine and after an hour it is evaporated to dryness and charred. The mass is then extracted with hot water and the solution evaporated t o dryness after adding a little sulphuric acid. Potassium in Milk-The milk is evaporated to dryness and the residue treated with nitric acid. The whole is evaporated to dryness and ignited to burn off most of the organic matter. The residue is then moistened with sulphuric acid and once more ignited. L. DE I(. The Determination of Calcium Carbonate in Soils by the Methods of Bernard and of Treite and its Significance in the Selection of Soils [for Vineyards].KARL VOTRUBA (Chem. Zentr. 1908 ii 1065 ; from Allgem. Wein-Zeit. 1908 No. 30).-Bernard’s method consists in gently powdering the soil passing it through a 0.3 mm. sieve and determining the carbon dioxide evolved in a calcimeter from the fine soil. I n Treitz’s method the soil is stirred with water allowed to settle for half a minute decanted alid allowed to settle for half an hour and the carbon dioxide given off from the deposit on treatment with acid determined. The two methods did not give concordant results in the author’s tests but in general itlappears that the amount of carbonate in the fine soil is more important than that present in coarse lumps.Other properties of the soil however have t o be taken into account in selecting soils for vineyards. E. J. R. Detection of Poisonous Metals. GE-ORGE D. LANDER and H. W. WINTER (Analyst 1908 33 450-452).-The following methods are suggested for a rapid and simple qualitative search for poisonous metals in organic substances such as viscera etc. A Reinsch test is first made for arsenic antimony bismuth and mercury; if a deposit is obtained on the copper foil numerous methods are avail- able for its further examination. A portion of about 50 grams of the sample is then treated with 50% nitric acid (in quantity sufficient to cover the substance) from 5 to 10 C.C. of copcentrated bulphuric acid being also added The mixture is heated until dense brown fumes are evolved diluted and filtered.The filtrate is rendered strongly alka- line with ammonia a slight excess of ammonium sulphide is added and the precipitated phosphates chromium hydroxide and iron lead mercury copper bismuth and zinc sulphides are collected on a filter and washed. The metals are thus obtained practically free from organic matter and may then be separated and identified by known methods. w. P. s.96 ABSTRACTS OF CHEMICAL PAPERS. Microchemical Analysis. IV. Mercury Bismuth Lead Copper Cadmium. NICHOLAS SCHOORL (Zeitsch. anal. Chem. 1908 47 729-754).-The sulphides of the metals are treated with nitric acid and the insoluble mercuric sulphide is separated ; a drop of the nitric acid solution is then heated on an object glass with a drop of sulphuric acid If on diluting with water a white insoluble residue remains it is probably lead sulphate and its presence is confirmed by other reactions.The sulphates of bismuth copper and cadmium are treated with water and if basic bismuth sulphate remains insoluble it is identified by the appearance of the microscopic crystals when it is converted into potassium bismuth sulphate. The solution containing the copper and cadmium is next evaporated the residue is heated to dull redness and treated with water ; cadmium sulphate dissolves whilst copper oxide remains undissolved. Cadmium may be identified by the shape of the crystals when it is converted into either cadmium oxalate or cadmium tetrarubidium chloride. Copper may be identified by the reaction described by Meerburg and Filippo (Abstr.1906 ii 52). w. P. s. Volumetric Estimation of Lead in Ores. JOSEPH A. MULLER (Bull. SOC. chirn. 1908 [iv] 3,1131-1133).-The author has examined the Schwatz volumetric process both in the case of lead nitrate solu- tions of known strength and of a mixture of known composition in- cluding the usual constituents of a lead ore and finds that it gives low results. These are due (1) to the adhesion of some lead sulphate (even in presence of excess of sodium acetate) to the lead chromate when this is precipitated by the standard dichromate used and (2) in the case of the mineral mixture to the difficulty of extracting the whole of the lead especially when the mixture contains ferric oxide as this is liable to form with lead oxide lead ferrate which is attacked with diEculty by sodium hydroxide solution.Weighing the precipitated lead chromate gives better results but it is preferable to weigh as the sulphide as recommended previously (Abstr. 1905 ii 118 119). T. A. H. Decinormal Solution of Potassium Permanganate. BERNARD COLLITT (Pharm. J. 1908 27 724).-Experiments showing that a standard solution of potassium permanganate suffers no loss in strength for at least twelve months if kept in the dark even although the bottle JOSEPH A. MULLER (Bull. Xoc. chim. 1908 [iv] 3 1133-1136).-The author has examined the volumetric methods described by Carnot (Abstr. 1889 311) and by Zulkowki. He finds that the former which depends on the use of a standard solution of hydrogen peroxide gives results which vary with the dilution of the solution titrated Zulkowki's process depending on the liberation from potassium iodide of iodine and titration of the latter with sodium thioaulphate gives trustworthy results if no other oxidising agent is present.En the latter case titration with a standard solution of a lead salt can generally be resorted to but as cshown in a may have to be frequently opened. L. DE K. Estimation of Chromic Acid.ANALYTICAL CHEMISTRY. 97 previous paper (see preceding page) it is safer to weigh the precipitated lead chromate. T. A. H. Electrolytic Estimation of Nickel. AUGUST SCHUMANN (Zeitsch. angem. Chm. 1908 21 2579-2583).-A criticism of the methods proposed from time to time. Fresenius-Bergmann's ammonia method is free from sources of error and contrary to general belief i t is not interfered with by the presence of nitrates or chlorides.Brand's ammonium carbonate method also gives excellent results but the author has not as yet tried this in the presence of nitrates and chlorides. Addition of sodium pyrophosphate is unnecessary. Classen's oxalic acid method cannot be recommended as the nickel deposit is contaminated with carbon. The electrolysis succeeds best by the use of a platinum-gauze cathode a platinum spiral as anode and a weak current. A sufficiency of ammonium sulphate should be present. L. DE K,. Volumetric Estimation of Nickel with Potassium Cyanide. HERMANN GROSSMANN (Chenz. Zeit. 1908 33 1223).-The author has applied this process to mixtures of nickel and cobalt.To the solution is added some sucrose to prevent precipitation of cobalt and the nickel is then precipitated by means of dicyanodiamidine sulphate ammonia and aqueous potassium hydroxide. The precipitate is collected on a filter and re-dissolved in warm dilute hydrochloric acid. When cold a slight excess of ammoria is added and the nickel 'is titrated with potassium cyanide as usual. Further experiments including the estimation of nickel in the presence of zinc are in progress. L. DE K. Separation of Tin Arsenic and Antimony; Analysis of Bronzes. DINAM (Chew,. Zentr. 1908 ii 1207-1208 ; from Mon. Xci. 1908 [iv] 11 600-602).-Three grams of the bronze are heated with 30 C.C. of nitric acid D 1.4 ; the filtrate contains zinc lead and the greater portion of the copper ; the precipitate contains arsenic anti- mony tin and a little copper and lead.It is dissolved in a boiling solution of 10 grams of oxalic acid and 5 grams of ammonium oxalate and after adding a little hydrochloric acid a current of hydrogen sulphide is passed through the hot liquid for two hours. The tin remains in solution and may be deposited electrolytically whilst the arsenic antimony copper and lead are precipitated as sulphides. On treating with boiling aqueous potassium hydroxide the copper and lead are left undissolved ; these are then dissolved.in nitric acid and the solution added to the main acid liquid. The alkaline solution is heated with excess of hydrochloric acid the filtrate is oxidised with potassium chlorate and after expelling the excess of chlorine the antimony is estimated iodometriccllly with potassium iodide and sodium thiosulphate.The precipitated arsenious sulphide is dissolved in potassium hydroxide and also estimated iodometrically in the same manner as the antimony. The acid liquid is concentrated t o about 15 c.c. 3 C.C. of saturated sodium acetate are added and the copper and lead are deposited by electrolysis; the liquid contains the zinc VOL. XCVI. ii. 798 ABSTRACTS OF CHEMICAL PAPERS. which is precipitated by boiling with sodium carbonate and finally weighed as oxide. If the bronze should contain phosphorus this will be found in the liquid from which the tin has been deposited electrolytically and it may be precipitated as ammonium magnesium phosphate or ammonium phosphomolybdate. If iron should be present in the alloy a portion of it will cont,aminate the zinc and another portion remains in the liquid from the tin deposit from which it may be precipitated with ammonium sulphide.L. DE K. Estimation of Antimony and Arsenic in Lead-Antimony Alloys. GEO. M. HOWARD (J. Arrzer. Chern. Soc. 1908 30 1789-1 790).-A slight modification of the author’s process (Abstr. 1908 ii 429). The finely-divided alloy is heated with hydrochloric acid until action ceases the flask is removed from the hot plate and 0.5 C.C. of nitric acid is added. As soon as the arsenic and antimony have dissolved the liquid is boiled for some five minutes and then treated as directed. If the antimony does not exceed 0.1 gram 5 grams of tartaric acid will be sufficient to prevent precipitation.If there is a large excess of lead chloride a larger amount of sodium hydrogen carbonate should be used when titrating the arsenic; the blue colour should be per- manent for at least one minute. In oxidising the arsenic 10 C.C. of 3% hydrogen peroxide generally suffices and the solution must be distinctly alkaline; if this is not so as shown by separation of sulphur a little more sodium hydroxide should be added. L. DE K. Identification of Dihydric Phenols. A Delicate Reaction for Resorcinol. T. SILBERMANN and N. OZOROVITZ (Chern. Zentr. 1908 ii 1022; from BuZ. SOC. Sci. BUCUYBSC~ 19OS 17 41-42).-With formaldehyde in acid solution the dihydric phenols give characteristic resinous insoluble condensation products. When resorcinol is heated with formaldehyde in presence of hydrogen chloride or sulphuric acid a very voluminous flocculent precipitate is slowly formed.The colour of this substance is very pale red but when it is added to con- centrated sulphuric acid o r heated with concentrated hydrogen chloride solution i t changes to a brilliant carmine-red and on the addition of water or when neutralised this colour changes to pale orange. The carmine-red or orange-coloured substance in the presence of free alkali changes to Bordeaux-red. An acid solution of resorcinol (1 100,000) gives a white turbidity with formaldehyde which becomes rose-pink on addition of hydrogen chloride and yields a red solution on the addition of excess of sodinm hydroxide. Catechol with formaldehyde in acid solution gives a very pale yellow flocculent precipitate which changes when boiled with concentrated hydrogen chloride solution to a violet-brown ; dilution with water or neutralisation of the acid changes it to a flesh-pink colour; excess of alkali produces a greenish-brown colour.Quinol requires more acid for condensation with formaldehydeANALYTICAL CHEMISTRY. 99 to take place; a very pale violet flocculent precipitate is obtained which changes to pale brown when boiled with strong hydrogen chloride solution diluted with water or when neutralised and t o olive-green in presence of excess of alkali. J. V. E. The Sodium Nitroprueside Reaction for Acetone. A. C. H. ROTHERA (J. Physiol. 1908 37 491-494).-The following modifica- tion of the test is recommended creatinine not reacting in the manner described. Five to ten C.C.of a solution of acetone in water or urine are taken and a solid ammonium salt (chloride bromide acetate or carbonate) added; then 2 or 3 drops of a freshly-made 5% solution of sodium nitroprusside and 1-2 C.C. of strong ammonia. A character- istic permanganate colour is produced. W. D. H. Detection and Estimation of Formaldehyde in Wine Stored in Barrels which have been Disinfected with Formaldehyde. FRIEDRICH SCEAFFER (Zeitsch. Nahr. Genussrn. 1908,16 674-676).- Barrels which have been treated with formaldehyde and subsequently steamed may still contain sufficient of the aldehyde to contaminate wine which is stored in them. The author has detected traces of formaldehyde in such mines by means of the test described by Arnold and Mentzel (Abstr. 1902 ii 480).Before being tested the wine should be distilled with phosphoric acid and the distillate rendered alkaline with sodium hydroxide in order to decompose the aldehyde- sulphurous acid compound which distils over ; after the lapse of fifteen minutes the mixture is acidified with sulphuric acid and the test is applied. For the estimation of formaldehyde in mine the latter is distilled with phopphoric acid until the volume of the distillate is about three-fourths of that of the quantity of wine taken. The distillate is rendered alkaline with sodium hydroxide and after fifteen minutes is exactly neutralised with sulphuric acid using rosolic acid as indicator. The neutral solution is then shaken with a slight excess of N/1 ammonia (about 2 C.C.are usually sufficient) and at the end of three hours the excess of animonia is titrated with N/10 sulDhuric acid. The estimation der>enda on the combination of the amionia with the aldehyde accordiig to the equation 6CH,O + 4NH = C,H,,N + 6H,O. w. Y. s. Colorimetric Method for the Estimation of Formaldehyde in Milk. EDWARD W. T. JONES (Chem. News l908,98,247),-The method depends on the coloration produced when a mixture of milk formalde- hyde and hydrochloric acid containing a small quantity of ferric chloride is heated. The reagent is prepared by dissolving 0.25 gram of pure iron wire in hydrochloric acid oxidising the ferrous salt with nitric acid and precipitating the iron as ferric hydroxide by the addition of am- monia; the precipitate is collected on a filter washed and then dis- solved in 500 c .~ . of concentrated hydrochloric acid. Ten C.C. of the sample of milk containing formaldehyde and 10 C.C. of the reagent are heated together for twenty-five minutes a t a temperature of about 80' ; 30 C.C. of water is next added and when cold the mixture is passed through 7-2100 ABSTRACTS OF CHEMICAL PAPERS. a filter the precipitate washed with a little water and the filtrate is diluted t o a volume of 100 C.C. The blue colour of the filtrate is then compared with the colorations obtained by similarly treating quantities of pure milk t o which have been added known amounts of formaldehyde. w. P. s. Characteristic Reaction of Uric Acid. DOMENICO GANASSINI (Boll. chint. farm. 1908 47 715-726).-The author gives the follow- ing test for the presence of uric acid or a urate which is not disturbed by the presence of proteins and is not given by xanthine hypoxanthine caffeine theobromine theophylline heteroxanthine pnraxanthine 1 7 - dimethylhypoxanthine 3-methylxanthine carbamide alloxan alloxantin allantoin creatine creatinine glycine tyro sine leucine hippuric acid nuclein nucleic acid or the bile acids.To a small quantity of uric acid or a urate dissolved or suspended in water 10% sodium hydroxide solution is added until the whole is dissolved giving a distinctly alkaline solution. Subsequent saturation of the liquid with potassium persulphate and gradual addition of 10% aqueous zinc sulphate until the precipitate formed no longer redissolves causes the precipitate to assume a bluish-green colour.The reaction is shown distinctly by 10-2Oc.c. of a 0.01% solution of uric acid and is still more sensitive if carried out directly on solid uric acid or a solid urate or the precipitated double urate of silver and magnesium. The reaction may be applied to the detection of uric acid in urine in the following manner Three C.C. of 10% sodium hydroxide solution are added to 10% of urine and the liquid filtered 5 C.C. of the filtrate being treated with 2 C.C. of 10% aqueous zinc sulphate. The gelatinous white precipitate formed when mixed on the filter with a little potassium persulphate will assume a bluish-green colour i f uric acid 1s present. I n blood traces of uric acid may be detected as follows A few C.C. of blood-serum are well mixed with one-half the volume of freshly- prepared Salkowski-Ludwig reagent and left for about twelve hours in the dark. The faint white or grey precipitate is collected and washed five or six times with water on a small filter being kept as far as possible away from the light. A little powdered potassium persulphate and 2 or 3 drops of 10% sodium hydroxide solution are then applied to the precipitate in which a bluish-green colour indicates the presence of uric acid.By this means the author has detected although not in all cases traces of uric acid in the blood of the ox and horse. The blood-serum of birds is also found to contain uric acid which is further met with in samples of blood from healthy and diseased human beings. T. H. P. Iodometric Estimation of Uric Acid [in Urine].FERNAND REPITON (Chem. Zentr. 1908 ii 1139 ; from Rev. gem. Chim. pure appZ. l908,11,285-286).-Twenty C.C. of urine are mixed with 5 C.C. of acetic acid and 20 C.C. of copper tartrate solution which has been bleached by means of a saturated solution of ammonium sulphite areANALYTICAL CHEMISTRY. 101 added. The copper solution should be standardised iodometrically. After the cuprous urate has settled the liquid is made up to 100 c.c. and an aliquot portion of the filtrate is taken to ascertain the amount of copper left in solution. In order to obtain it in the higher degree of oxidation 4 C.C. of sulphuric acid are added and the liquid is boiled t o expel the sulphur dioxide. When cold sodium carbonate is added until a precipitate forms which is then redissolved by means of acetic acid.Potassium iodide is now added and the iodine liberated titrated with standard thiosulphate. The difference in the titrations represents the uric acid L. DE I(. Detection of Salicylic Acid in Wine Milk Butter and Preserved Tomatoes. UMBERTO SAPORETTI (Boll. chim. farm 1908 47 751-755).-The following modified methods based on the coloration given by dilute ferric chloride solution with salicylic acid are more rapid and convenient than those usually employed and are capable of detecting salicylic acid in the dilution 1 80,000. Wine.-Ten C.C. of the mine are shaken in a test-tube with a mixture of 3 C.C. of ether and 1 C.C. of light petroleum previously acidified with 10% hydrochloric acid. The ethereal solution after separation is allowed to flow down the side of another tube containing a very dilute ferric chloride solution as also is a further quantity of the solvent after shaking with the wine.On evaporating the ether and light petroleum by gentle heating the lower liquid gradually assumes the characteristic violet colour. As certain substances in pure wines may give a somewhat similar coloration the presence of salicylic acid may be confirmed by adding a little of the coloured ferric chloride solution drop by drop to water which then turns violet. NiZk-Ten C.C. of the milk are heated to 60-70' with 3-4 drops of acetic acid and the clear liquid removed by a pipette is run t o the bottom of a beaker containing dilute ferric chloride solution; the appearance of a violet ring at the surface of contact of the two liquids indicates the presence of salicylic acid.Butter.-Five to ten grams of the butter are melted in a porcelain capsule and poured into a test-tube the capsule being then rinsed out with 7-8 C.C. of aqueous alcohol (1 part 95% alcohol to 4 parts of water) which is added to the test-tube. After being rendered faintly acid with 10% sulphuric acid the butter is shaken repeatedly warmed slightly and then allowed to set but not solidify. The supernatant liquid is then removed in a pipette and run to the bottom of a beaker containing dilute ferric chloride solution. If salicylic acid is present a violet ring appears where the two liquids meet. Preserved Tomatoes.-To 10 grams of the material,.placed in a porce- lain capsule are added a few drops of 10% sulphuric acid and about 5 C.C.of ether the whole beihg well mixed. The ethereal liquid is then poured into dilute ferric chloride solution and the operation repeated with a few C.C. of light petroleum which is also subsequently added to the ferric chloride solution. On gradually heating the latter if salicylic acid is present the lower liquid slowly assumes the characteristic violet colour. T. H. P.102 ABSTRACTS OF CHEMICAL PAPERS. Bang’s Method of Sugar Estimation and itB Application in the Analysis of Urine. A. C. ANDERSEN (Biochem. Zeitsch. 1908 15 76-94).-The experiments indicate that Bang’s method (Abstr. 1907 ii 136) is applicable to sugar estimations in urine. The error due to the reducing substance normally present in urine is small and this even can be almost entirely eliminated by treatment of the urine with lead acetate or mercuric nitrate.Bang’s method can also be applied to the estimation of sugar in molasses if the solutions are first clarified by the mercuric nitrate method. S. B. S. Estimation of Reducing Sugars. PERCY H. WALKER (BUZZ. Assoc. chim. sucr. dist. 1908 26 341-342).-Results of experiments are given showing that slightly higher figures are obtained when the precipitated cuprous oxide is weighed as such than when it is estimated electrolytically or converted into cupric oxide before weighing (Abstr. 19OS ii 902). The disadvantage of weighing the copper as cupric oxide is that the tables published by the author (Abstr. 1907 ii 585) cannot be used.w. P. s Estimation of Dextrose in Urine with the Weidenhaff‘s Fermentation Saccharometer. GEORG GREGOR (Chem. Zeiztv. 1908 ii 987-988 ; from Zeitsch. ally. Oesterr. Apoth. Ver. 46 41 9-420).-The author who has successfully employed this apparatus of precision recommends that the weight of the mercury should always be taken before each experiment as small globules are easily lost Analysis of Camphorated Oil for Camphor Substitutes. FREDERIC W. RICHARDSON and W. WALTON (Analyst 1908 33 463 -466).-The following process is proposed for the analysis of camphorated oil in order to detect arid estimate synthetic camphor oil of turpentine and essential oil of camphor any or all of which may b e present in addition to natural camphor. Ten C.C. of the camphorated oil are placed in a small retort and heated to a tempera- ture of 200° by means of an oil-bath; a current of dry carbon dioxide is passed through the retort during the heating and the neck of the retort is connected with a weighed two-necked Woulff’s bottle.A weighed small spiral glass condenser is fitted in the second hole of this bottle. The volatile substances collecting in the neck of the retort the Woulff’s bottle and condenser are weighed (the neck of the retort being cut off for this purpose) dissolved in carbon tetrachloride and the solutions are united. This solution is weighed and portions are used for the eqtimation of the specific gravity iodine number and polymerisation with sulphuric acid. The last-mentioned process is carried out by treating a weighed portion of the solution (about one-half) with one-third of its volume of sulphuric acid D 1.84 the acid being added slowly and the mixture cooled.The latter is then distilled in steam and the carbon tetrachloride solution separated from the distillate and weighed; the change in specific gravity and refractive index of the solution enables the weight of the tobal camphors 6s be calculated whilst the polarimetric reading in a when washing the apparatus. L. DE x.ANALYTICAL CHEMISTRY. 103 200 mm. tube multiplied by 0.22385 and divided by 0.95 gives the amount of natural camphor. This deducted frdm the total camphors leaves the quantity of synthetic camphor. When the amounts of tho two camphors are known the iodine number due to turpentine and oil of camphor enables the percentages of the last-named substances to be calculated.The.following iodine numbers are assumed in the calculation natural camphor 5 ; synthetic camphor 7 ; essential oil of camphor lS0 and oil of turpentine 370. w. P. s. Gasometric Estimation of Urea. A. RONCHBSE (J. Pharm. Chim. 1908 28 444-452 ; Bull. SOC. chirn. [iv] 3 1135-1141).- Ten C.C. of urine are mixed with 10 C.C. of dilute solution of basic lead acetate (100 C.C. officinal solution and 150 C.C. of water) and 10 C.C. of the filtrate which is now free from uric acid are treated in the usual manner with sodium hypobromite. A check experiment is then made by means of 5 C.C. of a 2% urea solution and the volumes of nitrogen evolved are compared. If the urine contains sugar a judicious amount of dextrose should be added to the urea solution.If ammonium salts are present these evolve nitrogen which would count as urea. I n accurate investigations it is therefore necessary to estimate the ammonia separately and to calculate the result into urea. The following method is recommended 10 C.C. of urine are diluted to 100 C.C. with water free from carbon dioxide and a few drops of phenolphthalein are added. AT/10 sodium hydroxide is slowly added until the liquid turns a pale rose colour. Twenty C.C. of neutralised formaldehyde (1 1) are now added and the solution is titrated with N/10 sodium hydroxide until the liquid turns pink. A correction is made by adding 0.1 C.C. to every 3 C.C. of alkali used. The sodium hydroxide represents the ammonia. L. DE K.Estimation of Urea in Urine. STANLEY R. BENEDICT and FRANK GEPHART (J. Anzer. C?Lem. Xoc. 19OS 30 1760-1764).-The following process is recommended five C.C. of urine are placed in a test-tube and mixed with 5 C.C. of dilute hydrochloric acid (1 4). The mouth of the tube is covered with a cap made of lead foil and it is then placed in a small autoclave which is heated for nn hour and a half at 150-155'. When cold the contents of the tube are transferred to a 800 C.C. Ejeldahl distilling flask 400 C.C. of water and 20 C.C. of 10% sodium hydroxide are added and the ammonia formed is distilled and titrated as usual. Allowance should be made for pre-existing ammonia. L. DE K. Application of the Carbamino-reaction V. HANS LIEBERMANN (Zeitsch. physiol. Chem. 1908 58 84-91).-Various basic substances in solution were treated in the cold with lime-water and carbon dioxide alternately in the presence of phenolphthalein the gas being passed into the solution until the indicator was only faintly coloured. The filtered liquid was afterwards warmed to 20' with excess of lime water (and in a few cases boiled) and the calcium carbonate thus precipitated was weighed and the nitrogen in the filtrate estimated.In this way the ratio N CO and the degree of completeness of the104 ABSTRACTS OF CHEMICAL PAPERS. carbamino-reaction are ascertained. The ratios found were as follows for piperazine 0.95 piperidine 0.93 coniine 1.56 tetrahydroquinoline 4.07 tryptophan 1 -55 glucobamine 0.99 taurine 0.93. Estimation of Vegetable Alkaloids by means of Mercuric Potassium Iodide [Mayer’s Solution].GUNNAR HEIKEL (Chenz. Zeit. 1908 32 1149-1151 1162-1163 1186-1187 1212-1213). -Mayer’s reagent (6.775 grams of mercuric chloride and 25 grams of potassium iodide per litre) h:ts been used for the estimation of alkaloids by simply adding it to the slightly acid solution so long as a pre- cipitate is formed. The author has sensibly improv’ed the method by adding a larger amount of the reagent than necessary and then titrating the excess with potassium cyanide the excess of which is in turn titrated with standard silver nitrate in presence of ammonia ; the potassium iodide serves here as an indicator. The author communicates a large number of expsriments showing the amount of Mayer’s reagent required to precipitate 0.1 gram of the more important pharmaceutical alkaloids. The results which in some cases depend somewhat on concentration and acidity are not scienti- fically accurate but sufficiently near the truth for pharmaceutical purposes. When applying the process t o drugs these are as a rule extracted with chloroform in presence of ammonia. The solvent is then evaporated and the residue taken up with water acidified with sul- phuric acid and the acid solution is titrated as directed. I n other cases they are simply treated with acid water. Plants are extracted with a solvent immiscible with water and this is lhen shaken with acid water. For exact details of working in the assay of the various drugs and their preparations the original paper should be consulted. S. B. S. L. DE K. Behaviour of‘ Gelatin and Proteose to Bromine Water. ERNST SALKOWSKI (Zeitsch. pl,pioZ. Chem. 1908 57 526-528).- The addition of bromine water to a solution of gelatin causes the formation of a sticky precipitate which has been described as characteristic. h solution of proteose (or gelatose) behaves however in the same way. W. D. H. Diazo-reaction of Atoxyl. PAUL EHRLICH and ALFRED BERTHEIM (Chem. Zeit. 1908 32 1059).-The authors call attention to the fact that the reaction recently described by Covelli (Abstr. 1908 ii 1000) had been described in the literature previously; compare Ehrlich and Bertheim (Abstr.. 1907. i. S12) Blumenthal and Herschmann (Abstr. 1908 (1 613),’and Bertheim’ (Abstr. 1908 i 591). J. V. E. 9

ISSN:0368-1769    

DOI:10.1039/CA9099605089

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

105 General and Physical Chemistry Reflective Power of Ethyl Alcohol. HEINRICH RUBENS and ERIC LADENBURG (Sitxungsber. K. Akad. Wiss. Berlin 1908,1140-1143). -By means of a micro-radiometer the authors have measured the reflective power of ethyl alcohol for ultra-red radiation. In order to avoid errors resulting from the absorption of the radiation in the vapour above the liquid this was coded to a temperature of about - 20. The experimental data indicate the existence of selective reflection this being more pronounced than in similar experiments a t 18'. The maxima on the curve representing the reflective power as a function of the wave-length are all found to be displaced towards the visible spectrum by a lowering of the temperature from 18' to - 2 O O . Whether this is due to the diminution in the absorption of the alcohol vapour in contact with the liquid has not been established.H. M. D. Refraction and Dispersion of Krypton and Xenon and their Relation to those of Helium and Argon. CLIVE CUTHBERTSON and M. CUTHBERTSON (Yroc. Roy. Xoc. 1908 A 81 440-448).-The measurements were made by a method previously described (Cuthbert- son and Metcalfe Abstr. 1908 ii 545). The values of (p - 1).1OG for the green mercury line (h=5461) are for krypton and neon respectively 428.74 and 705.49. The dispersion for krypton is given by the formula p - 1 = 0.0004189(1+ 6*97/h2. loll) and that for xenon by p - 1 = 0.0006823(1+ 10*14/h2.1011) both gases being at normal temperature and pressure. When the refractivities for infinite wave-lengths of helium neon argon krypton and xenon are compared the numbers are found to be very nearly in the ratio 1 2 8 12 20.If the values of b in the equation p - 1 = a(1 + b/X2) are plotted against the refractivities for infinike wave-lengths a straight line can be drawn through the points representing helium krypton and xenon ; the corresponding point for argon is also quite close. On the other hand mercury does not fall into line with the other four monatomic elements in respect of the relationship between refractive and dispersive power. H. M. D. Spectroscopic Investigation of the Behaviour of Metallic Salts in Flames of Different Temperatures. HERBERT AUERBACH (Zeitsch. wks. Photograph. Photophysik. Photochem. 1909 7 30-39).- The apparatus used and details of the photographic method of regis- tration are described.For the production of spectra corresponding with different temperatures the Bunsen ordinary blowpipe and oxygen blow-pipe flames have been employed. No experimental results are given in this part of the paper. H. M. D. VOL. xcvl. ii. 8106 ABSTRACTS OF CHEMICAL PAPERS Radiation and Temperature of the Flame of the Buneen Burner. E. BAUER (Compt. rend. 1908 147 1397-1400).-The absorption and emission of certain rays by illuminating gas flames has been measured. The radiation from a source traversed a con; siderable thickness (3-5 cas) of a homogeneous flame it then passed through a hole in a screen was reflected three times from a polished surface of fluorspar and mas then examined with a micro-radiometer.The absorption which is due to the vapour of water is selective; a flame which absorbs only 11% of the rays emitted by a solid substance giving a continuous spectrum absorbs 28% of the radiation from anothet gas flame. From the emission and absorption measurements with the rays emitted by a solid substance and a knowledge of the emissive power of a black substance in the same position as the flame the temperature of the flame a little above the blue interior cone has been calculated by application of Kirchhoff’s law ; it amounts to 1760 & 50’. Extension of the Principal Series of the Sodium Spectrum. ROBERT W. WOOD (Phil. Nag. 1908 [vi] 16 945-947*).-The ultra-violet absorption spectrum of sodium vapour consists of a Balmer series of lines of which the author has photographed thirty this making the longest Balmer series known.In this series the D-lines appear as the third member whilst the end is a t X 2411. The photographs were obtained by passing the light from a cadmiumspark through a steel tube about one metre long containing sodium vapour at dull-red heat under nitrogen pressure of 15 cms. Fraunhofer Lima of Thallipm and an Error in Rowland’s New Table of Standard Wave-Lengths. CARL FHITSCH (Physihl. Zeittfcch. 1908 9 900-901).-The author points out that Rowland’s table of wave-lengths represents certain thallium lines as belonging to thorium. The spectral line measurements of thallium made by different observers are compared. Re-determination of the Wave-Lengths of the Iron Lines used for Comparison Purposes.A. H. PFUND (Zeitsch. Wit?& Photograph. Photophysik. Photochem. 1909,’? 1-16).-At the instance of the International Union for Co-operation in Solar Research the author has re-determined the wave-lengths of certain iron lines by the interference method of Fabry and Perot. Details are given of the apparatus used and of the method of mounting silvering and polishing the plates of the interferometer. The measurements are tabulated and compared with the results obtained by the same method by Fabry and Buisson and by Eversheim. The independent series of measurements are in very good agreement. Thermal and Chemical Absorption in Banded Spectra JOHARNES STARK (Physikd. Zeitsch. 1905 9 889-894).-The previous speculations of the author (compare Abstr. 1907 ii 147 417; 1908 ii 138 746 911) are supplemented by a consideration of the relationships between coupled bands of the nature of the double * aiid Phyez‘kal Zcitsch.1909 10 88-90. G. S. R. J. C. H. M. D. H. M. D.GENERAL AND PHYSICAL CHEMISTRY 107 and triple linkings in unsaturated compounds of the so-called oxide ’spectra of the metals and of the uitra-violet absorption of saturated valency electrons. In the second part of the paper application of the author’s ideas is made to photochemical phenomena. Primary and secondary photo- chemical changes are distinguished. Primary changes are characterised by the fact that certain valency electrons absorb more energy in the form of light than that corresponding with the energy of combination of the electrons with the atomic or molecular remainders.Three general relationships which hold for primary photochemical changes are deduced from the author’s hypothesis. Theory of Absorption in Gases. L ~ O N BLOCH (Compt. T e d . 1908 14’7 1284-1 286). -According to Drude’s theoryiof dispersion the motion of the electrons is affected by friction and the coefficient of friction T is assumed to be constant (independent of the wave-length). The author shows that in the case of absorption in gases c is a function of the wave-length. Employing the kinetic theory of gases the formula obtained leads to the conclusion that r varies aproximately as the square root of the absolute temperature a deduction in agree- Rotatory Power at Low Temperatures and the Relation between the Absorption of Light and Rotatory Polariaation in Crystale of Cinnabar.JEAN BECQUEREL (Compt. rend. 1908 147 1281-1284).-Cotton (Th&e 1896) has shown that there is a connexion between absorption of light and rotatory power in solution and the author now shows by experiments with well-formed crystals of cinnabar that there is a similar relationship in active crystals. The curve of rotatory dispersion at 18’ and -188O and the flutings in the spectrum at the same temperatures are shown side by side on the same figure. The rotatory power increases rapidly near the absorbed region. On cooling to - 18W the yellow and a part of the red appear and the great rotation appears no more in the orange but is thrown back into the green from which it is evident that the great rotatory dispersion is connected with the absorption.Cinnabar posseses considerable magnetic rotatory power and this property is being further investigated. Magnetic Rotatory Power of the Vapour of Calcium Fluoride and of Nitrous Oxide in the Neighbourhood of their Absorption Bands. A. DUFOUR (Compt. Tend. 1908 147 1471-1472).-1n the case of calcium fluoride the three bands X = 6037 X = 6050.8 and X = 6064.5 were examined. The last shows the normal Zeeman effect the other two the inverse phenomenon. The nitrous oxide absorption bands X = 5854.9 and X = 5846.8 show the ordinary whilst X = 5925.4 and X = 5856.9 exhibit the inverse effect. H. X. D. HUGO RAUFFWANN (Bey. 1908 41 4396-441 2).-Yellow nitroquinol di- H. M. D. ment with recent work by J. Becquerel. Q s. G. S. Nitroquinol Dimethyl Ether and Theory of Solution.S-2108 ABSTRACSS OF CHEMICAL PAPERS methyl ether yields coloured solutions in dissociating solvents and practically colourless solutions in non-dissociating solvents (Abstr. 1907 i 127). Hantzsch claims (Abstr. 1908 ii 447) that the ordinary yellow preparation cannot be the true nitroquinol dimethyl ether ; the latter is colourless and existent in solutions in feebly dissociating or non- dissociating solvents. His claim is based on the assumptions that all true nitrecompounds are colourless and that the molecular refraction of nitroquinol dimethyl ether in feebly dissociating solvents is only slightly greater than the calculated value whilst in solutions in strongly dissociating solvents a pronounced exaltation of the molecular refraction is observed.The author points out that Hantzsch contradicts himself since he states’(Abstr. 1907 i 513) that nitrobenzene shows absorption in the extreme violet which is only another way of saying that nitro- .benzene is not colourless. With regard to the second point it is known that substances containing auxochromes in the benzene nucleus exhi bit abnormally high molecular refractions. Therefore the true nitroquinol dimethyl ether must be that form existent in solutions in strongly dissociating solvents that is to say the yellow modification. The author however rejects the theory of the existence of several modifications of nitroquinol dimethyl ether and accounts for the varying colour of its solutions in different solvents by a novel concep- tion. The outlines of the theory are as follows Since the change of colour of a fluorescent substance in different solvents occurs in general without change of constitution (Abstr.1904 ii 52S) the conception of constitution alone is insufficient. A constitutively unchangeable substance must have some capacity of change within its molecule so that the molecule under different conditions can assume different states. The graphic representation of such states which necessitates the theory of the divisibility of valencies is called the conditioning formula. The substance has in general a single unchangeable constitutional formula and several conditioning formula The constitutional formula is an ideal state to which the conditioning formulae approximate more or less according to the conditions.Furthermore the author assumes that the divided valencies represent lines of force. A line of force starting from an atom of a molecule may terminate either in another atom of the same molecule or in R different molecule the latter case being important in the case of solutions. The molecules of a dissociating solvent have the power of attracting to themselves the lines of force issuing from the molecules of a solute. Non-dissociating solvents on the contrary tend to make the lines of force terminate in the molecule in which they originate. By this theory the author attempts to account for the change of the fluorescent colour of a substance in different solvents (Abstr. 1907 ii D ~ S I R ~ GERNEZ (Ann. Chim. PAY& 1 908 [viii] 15 516-556).-A resume of work already published (compare Abstr.1905 ii 365 430 431; 1908 ii 748) together with a claim far priority against Trautz (Abstr. 1905 ii 494 662). Contrary to Tschugaeff’s generalisation (Abstr. 1905 ii 132) d- I- and r-erythritol 519). c. s. Triboluminescence.GENERAL AND PHYSICAL CHEMISTRY. 109 all exhibit triboluminescence (Bertrand Abstr. 1900 i 424 ; Maquenne Abstr. 1902 i 131). M. A. W. Disintegrating Action of Light and Optical Sensitisation. JOHANNES STARK (Physikal. Zeitsch. 1908 9 894-900).-The dis- integrating effect which ultra-violet light has been found to exert on gold-leaf exposed to its action is shown to be in accordance with theoretical requirements. An experiment is described which appears to show that positively charged atoms are emitted in consequence of the absorption of ultra-violet light.The action of sensitisers in promoting certain chemical changes is discussed in terms of the author’s theory. H. M. D. Concerning the [Luminiferoue] Ether. W. A. KURBATOFF (J. Rzlse. Phys. Chem. Soc. 1908 40 1468-1471).-The author discusses the ether in relation to the atomic and electron theories. T. H. P. Action of Radium- and Rontgen-rays on the Colours of Precious Stones. CORNELIO DOELTEB (Monatsh. 1908 29 11 45-1 170).-A large number of observations are recorded relating to the changes in colour of precious stones and coloured glasses on exposure for different lengths of time to the action of radium- and Rontgen-rays. The colour changes are expressed in terms of the Radde scale. The two kicds of rays appear to act similarly on the coloured minerals.On account of the shorter periods of exposure in the case of the Rontgen-rays a comparison of the activity of the two types of radiation is not possible. I n certain cases the colour changes produced by tbe action of radium are reversed when the stones are heated to about 300° in oxygen or nitrogen. The nature of the colouring substances is discussed. Amethyst smoky quartz rose quartz and citrine are said to contain traces of iron thiocyanate yellow diamonds traces of iron and possibly cerium ruby traces of chromium and possibly iron. Chromium is also probably present as the chief colouring agent in yellow and green corundum and in certain sapphires. H. IN. D. Decay of Radium Emanation when Dissolved in Water.Josh MuRoz DEL CASTILLO (Anal. Fit?. &uim. 1908 6 488-489).-A claim for priority (compare Moore Abstr. 1908 ii 651). W. A. D. Radioactivity of the Atmosphere on Mountains. ALBERT GOCKEL and TH. WULF (Physikal. Zedsch. 1908 9 907-911).- Measurements have been made of the induced activity collected on wires suspended for periods of twenty-four to one hundred hours at various points in the neighbourhood of the Matterhorn. The decay curves indicate that a t a height of about 3000 metres the amount of induced thorium activity is relatively small varying from 0.5% to 10%. The activity of collected rain-water was found to be of the same order of magnitude as that collected in Freiburg (Swit8sTland) at a height of 650 metres.110 ABSTRACTS OF CHEMICAL PAPERS With a special type of electrometer the ionisation due to very penetrating rays mas examined.No influence of elevation on such ionisation could be detected and the authors surmise that this penetrating type of radiation emanates from the earth’s surface. H. M. D. Radioactivity of Italian Gaseous Emanations. RAFFAELO NASINI and MARIO G. LEVI (Atti R. Accad. Linmi 1908 [v] 17 ii 551-553).-The authors have measured the radioactivities of a number of gases of various Italian origins of which they also give certain analytical data. The greatest radioactivity was exhibited by the gas composed partly of hydrogen sulphide from the thermal springs of Abano (Padua). T. H. P G. COSTANZO and C. NEGRO (Jahrb. Radioaktiv. Elektronik 1908 5 395-402. Compare Abstr.1908 ii 551).-The activity of fresh rain-water collected during March and April 1908 was examined by bubbling air through it and leading the gas into the ionisation chamber of an electroscope. I n some cases the rate of discharge was greater when the electroscope was positively charged in others when the charge was negative I f the rain-water is perfectly fresh and especially if its fall is accompanied by atmospheric disturbances of an electrical nature the negative ions are in excess. Radioactivity of Waters from Alange. Josl Mu3oz DEL CASTILLO (Aml. Pis. Quirn. 1908 0 489).-The waters of Alange which have great value in the treatment of nervous diseases have a radioactivity of 1495.9 volts per hour litre. MAX BAMBERGER (Monatsh. 1908 29 1131-1 140).-The radioactivity of spring-water emanating from the South Bohemian granite region in the neighbourhood of Schloss Tannbach has been found to be very high 47-52 Mache units.The rate of decay of the induced activity indicates that the activity is due to disintegration products of radium Radioactivity of Roumanian Mineral Waters. DRAGOMIR HURMUZESCU and N. PATRICIU (Ann. Sci. Uniu. Jccssy 1908 5 159-1 65).-From measurements of the ionising power of the emana- tiop obtained from various mineral waters the authors have compared their radioactivities. These are of the same order of magnitude as the Swiss waters examined by Sury Sarasin Guye and Micheli if the highly radioactive waters of Dissentis and Lavey-les-Bains are excepted. H. X. D Radioactivity of Certain Spring-waters of the Semmering Province.MAX BAMBERGER (Mmatth. 1908 29 1141-1144).- Numbers representing the radioactivity of spring-waters are recorded. The springs emanating From quar tz-phyllite are the most radioactive whilst those from limestone exhibit the property very feebly. Ionisation Phenomena caused by Rain-water. H. M. D. W. A. D. Radioactivity of Certain Springs in Upper Austria. H. M. D. H. M. D.GENERAL AND PBYSICAL CHEMISTRY. 111 SpeqifIc Rdioaotivity of Thorium and ifs Produota. GEOBG~ C. ASHMAN (dmsr. J. SOi. 1909 97 65-72),-The specific aotivity a0 thorium has been deduced from experimental measurements of the activity of new and old thorium (1) freed from the easily separated products thorium=X emanation thorium-4 -23 and -C (2) after a period sufficiently long for the disintegration products to h v e aocumulated in the equilibrium quantities In order to separate thorium and radio-thorium from the other dis- integration products the authors have made use of m-nitrobenaoic acid After four precipitations of the thorium at 80' and at intervals of two hours the disintegration products are completely removed ; the precipitated thorium maitrobenaoate is then heated over a Bunses flame and finally for ten minutes over the blow-pipe.From the measurements specified above the author finds that the specific activity of thorium is 119 This represents 11% of the total activity of the thorium when the equilibrium condition has been reached. Of the remaining activity 20% is due to radio-thorium and 69% to thorium-X and its subsequent products.Heat Development due to Radioactivity of Thorium Oxide. G. B. PEGRAM and H. WEBB (Chem. Zentr. 1908 ii 1851 i from Le Radium 1908,5,271-276).-By means of a thermo-couple the temperature difference has been measured between 4 kilos. of thorium oxide in a Dewar vessel supported in a partly evaouated metal cylinder which was surounded with ice and the ice jacket. A similar measurement was made when the thorium oxide was heated by pass- ing a known current of electricity through a wire embedded in the mass. From these results it is found that the liberation of heat per second per gram is equal to 1.11 x gram- calories per hour per gram. T. H. LABY and G. W. C. KAYE (Phil. Mag. 1908 [vi] 16 879-889).-The authors have measured the ionisation produced by y-rays of radium in air hydrogen and carbon dioxide a t pressures from one to seventeen atmospheres.The y-rays passed through 7 mm. of aluminium and 10 mm. of brass into a flat chamber containing an electrode and filled with the gas under investigation. The ionisation directly induced by the y-rays is supposed to be small in amount and proportional to the pressure of the gas. The main effect is that of secondary p-rays from the alum- inium electrode ; this also varies as the pressure. Secondary P-rays excited in the gas which would produce an ionisation proportional to the square of pressure are not in evidence. The amount ,of ionisation produced in the case of hydrogen was approximately proportional to the pressure. In air and carbon dioxide the ionisation iucreased less rapidly than the pressure part- icularly a t high pressures.This phenomenon is attributable to a soft tertiary radiation produced in these gases by secondary p-rays. This would give a relatively larger effect at low pressures since at higher pressures the gas would be more opaque to it and the range of the prticles would be smaller. H. M. D. watts or 9.60 x J V. E. Gaseous Ionisation and Premure. R. J. C.112 ABSTRACTS OF CHEMICAL PAPERS. Experimental Investigation of the Nature of y-Rays. WILLIAM H. BRAGG and JOHN P. V. MADSEN (Phil. Mag. 1908 [vi] 16 918-939).-The authors adduce further experimental evidence in favour of the theory that y-rays are material and consist of p-particles combined with a positive charge (Abstr. 1908 ii 556).The y-rays from radium were purified as well as possible from p- rays by passing through a magnetic field and then allowed to impinge on plates of various elements. Measurements were made of ionisation on both sides of the plates that is of reflected secondary @-radiation and of emergent secondary P-radiation. The reflected secondary p-radiation depends very largely on the atomic weight of the material of the plate employed but the emergent p-radiation which is almost always greater is of the same order for all the elements. The production of @rays by hard y-rays appears to follow a density law independent of atomic weights but softer y-rays are affected by atomic considerations in that heavier atoms are the more absorbent and produce more secondary p-radiation.The speed and penetrating power of secondary p-radiation are governed by the corresponding properties of the primary y-radiation. The y-rays of radium produce secondary /3-rays which closely resemble the primary @rays of radium in speed. It is argued that the energy of the secondary p-ray does not come from disintegrated atoms but from the exciting primary y-ray. The authors' theory although it requires the existence of positive electrons is held to be simpler and more complete than that advocated by J. J. Thomson. The theory is also applicable to X-rays. R. 5. C. Law of the Optimum of Cathodic Phosphorescence in Binary Systems. GEORGES URBAIN (Compt. rend. 1908 147 1472-1 474).-The discovery of the general relationship in question is not due to the author but to Lecoq de Boisbaudran.I f instead of referring to the entire phosphorescent spectrum the component parts are taken into consideration it is possible to give the law of the optimum a more precise form. According to this if the relative proportions of the active substance and the diluent are varied each phosphorescent band passes through a maximum. Although the maxima for different bands do not necessarily correspond with the same composition of the binary system the proportion of the active eomponent is always very small. Minimum Quantity of Electricity. N. L. M~LLER (Jal~rb. Radioaktiv. Elektronik. 1908 5 402-408).-An explanation is given of the fact that the mass of the a-particle according to electro- magnetic measurements is only 2 whereas if the a-particle be a helium atom it should be 4.If Nis the number of ions in a gram equivalent then 2 x 96540,/N is the quantity of electricity necessary for the separation of a molecule of hydrogen by electrolysis. This is supposed to be taken up by the hydrogen ions at the negative pole. Denoting the quantity by 6 the process of formation of a hydrogen molecule is represented by the equation 2H' + e = H2r. Other molecules oan H. X. DGENERAL AND PHYSICAL CHEMISTRY. 113 be similarly formulated and in the case of helium the formula of the atom is Her whereas that of the a-particle is He and its mass is equal to 2. The direct measurements of ionic charges are discussed in terms of the author's hypothesis. H. M. D. Variation in the Electrical Conductivity at Constant Temperature of Mineral Waters Containing Radium.Jos& MuRoz DE CASTILLO and FAUSTINO DIAZ DE RADA (Anal. Pis. Quim. 1908 6 485-488).-Measurements are given of the electrical conductivity and radioactivity of a number of natural Spanish mineral waters. The authors are collecting data which will enable them to discuss the relationship existing between the changes of conductivity and radioactivity of natural waters. W. A. D. Relation of the Charge to the Mass of the Electron. Comparison of the Values Deduced from the Zeeman Effect and from Recent Measurements with Cathode Rays. A. COTTON and P. WEISS (Compt. rend. 1908 147 968-970).-From measurements of the distance between the side components of certain lines in the spectrum of zinc which become triplets in the magnetic field the value 2 x 1.767 x 10-7 is obtained for elm (e=electric charge m=mass of electron) on the basis of the theory of Lorente; a result practically double that obtained for t,he same ratio from measurements with slow cathode rays.From similar measurements on the helium Bpectrum however Lohmann (Abstr. 1908 ii 243) obtains e/m = 1.77 x 10-7 a value in good agreement with that obtained from observations on cathode rays. G. S. Electrical Resistance of the Alkali Metals Gallium and Tellurium. ANTOINE GUNTZ and WITOLD BRONIEWSKI (Compt. rend. 1908 147 1474-1 477).-The metals were introduced into capillary U-tubes the resistances being compared directly with that of mercury. Sodium potassium rubidium and caesium were obtained from the chlorides by the action of calcium and lithium by decomposition of the hydride.The specific resistances of these metals are recorded for a series of temperatures between - 18'7' and the melting points of the metals. At 0" the values are caesium 19.30 rubidium 12.80 potassium 7.01 sodium 4-30 lithium 8.55. Corresponding with the contraction which takes place on fusion the specific resistance of gallium is greater in the solid than i n the supercooled liquid condition. For the solid the value at 0" is 53.4. The specific resistance of tellurium at 0' is 0.102; it increases with the temperature attains a maximum at about 50° and then diminishes until the melting point is reached. H. M. D. E.M.F. of the Cadmium Normal Element at 0". I. ERNST COHEN and HUGO R. KRUYT (Zeitsch. physikal. Chew. 1909 65 359-370).-Jouaust (Compt.rend. 1908 147 42) has stated that whilst the behaviour of cadmium elements made up with an amalgam gostaining 12.5% of cadmium by weight is regular down to 0" the114 ABSTRACTS OF CHEMICAL PAPERS E.N.P. of different cells containing a 10% cadmium amalgam show9 deviations of several ten-thousandths and these cells show certain other irregularities. The authors now show that there is a small but probably real difference (since it is always in the same direction) not exceeding 0.2 millivolt between cells made up with 10% and 12pL amalgams respectively and consider that this small difference is due mainly to the difference in the concentration of the amalgams i n the two cells in accordance with the equilibrium relations discussed by By1 (Abstr.1901 ii 507). The differences however are not muah greater than those observed with '' identical " cells made up with the same amalgam which may also amount to 0.2 millivolt. The statement of Jouaust (Zoc. cit.) that at 0' the use of a 12.5% amalgam is to be preferred is therefore inaccurate. Certain other of Jouaust's statements are criticised but it is admitted that a further investigation of the electromotive behaviour of cadmium -amalgams betwe& 0' and 30' is desirable. G. s. Electrolytic Processes at the Surface of Electrodes. HANEI G. MOLLLR (Zeitsch. physikal Chm. 1908 65 226-254).-According to Nernst the phenomenon of supertension ( ' I uberspannung ") is connected with the capacity of the electrode material to occlude gases. The author considers that the power of occluding gases is connected with the molecular forces between electrode and gas and hence with surf ace tension phenomena.These theoretical deductions have been confirmed experimentally ; it is shown that there is parallelism between the supertension and the surface tension between gas and electrolyte and also between the supertension and the angle at the junction of gas and electrode. The supertension at different electrodes has been determined by constructing curves representing the variation of strength of current with B.N.F. and the precautions required to obtain accurate results are fully described. The angle 8 between gas and electrode was read off directly by means of a microscope capable of turning on its axis and a special method for obtaining conditions suitable for measurement is described.The relationship between supertension and the two capillarity factors mentioned above has been proved by experiments with mercury at temperatures between 0' and lo' and also with other electrodes the surfaces of which were of different degrees of roughness and in some cases were covered with a thin layer of fat. The relation between 8 and the supertension ?T is represented with great accuracy by the equation T = (eae - l ) / b which holds for all temperatures and all electrodes under any conditions of surface For hydrogen and N/lO sulphuric acid the constant a=O*O264 and b = 9 . It has not hitherto been possible to determine the absolute value of the surface tension at the junction of solid metals but the curve representing the variation of the angle 8 as a function of the polarisation must be parabolic and have a maximum at the game point as the electro-capillary curve.It is shown experimentally thatGENERAL AND PHYSICAL CHEMISTRY. 115 &be mtlximum is the same for all the metals and electrolytes examined provided the electrolyte contains metallic ions but no complex ions and that this value is at zero potential. If the metal is capable of forming complex salts the maximum is displaced. The important result is thus established that the potential difference between electrode and electrolyte disappears when the surface tension at the electrode attains a maximum value ; hence trustworthy results for absolute differences of potential are obtained by the use of the capillary electrometer.G. S. [Oxide Theory of the Oxygen Electrode.] EMIL BOSE (Zeitsch. EZektrochem. 1909 15 1 l-l2),-Polemical in reply to Lorenz (this vol. ii 15). T. E. Electromotive Behaviour of Mixtures of Uranyl and Uranous Salts. ROBERT LUTHER and ARTHUR C. MICHIE (Zeitsch. Elektrochem. 1908,14,826-829).-Uranous salts are strong reducing agents even in acid solutions ; the oxidation by atmospheric oxygen is accelerated by iron salts platinum black and especially by copper salts. The difference of potential between a platinised platinum electrode and a solution of uranous and uranyl salts in sulphuric acid is given by E = c0 + RT/2Plog[U02"][H* J4/[U""] where co is 0.419 volt more positive than the normal calomel electrode or 0.696 volt more positive tban the normal hydrogen electrode.The E.M.P. of mercury-mercurous sulphate electrodes in 0*1N to 1-0N-sulphuric acid is very little affected by the strength of the acid. This is shown to be in quantitative agreement with Luther's views of the dissociation of sulphuric acid (Abstr. 1907 ii 610). T. E. Minimum of Conductivity in the Titretion of Acids. ALFRED THIEL (Zeitsch. Elektrochern. 1909 15 1-4).-Bruni (Abstr. 1908 ii 935 1012) pointed out that the equation by means of which the author calculated the dissociation constants of weak acids from the position of the minimum conductivity of the partly-neutralised solutions (Abstr. 1908 i 787) was based on incorrect assumptions. I n the present paper the author gives the correct equation for the case that the acid is titrated with 0*1N sodium hydroxide (the volume of the solution increasing).The assumptions made are the same as those made by Bruni and the resulting equation becomes identical with his for the limiting case that the volume of the solution does not change during neutralisation. T. E. Formation of Salts and Basicity of Acids. 111. GIUSEPPE BRUNI and 0. SANDONNINI (Zeitsch. Elektrochem. 1908 14 823-825. Com- pare Abstr. 1907 ii 935,1012).-The theoretical equation previously obtained indicates that when an acid the conductivity of which is less than that of its neutral salt is progressively neutralised the con- ductivity must pass through a minimum which is displaced towards the salt end of the curve with increasing strength of acid and increasing dilution.The existence of this minimum is now proved for formic and acetic acids and p-nitrophenol. In all these cases it lies very close to the acid end of the c u m . T. E116 ABSTRACTS OF CHEMICAL PAPERS. Influence of Temperature on the I n t e r d Energy and the Free Energy of Electrolytic Dissociation of Weak Acide and Bases. HARALD LUND~N (J. China. phys. 1908,6 681-698).-The methods by which the heats of dissociation and of neutralisation may be calculated from the hydrolysis and dissociation constants are discussed. The relations between the heats of dissociation and neutralisation respectively and the absolute temperature !P are best expressed by formulae of the type U=f(a b T) for example U= a + bT (U= internal energy ; a and b are constants).The resulting formula are applied to calculate the changes of internal energy and of free energy obtainable in the electrolytic dissociation and neutralisa- tion of a number of weak acids and bases. The temperature-coe5cients of the internal energy dU/dT and of the free energy dA/dT and the inferior and superior limits of these coefficients have been obtained. Brom Nernst's theorem it is shown that dA/dT and dU/dT should have the same absolute value but be of opposite sign a deduction which is in moderate agreement with the facts. Magnetic Properties of Simple Substances. P. PASCAL (Compt. rend. 1908 147 1290-1292. Compare Abstr. 1908 ii 756 927).-It is shown that for diamagnetic substances of the same valency and of analogous chemical properties the atomic susceptibility x (the product of specific susceptibility and atomic weight) is an exponential function of the atomic weight a ; hence the formula logex=a+Pa applies where a and p are constants for the same group but vary especially p with the valency.The validity of the law is shown by observations on the halogen sulphur,and phosphorus groups. It holds independently of the temperature. G. S. Magnetic Dichroism of Calcite and Dolomite admixed with Liquids. GEORGES MESLIN (Compt. rend. 1908 147 1277-1279). -Calcite and dolomite form in association with a number of liquids systems which show magnetic dichroism but the sign of the effect is contrary throughout for the twp substances. I n both cases the change of sign takes place when the refractive index of the liquid exceeds 1.600 ; for calcite the change is from positive to negative at this point and conversely for dolomite Magnetism of the Rare Earths.B. URBAIN and GUSTAV JANTSCH (Compt. rend. 1908 147 1286-1 288).-The magnetic susceptibility of t h e pure sesquioxides of a number of rare earths has been deter- mined with the following results Element ............ Nd. Sa. Eu. Gd. Tb. Dy. Atomic weight ... 144'3 150.4 152.0 157.3 159.2 162.5 Magnetic power ... 33'5 6.5 38.5 161.0 237'0 290.0 G. S. G. S. The relative numbers in the third line are referred to the value for cobalt sulphate heptahydrate = 39.7. The above and other results indicate that there is maximum of magnetic power in the cerium group and a second in the yttrium group. As the magnetic power differs so greatly for closely-allied elements it may be used as a test far the camposition of mixtures.G. S.GENERAL AND PHYSICAL CHEMISTRY. 117 Measurement of Very Low Temperatures. XXII. The Thermo-element Gold-Silver at Liquid Hydrogen Tempera- tures. E KAMEBLINUH ONNES and J. CLAY (Proc. K. A h d . Wetemch. Anasterdam 1908 11 344-345).-The temperature-coefficient of the E.M.K of the gold-silver thermo-element increases rapidly with falling temperature. The great sensitiveness of the element at the temperatures of liquid hydrogen renders it suitable for temperature measurements in this region. H M. D. New Model of the Calorimeter of N. A. Hesehus and Determination by its means of the Specific Heat of Alloys of Tin and Bismuth. N. MARENIN [J. Buss. PAYS. Chem. Xoc. 1908 40 393-398 ; (Phys.Part) ].-This modification of Hesehus’ calori- meter (J. Phys. 1888,489) allows of the weight of water in the calori- meter tube being determined by weighing this tube alone instead of the whole calorimeter. The author has measured for alloys of bismuth and tin containing from 0 to 100% of bismuth (1) the temperatures of fusion ; (2) the specific heats which increase continuously with the content of bismuth and (3) the densities which diminish continuously as the percentage of bismuth increases. T. H. P. Specific Heat of Solid Substances. MAX THIESEN (Ber. Dezct. physikal. Ges. 19OS 6 947-952. Compare Abstr. 1908 ii 653 808 ; Griineisen Abstr. 1908 ii 653).-A consideration of specific heat data for elements in the solid condition leads the author to conclude that the coefficient of expansion and the specific heat vary with the temperature quite differently.With rise of temperature the coefficient of expansion increases the more rapidly. Although the formula given by the author can be used to calculate specific heat values for a wide range of temperatures the empirical relationship pointed out by Griineisen is incorrect. The remainder of the paper is devoted to a consideration of Einstein’s theory of the solid state of aggregation as furnishing a satisfactory basis for a theory of the specific heat of solids. H. M. D. Plait Point Temperatures of the System Water-Phenol. A. KEESINU (Proc. K. Acad. Wetensch. Amsterdam 1908,11 394-397). -Measurements ol critical temperatures for mixtures of water and phenol have been made by heating quartz tubes containing mixtures of known composition in the vapour of pure benzidine in contact with an atmosphere of nitrogen.A minimum critical temperature (357’) was found corresponding with 10% of phenol. The temperatures for pure water and phenol respectively are 3 6 4 ~ 7 ~ and 419.2O. The curve connecting the critical temperatures for mixtures between 10 and 100% of phenol exhibits a point of inflexion. H. M. D. Variation of Trouton’s Constant in a given Homologous System. W. A. KURBATOFF (J. Rws. Phys. Chem. Soc. 1908 40 1493-1501).-The author has collected or calculated the values of Trouton’s constant for members of the following series (1) elements ; (2) inorganic compounds ; (3) saturated hydrocarbons ; (4) poly-318 ABSTRACTS OF CHEMICAL PAPERS.methylene compounds j ( 5 ) homologues of benzene ; (6) ethers and (7) esters. The values for series (3) (Q) and (5) show that the value of the constant diminishes as the molecular weight and boiling point rise. In the first two of these series the constant exhibits a maximum value at b. p. 100-125O. With the ethers too the constant diminishes rapidly as the molecular weight increases. T. H. P. Melting Points. P. B. DALLTMORE (Phawn. J. 1908 [iv] 27 802).-A form of apparatus is described by means of which the m. p.'s of fatty acids waxes and similar substances can be readily determined. It consists of a glass U-tube one arm of which is longer than the other and open at the top. The upper end of the shorter arm is bent at right angles and drawn out to a fine point having a small aperture a t the end.The tube is completely filled with the melted substance and when cold is attached to a thermometer and heated in the usual way the open end of the longer arm being slightly above the level of the liquid in the bath. As soon a8 the m. p. is reached a drop of liquid is forced out of the aperture by the weight of the liquid in the longer arm. E. G. Hydrogen Polysulphides and Cryoscopy. EZIO PAT ERN^ (Atti R. Accad. Lincei 1908 [v] 17 ii 627-633).-1n criticising the conclusions drawn by Bruni and Borgo (Abstr. 1908 ii 102) concerning the formulix of hydrogen polysulphides the author points out that the cryoscopic constant of bromoform is variable and that no values obtained for the molecular weight of sulphur correspond exactly with the molecule S (compare Orloff J.Russ. l'hys. Chem. SOC. 1903 35 642). The calculation made by Bruni and Borgo of the apparent molecular weight when one of the molecules H,S H,S and H,S or a mixture of them exists in solution is faulty since the same results are obtained in all cases where the relation between the numbers of hydrogen and sulphur atoms is constant the total number of molecules also remaining unchanged. The uncertainty of the results obtained by these authors is confirmed by the wmk of Tanatar Choina and Kozireff (Abstr. 1895 ii 41) who found that the depressions of the freezing point of water caused by organic non- electrolytes are not altered sensibly by adding to the water 10 or 20% of methyl or ethyl alcohol whilst with salts the addition of alcohol increases the depressions obtained in water alone.The author has measured the freezing-point depressions of bromo- form produced by varying quantities and proportions of sulphur and carbon disulphide. The mean difference between the experimental results and the calculated ones is 6.8%. Further Bloch and Hohn (Abstr. 1908 ii 5'79 580) and Schenck and Falcke (Abstr. 1908 ii 762) have shown that crude hydrogen polysulphide is not a mixture of H,S H,S H2S7 and H,S but that it contains the two sulphides H,S and H2S3. The melting-point curves of mixtures of selenium and iodine obtained by Pellini and Pedrina (Abstr. 1908 ii 833) do not showGENERAL AND PHYSICAL CHEMISTRY. 219 that these dements do not form a compound but onIy that such compound decomposes before the eutectic temperature is reached.Olivari’s conclusions (this vol. ii 37 39) are also criticised. Law of Corresponding Boiling Points. ULRICH DUHRING (Zeit8cI.b. phgsikacl. Chem. 1909 65 338-340).-8 claim for priority with reference to the discovery of the law in question recently ascribed by Johnston (Abstr. 1908 ii 358) to Ramsay and Young. G. S. T. H. P. Relation between the Capillary Clonstants and the Latent Heat of Vaporisation of the Solvent. PAUL WALDEN (Zeitsch. physikal. Chm. 1909 65 257-288. Compare this vol. ii 122).- It is shown from the available data for over sixty liquids that there is a simple relationship between the heat of vaporisation A and the specific cohesion a2 (a2 = rh where ii is the height to which the liquid rises in a capillary tube of radius r mm.) both determined at the boiling point ; for non-associated liquids A/a2 = 17.9 ; for associated liquids A/az is greater than 17.9.Conversely the heat of vaporisation can be calculated from the above relationship when the specific cohesion at the boiling point is known and a more complex formula is deduced by which the value of X at the boiling point can be calculated from the value of a2 at lower temperatures. When liquids with very divergent boiling points are compared the relationship beween a2 and X is represented more satisfactorily by means of the formula Alas = 46*0/1ogT, where 2’ is the boiling point of the liquid on the absolute scale. By combining the last formula with Van’t Hoff’s formula for the molecular elevation 3 of the boiling point E - OS02P/W the relationship between specific cohesion at the boiling point and boiling-point constant is obtained in the form E = 0~00~43T’,,210g2‘u/u2 a formula which permits of the calculation of E with considerable accuracy.It is further shown that the molecular cohesion Ma2 the molecular heat of vaporisation iKA and the boiling point on the absolute scale are additive in character. For compounds containing only hydrogen oxygen (bivalent) nitrogen (tervalent) and carbon the formula Ma2 = 11*5Sn where 8n represents the sum of the valencies holds within very wide limits. The formula is not valid for compounds containing the halogens on any of the usual assumptions as t o their valehcy nor does it hold for water ammonia or methyl alcohol.The further relations I ’ m = 11 -2273 and MA = 2402n are also shown to hold ih rdany cases. Finally from the formula A/a2 = constant the conclusion is drawn t h a t the molecules of all non-associated liquids are approximately of Latent ‘Heat of Evaporation of isoAmyl Ether. W. A. KURBATOFF (J. Rugs. Phys. Chem. SOC. 1908 40 1471-1474).-The mean specific heat OF isoamyl ether between 24O and 170’ is 0.5721 &0*5% the latent heat of evaporation p being 53.1 cals. with an accuracy of about 1% and Trouton’s constant K 18.8. T. H. P. the same diameter at their respective boiling points. a. s.120 ABSTRACTS OF CHEMICAL PAPERS Latent Heat of Elvaporation and Specific Heat of Naphtha. lene. W. A. KURBATOFF (J. RUSH. Phgs. Chm. Xoc. 1908 40 1474-1477).-Taking the specific heat of naphthalene as 0.32 at 20' and 0.7 at 215O the latent heat of evaporation is found to be 74.7 cals.and Trouton's constant 19.3. The latter figure confirms the observation that in an homologous series Trouton's constant diminishes as the boiling point exceeds 100'. Latent Heat of Vaporisation of Benzoin &oButyl Ether. W A. KURBATOPF (J. Rzcss. Phys. Chem. Xoc. 1908 40,1477-1480). -The latent heat of vaporisation of benzoin isobutyl ether is found to have the mean value 55.7 cals. the greatest deviation from this mean being 1.2%. From this value Trouton's constant is calculated to be 19.3. The only substance having a high boiling point and a high Trouton *constant (21.5) is mercury which is not comparable with other substances owing to the extreme simplicity of its molecular structure T.H. P. Latent Heat of Vaporisation of Acetic Anhydride and Determination of the Association of Liquids. W. A. KURBATOFF (J. Russ. Phys. Chem. Xoc. 1908 40 1480-1487).-The author shows that the value of the Ramsay-Shields constant for determining whether a liquid is associated is greatly diminished by the observations (1) that the magnitude of the constant changes with the molecular weight and that (2) change oE the constant with rise of temperature occurs even with non-associated compounds. The author's measurements of the specific heat of acetic anhydride lead to the meau value 0.4551 f 0.33% for the range of temperature 20-138O. The latent heat of vaporisation is found to be 93.6 + 0.5% at 1384 Trouton's constant calcuated from these results is 22.9.Acetic anhydride is hence associated and is converted into simple molecules a t the moment of boiling. Lithium Strontium and Barium Oxides. ROBERT DE FORCRAND (Ann. Chim. Phys. 1908 [viii] 15 433-490).-8 detailed account of work already published (compare Abstr. 1907 ii 615 683 928; 1908 ii 155 493 764). Using the corrected value for the heat of solution of strontium oxide (Abstr. 19OS ii 765) the heat of formation of strontium oxide is 138.64 Cal. and not 137.6 Cal. as stated (Abstr. 1908 ii 155). The heats of formation of the peroxides of calcium strontium and barium are 157.37 153.07 and 145.58 Gal. respectively and not 157.33 152.10 and 145.71 Cal. as stated (Zoc. cit.) WILLEM P. JORISSEN (Chern.Weekblad 1908 5 8'75-888).-A summary of the literature on heat of hydration and a criticism of the results obtained. A. J. W. T. H. P. T. H. P. M. A. W. Heat of Hydration. Heats of Dissociation of some Electrolytes in Organio Solvents. PAUL DUTOIT and H. DUPERTHUIS (J. Chim. Phys. 1908,8 699 -725).-'I!he electrical conductivity and hence the degree of ionisa- tion of sodium iodide in ethyl propyl isobutyl and isoamyl alcohols,GENERAL AND PHYSICAL CHEMISTRY. 121 and in acetone and pyridine has been determined at intervals of 10' between 0" and 80" (in the case of acetone up to 40") and similar measurements have been made with potassium iodide and sodium and potassium thiocyanates in pyridine. The dilutions employed were from 1000 to 20,000 litres per mol. of salt within which limits Ostwald'b dilution law applies in most cases so that the degree of dissociation can be accurately determined.From the results the heat of dissocia- tion has been calculated by Van't Hoff's formula. Contrary to Walden's statement (Abstr. 1907 ii 437) the heat of dissociation of a salt has not the same value in different solvents ; for sodium iodide as solute it is positive in ethyl alcohol zero in acetone and negative in the other alcohols and in pyridine. Further the heat of ionisation also varies greatly with the temperature in most cases ; in isoamyl alcohol it is - 2008 cal. at 15' and - 16,760 cal. at 75'. On the other hand the heats of ionisation in pyridine of the four salts above mentioned are nearly equal and do not vary much with temperature The fact that for what is presumably the same reaction NaI = Na' + 1' the thermal effect in different solvents is very different indicates that the process in question is not simple; it is probable that combination between ions and solvent is of importance. The differences between the authors' results and those of Walden are ascribed to the fact that the latter observer used erroneous values for the molecular conductivity at infinite dilution obtained by extrapolation from relatively con- centrated solutions G.S. The Density of Liquids Below Zero. JEAN TIMYERMANS (Bull. Xoc. chim. Belg. 1908 22 427-439).-It has been shown previously (Abstr. 1908 ii 85) that none of the liquids studied has a maximuui densityanalogoiis to that of water at 4O. The original experiments which were accurate to the extent of 1 in 1000 have now been repeated more exactly the error not exceeding 1 in 10,000.The present paper relates to the apparatus and experimental methods employed. The measurements were made by means of the dilatometer. A series of the latter were employed in order t o avoid capillary tubes of unwieldy length to cover the range of temperature considered and were calibrated with an accuracy of 1 in 20,000. The apparent internal volume of the dilatometers at 0" was not altered by two hours' immersion in liquid air. The errors due to the meniscus were corrected in the case of mercury as calculated by Schalkwyk and by Gackel and in the case of liquids which '' met " glass by assuming the surface of the liquid in the capillary to be hemispherical.This correction amounts to about 1/10,00Oth of the volume to be measured. With very volatile liquids a correction amounting to about 1/10,00Oth of the total weight had to be made for the weight of saturated vapour in the dilatometer above the surface of the liquid. The densities of the liquids at 0' compared with that of water at 4' were taken as standards and were determined by means of an Ostwald-Perkin pyknometer. The apparatus for maintain- ing the dilatometer at constant and uniform temperatures below 0" consists of a tube to contain a pure liquid (for cooling the dilatometer) solidifying at 8 known temperature below Oo surrounded by a Dewat YOL. XCVI. ii 9-1 22 ABSTRACTS OF OHEMICAL PAPIRS tube provided with a tubulure and stopcock which again is surrounded by another Dewar vessel the walls of thelatter being silvered except over a small space left transparent for reading the volumes in the dilatometer.The outer vessel must be maintained (by means of liquid air or carbon dioxide) at least 15-20° below the solidification point of the cooling liquid. Air is kept between the walls of the inner Dewar vessel until the cooling liquid (which must be kept continually stirred) solidifies (this should occur rapidly throughout the entire liquid) when it is pumped out until the internal pressure is 60-200 mm. according to the difference of temperature of the inner tube and the outer Dewar vessel. This prevents further cooling of the cooling-bath and enables the latter to be kept at a known constant and uniform temperature for some hours.Thus the volume of liquid in the dilatometer can be measured at fixed uniform temperatures below 0'. The temperatures are determined by a Callendar resistance thermometer in conjunction with a Callendar-Griffin bridge by means of which resistances can be measured t o 1/10,00Oth of an ohm. The exact evaluation of the temperature is made according to the calculations of Travers and Gwyer (Abstr. 1905 ii 372). The sole systematic errors of any importance in the work are (1) that in the calibration of the dilatometers equal to 1/20,00Oth of the density (2) that in reducing the scale of the platinum resistance thermometer to the scale of the gas thermometer equal to 1/10,00Oth of the density. The results obtained for ethyl acetate show that the density of this liquid varies according to the expresson Dt = 0.92540 - 0*0011863t Dt being the density at -to t the temperature interval below O' and 0.92540 the density at 0".The greatest difference between the observed densities and those calculated by this formula is only 0*00014. E. H. Expansion Coefficisnt Speciflc Gohesion Surface Tension and Molecular Weight of Solvents. PAUL WALDEN (Zeitsch. physihl. Chem. 1908 65 129-225).-The densities of a number of carefully purified liquids which have considerable solvent power have been determined a t Oo 25" and 50°. From these results and the available experimental data on the density specific cohesion and surface tension of a large number of liquids and the variation of these properties with the temperature certain relationships are deduced between these properties themselves and between the physical properties and molecular weights of the solvents in question.The general formula Vt = Vo/(l - I$) proposed by Mendelkeff to represent the variation of the density of liquids with temperature has been tested by application to the data for forty-nine different liquids including some liquefied gases. It is valid for liquids boiling below loo" but only mQderately so for liquids boiling a t bigher temperatures k varies for different liquids between 0*000178 and 0.00316. For non-associated substances the '' expansion modulus," k is inversely proportional to the critical temperature t on the centigrade scale and in many cases kt,=0*34. For certain liquefied gases and other liquids with low critical temperatures the value of kZ\=GENERAL AND PHYSICAL CHEMISTRY.123 constant = 0.49 the critical temperature being measured on the absolute scale. There is also parallelism but not proportionality between the expansion modulus and the compressibility of liquids. The data a6 to the surface tension y for over fifty liquids are taken from the results of Ramsay Guye and others ; those for the '' specific cohesion," a% are mostly calculated from the values of y by means of the equation uz= 2~/9*81cl where d is the density. In some cases the y values are calculated from the experimental values of a2 by means of the same formula. The variations% of the surface tension and the specific cohesion respectively with the temperature are repre- sented through a wide range of temperature by the equations yt = yo( 1 -@ and at2 = a,2(1- k,t) where p and k are constants for any one liquid but vary with the nature of the liquid.It is sbown that for non-associated liquids constant = 0.94. From these equations the critical temperature can be calculated when /3 or k are known and it is shown that the calculated and observed results are in good agreement. Other methods which have been suggested for calculating critical temperatures are discussed. Further the quotient of the latent heat of evaporation at the boiling point A by the specific cohesion at the bame temperature is constant and -17.9. Combining this with the mathematical expression for Trouton's rule JlAu/Tu=20*7 where M is the molecular weight of the liquid the equation MC~~~/Y' = 1.16 is obtained and is shown to be valid for non-associated liquids (compare Kistiakowsky Abstr.1906 ii 655). For associated liquids this expression is no longer constant but is smaller the more the liquid is associated. We have thus a new method for determining the molecular weight of liquids which appears to give more consistent results than any other method so far suggested. In the first instance the above equation only applies to observations at the boiling poiat but a rather more complicated equation is derived which admits of the calculation of the molecular weight from capillary observations at any temperature. When allowance is made for the fact that Trouton's rule is only valid over a limited range of temperature a more accurate formula M= 0-4351'JogTc/cc2 is obtained and is applied to the determination of the molecular weight of liquefied gases and other liquids.Of the ten liquefied gases considered only hydrogen chloride is considerably associated (association factor = 1-32). The association factor for cadmium is rather less than unity; it is therefore monatomic in the liquid state. When instead of the specific cohesion the surface tension y is used the expression $A/Yyu=3*64 is obtained where Y is the molecular volume and the other factors have the same significance as above. Combining this with Trouton's rule we obtain YyU/Tu = 5.67. These expressions are shown to be valid for a large number of non-associated liquids but for associated liquids the quotients are less than 3.64 and 5.67 respectively and from.the observed values the degree of association can be calculated. According to Eiitvcis-Ramsag-Shields the temperature-coefficient of = constant = 1 *16 and that k,t 9-2124 ABSTRACTS OF CHEMICAL PAPERS the molecular surface energy " should be constant for non-associated liquids that is d(yVj)/dt = constant = 2.12. The above considerations however lead to the conclusion that d(yV)/dt should be constant and it is shown by application to twenty-four typical liquids that the latter expression varies less than the former ; the mean value is 8.80. For associated liquids the value is less and from the above equation the degfee of association can be calculated as in the case of the Eotvos equation. The results obtained by the two methods are in satisfactory agreement.G. S. Liquefaction and Compressibility of Gaseous Mixtures. A Case in which Combination Occurs. E. BRINER and E. CARDOSO ( J . C'hi7n. Phya 1908 6 641-680).-The gases were liquefied by means of liquid air or solid carbon dioxide and ether and purified by fractional distillation. The compression was effected with a Cailletet pump the compression tube contained a stirrer worked by a magnet and the pressure was measured on a nitrogen manometer. The compressibilities and vapour tensions of certain binary mixtures and of the components separately have been determined at different temperatures. A mixture of sulphur dioxide and methyl ether in equivalent pro- portions liquefies with very little alteration of pressure and the vapour- pressure curve of the system shows a minimum a t the same composition from which the conclusion is drawn that a compound SO,,Me,O exists.The critical temperature of a mixture of this composition is 152-5" between those of the compouents and the critical pressure 62 atmo- spheres. From the variation of the pressure of the binary mixture with temperature it is calculated by means of Van't Hoff's equation that the heat given out by the reaction Me,O(gas)+SO,(gas)= Me,G,SO,(solid) is 11.8 cal. between 50° and 100' and 8.7 cal. between 13s' and 147'. No evidence of combination has been obtained in the following binary systems methyl ether and methane methyl ether and carbon dioxide and methyl ether and nitric oxide. G. S. Relation between Surface Tension and Speoiflc Volume of Non-associated Liquids. REGINALD 0.HERZOCI (Zeitsch. E'kktro- cherra. 1908 14 830-831 ).-By combining Avenarius' equation for the dependence of specific volume on temperature with Van der Waals' equation for surface tension and temperature the author obtains logy + pv = c where y and v are surface tension and specific volume a t the same temperature and p and r specific constants of the substance. The relation is shown to hold good for six liquids. The relation p = 5.28 times the critical density is also trua T. E. Supertension and Viscosity. CHARLEEI MARIE (Cornpt. rend. 1908 147 1400-1402).-The effect of variations in the viscosity of the electrolyte on the excess voltage required to liberate hydrogen at different electrodes dipping in N/l-sulphuric acid has been examined.When the supertension is small the effect of increased viscosity is slight thus 0.5% of gelatin raises the supertension a t platinisedGENERAL AND PHYSICAL CHEMISTRY 125 platinum electrodes at most by 0.001 volt but for metals with high supertension the effect is much greater thus 0.1% of gelatin raises the supertension a t lead electrodes by 0.05 volt. G. S. Viscosities and Limiting Conductivities. PAUL DUTOIT and H. DUPERTHUTS (J. Chim. Phys. 190S,6 736-731).-Walden (Abstr. 1906 ii 335) has shown that for tetraethylammonium iodide i n organic solvents the product of the viscosity 7 of the solvent and the molecular conductivity at infinite dilution pa is independent of the nature of the solvent and of the temperature i y .~ ~ = 0.7 approximately. The authors have determined the viscosities at intervals of loo between OOand 40' (in some cases up t o SOo) of the seven solvents already mentioned (see this vol. ii 120) and show that Walden's rule is not of general validity. The product qpm is not the same for the different solvents nor does it tend towards a fixed value as the temperature rises. A t 0' the extreme values are 0.374 (in isoamyl alcohol) and 0,573 (in pyridine) and at 80' the extreme values are 0.225 and 0.559 (in the same solvents). Further 7pw varies with the temperature; in four of the solvents it diminishes and in one it hcreases with increase of. temperature. The variations are consider- able in some solvents ; from SOo to Oo qpa increases by 47% in isoamyl alcohol and by 25% in isobutyl alcohol.G. S. Adsorption. LEONOR MICHAELIS and PETER RONA (Biochem. Zeitsch. 1908 15 196-21 6).-Determinations were made of the adsorption of acetone by charcoal and the results were found to agree with the theory of Gibbs and Freundlich. The adsorbabilities of acetone in the presence of acetic acid or acetic acid in the presence of acetone by charcoal were also determined and it was found that the simultaneous presence of two adsorbable substances diminished the adsorbability of either. The phenomenon of the diminution of adsorbability by the presence of a second adsorbable substance was not observed however in the case of proteins and certain dyes. I n the case of the former substances there is a further peculiarity in that the adsorption process is not reversible.This was thought t o be due to the conversion of the protein into an insoluble form such as takes place on coagulation but the same phenomenon takes place when albumoses are adsorbed and it was experimentally shown that in this case the presence of acetone does not diminish its adsorbability by charcoal. The conclusion is drawn that the adsorption of proteins is not a simple mechanical process but depends probably on the electrical properties of the surfaces. s. B. s. Coefficient of Diffusion. BASIL W. CLACK (Phil. Mag. 1908 [vi] 16 863-879).-The author has endeavoured to elaborate an accurate method of measuring the diffusion coefficients of dissolved salts and to determine to what extent diffusion depends on concen- tration.The solutions under investigation were enclosed in a glass bulb into which a diffusion tube 4 cm. long was sealed in such a way that the end projected 2 CIP. ioto the bulb The bulb was suspended is126 ABSTRACTS OF CHEMICAL PAPERS. distilled water beneath the pan of a delicate balance SO that the weight of its contents could be neasured automatically from time t o time. As salt diffused out of the bulb tha solutions contracted and water entered to make up for this contraction at nearly constant rates so long as the concentration was not appreciably diminished. A steady distribution of concentration being established in the diffusion tube an equation could be deduced connecting the rate of loss of weight of the bulb with the coefficient of diffusion. The results obtained are held to show that the method is capable oE yielding accurate values when certain conditions of experiment are observed.The following diffusion coefficients a t 0’ are given KNO in 10% solution 0,844 in 5% solution 0.870; KCl in 20% solution 0.972 in 10% solution 0.954. R. J. C. Osmosis of the Alkali Haloids. FRANZ WIEMERS (Ann. Physik 19OS [iv] 27 1081-109S).-Measurements have been made of the relative changes in concentration which take place in solutions of the halogen salts of the alkali metals when the solutions are separated from water by a membrane of pig’s bladder. The data are used to calculate the so-called endosmotic equivalent the quantity of water which in a given time replaces unit quantity of the dissolved substance. The endosmotic equivalent decreases as the molecular weight of the dissolved haloid salt increases.It is independent of the temperature although the absolute magnitude of the two diffusion currents increases with rise of temperature in consequence of the greater velocity of the molecules. With increasing concentration of the solution the diffusion currents incream in magnitude but since the flow of water increases more rapidly than that of the salt solution the endosmotic equivalent is greater the more concentrated the solution. H. M. D. Osmotic Pressures of Aqueous Solutions of Calcium Ferro- cyanide. I. Concentrated Solutions. EARL OF BERKELEY ERNALD G. J. HARTLEY and C. V. BURTON (Phil. Frans. 19OS A 209 177-203).-Porter’s equation taking account of the effect of compressibility of solvent and solution on the relation of osmotic to vapour pressures (Abstr.1907 ii 743; 1908 ii 670) can be modified and applied to determinations of vapour pressure made in air a t atmospheric pressure instead of under vacuum conditions. Whilst Porter’s equation yields results differing from the authors’ experiments by 2 or 30/ the modified equation is in close agree- ment with experiment. The authors have endeavoured to increase the accuracy of their vapour-pressure determinations i n order to render the correction for compressibility significant. Determinations were made a t 0’ of osmotic pressure vapour pressure and compressibility of concentrated solutions of calcium ferrocyanide. The purest salt recrystallised to eliminate potassium consisted of yellow crystals containing 11 H,O. I n previoiis measurements of vapour pressure by the bubbling method an unexplained loss of weight occurred in the whole apparatusGENERAL AND PHYSICAL CHEMISTRY.127 as well as in the particular bulb containing the solution. The complete elimination of rubber bubing from the apparatus and the substitution of mercury seals although an advantage was not entirely satisfactory because a ponderable amount of mercury now volatilised. Finally plat inurn-irid ium connecting tubes with ground-in junctions. were used throughout and no appreciable source of error was found in the method so modified. Determinations of osmotic pressure were carried out as previously described (Abstr. 1906 ii 599). The amount of calcium ferrocyanide leaking through the copper ferrocyanide membrane was found to be practically nil A special form of piezometer was employed for compressibility determinations.The compressibility tube was made of Jena glass the compression coefficient of which has been determined by Straubel to be 228 x 10-8. A check experiment made by the authors gave the value 223 x loTs. Possible sources of error particularly those due to temperature were carefully guarded against. The concordance of observed osmotic equilibrium pressures and those calculated from vapoiir pressures and compressibilities by the modified Porter’s equation is held to indicate a satisfactory agreement between experiment and thermodynamic reasoning R. J. C. Contact Pyrogenetio Oxidation of Eydrogen and Carbon Monoxide by Air E.I. ORLOFF (J. Buss. Phys. Cham. Soc. 1908 40 1590-1595),-The author has studied the oxidation of excess of hydrogen and of carbon monoxide by air in presence of copper or platinum gauze under such conditions that the contact material is heated by the oxidation process. The results are given in detail and do not admit of condensation (compare following abstract). T. IT. P. General Conditions of Contact Oxidations accompanied by Auto-heating of the Contact Layer. E. I. OBLOFF (J. Russ. P~TJB. Chem. Soc. 1908 40 1596-1603. Compare preceding abstract),- These contact oxidations are divided into two classes (I) reversible reactions such as 2H2+02 t 2H,O 2SO,+O2 ZZ 2SO and 4HCl+ 0 dH20 + 2C1 ; (11) reactions which are not reversible under the experimental conditions such as 2CO + 0 = 2C0 and 4NH + 30 = 2N2 + 6H,O.Class I.-In this case the velocity of flow of the mixed gaseg is without influence on the magnitude of P.C,/C,!a which has the con- stant value 0.55 C and C representing the initial concentrations of the hydrogen and oxygen respectively and C the concentration of the water vapour. In contact with the heated layer of copper or platinum gauze the gases occupy a volume Vm greater than the volume V they occupy after leaving this layer and cooling. If T is the ratio of the initial speed to the mean speed of the gases and 1p and Kl the concentrations of the hydrogen and oxygen respectively in the final gases (C2.Cl/r2)v2 = (K2E,)”. Inserting the values of C2C,/r2 and P . K l given by the four experiments previously described (see preceding abstract) the quotient Vm/V is found to be 6 6-87 6.87,128 ABSTRACTS OF CHEMICAL PAPERS.qnd 6.8. If to represents the fall of the temperature of the gases on leaving the heated contact layer Vm/V= 273/(273 - t ) from which to = 227O 233O 226O and 230'; using a contact layer 8-12 cm. in length the actual difference of temperature between the heated and unheated parts was found to be approximately 230'. Class II.-In this case not only the concentrations but also the speed with which themixed gases meet the contact layer is of import- ance and unless the velocity of flow reaches a certain value in each particular case no heating of the contact layer takes place. For the oxidation of carbon monoxide and methyl and pt-opyl alcohols the con- stant C2C,/P2 has the values 0 *022-0-031 0.00103 and 0-000103 respectively C and C being the initial volume concentrations of the carbon monoxide etc and of the oxygen respectively and Y the mean velority of the gaseous mixture.From the equation (C2Cl/r2)" = (XZKJy it is calciilated by means of the experimental numbers obtained (see preceding abstract) that X / Y = 2 * 0 4 3.21 and 3.1. It is found experimentally that the ratio of tbe absolute temperature of the heated portion of the contact layer to that of the cool portion T1/Tz has the approximate value 2 from which it is deduced that Ti/T2= X/Y. Replacing X and Y in the equation given above by T1 and Y\ respectively an expressiou is obtained showing that increase of r decrease of V and increase of Tl/T2 all cause increase of the reaction between carbon monoxide and oxygen. With methyl and propyl alcohols the primary oxidation is accompanied by decomposition of the alcohol and oxidation of the decomposition products whilst with ammonia part of the nitrogen originally formed is oxidised to oxides of nitrogen.T. H. P. Polyiodides. P. OLIVARI ( A t t i R. Accad. Lincei 1908 [v] 17 ii 584-590).-The author has studied the influence of the solvent on the relation z/y = 8 between the concentration x in gram-mols. of iodine dissolved and the concentration of an insoluble iodide (KI) passing into solution to form polyiodides (K12n+l). The results show that all the alcohols acids esters ketones cyauo- and nitro-derivatives on which iodine has no chemical action allow of the formation of polyiodides.The solubility of potassium iodide in presence of iodine increases approximately with the dielectric constant of the solvent. With solvents having analogous chemical functions the ratio 0 and also x increase and consequently the absorption of potassium iodide diminishes with increase of the molecular weight of the solvent that is with increase of its anomalising power and with decrease of its dielectric constant. Comparison of the results obtained with solvents having different chemical functions shows that the absorption of potassium iodide depends on the anomalising property as well as on the dissociating power of the solvent. The solvents which increase the ratio 8 do so in the following order acetic acid (9*7) ethyl acetate (6.1 l) ethyl alcohol (25-8) nitrobenzene (36*4) ethyl bromide (9) hydrocarbons (Z) the numbers in brackets representing the respective dielectric constants.As regards anomalising power the series CO,H CO,R OH NO Br 1GENERAL AKD PHYSICAL CHEMISTRY. 129 Me is in very good agreement with the series given by Auwers (Abstr. 1903 ii 268) considering that these groups are not uuited t o the same radicle in the solvents investigated. With different iodides and the same solvent it is found t h a t when the solutions of iodine are dilute almost identical values of 6 are given by the iodides of any one group of the periodic system With concentrated solutions however deviations occur in a definite sense which seems to indicate that they bear a relation to the electropositive character of the metal.Diminution of the latter character is accom- panied by a diminution in the absorption of the iodide by a nitro- benzene. solution of iodine. T. H. P. Kinetics of Alkylation. HEINRICH GOLDSCHMIDT (Zeitsch EZek trochem. 1909 15 10-11).-The experiments of Acree and his upils (Abstr. 1908 ii 919) do not prove the existence of tautomeric r orms in solution as they are equally well explained by the supposition that the alkyl halide is added on t o the anion of the salt in two different ways the two complex ions yielding the 0- and N-ethers tespectively . T. E. Researches on the Formation of Eaters. HEINBICH GOLD- SCHMIDT [with M. ASRIEL v. KOREN LUND and OLAF UDBY] (Zeitsch. Elektrochent. 1909 15 4-lO).-Kailan (Abstr. 1908 ii 936) finds that the rate of esterification of trichloroacetic acid without a catalyst is not in agreement with the theory of hydrogen ion catalysis.The author therefore gives a rAsum6 of the unpublished results which he has obtained during the past few years. The rate of esterification of tri- and di-chloroacetic acids is increased slightly by the addition of a salt of the acid. that of formic acid is much diminished. With di- and tri-chloroacetic acids the reaction is of the second order ; with formic acid the second order constants rapidly diminish but are constant in presence of a formate ; the aromatic sulphinic acids give a reaction lying between the first and second orders. Probably in these cases the hydrogen ion catalysis is of secondary importance some other reaction accounting for the main part of the ester formation.The esterification of formic acid using picric trichloroacetic tri- chlorobutyric and dichloroacetic acids as catalysts was studied in alcohol dried with calcium. The addition of the piperidine salt of the acid diminishes the rate of change the effect being larger with the weaker acids. The catalytic action of hydrogen chloride is not affected by the addition of a chloride. The conductivity of the alcoholic solutions of the acids was also measured and the catalytic action is found to be almost proportional to the conductivity of the solutions. The rates of esterification of formic acid by picric acid in different concen- trations are also nearly proportional to the conductivities of the solutions. With weaker acids the agreement was not so good possibly the non-dissociated complex of catalytic acid and alcohol reacts slowly with the acid to form the ester the effect being superposed on that of the hydrogen ion.The addition of water to a solution of hydrogen chloride in absolute alcohol diminishes its130 ABSTRACTS OF CHEMICAL PAPERS. conductivity to a minimum; for all other acids the conductivity increases steadily. It follows from the theory of hydrogen ion catalysis that the ratio of the catalytic accelerations produced by two acids must be independent of the nature of the acid undergoing esterification. The ratio of the rates of esterification of acetic acid in presence of hydrochloric and picric acids is 13.5 ; for propionic acid it is 13.1 ; for m-butyric acid,;l3*l ; for phenylacetic acid 13.8 ; and for phenylpropionic acid 13.0.The ratio of the accelerations of hydro- chloric and sulphosalicylic acids is also found to be the same with five acids. The formation of isobutyl and methyl esters in presence of hydro- chloric acid is studied. The equation obtained by the aiithor and Udby (Abstr. 1907 ii 852) applies in these cases as well as in that of the ethyl esters. The rates of esterification of acetic and phenylacetic acids are determined at different temperaturep and the temperature- coefficients found to be the same All these results are in good agreement with the theory of hydrogen ion oatalysis developed by the author (Abstr. 1907 ii 853). The self-esterification of an acid however appears to be mainly due t o some other reaction.T E. History of the Discovery of the Rules of the so-called (( Steric Hindrance.” FRIEDRICH KEHRMANN (Ber. 1908 41 4357-4358).-8 claim for priority in the statement of the phenomanon of steric hindrance. The author foreshadowed this in 1888 (Abstr. 1889 243) and called attention (inter alz’a) to the difficulty of esterifging o-substituted carboxylic acids in 1890 (Abstr. 1890 484) whilst V. Meyer’s first paper on this subject was published in 1894 (Abstr. 1894 i 243). J. C. 0 Physico-chemical Investigation of the Reactions between Egg-albumin and Acetic Acid. LUDWIK ZOJA (Zeitsoh. Chem. Ind. Kolloide 1908 3 249-269).-On the addition oE acetic acid to dialysed egg-albumin the viscosity of the resulting solution increases with time and under certain circumstances the end result is a solid jelly The process of gelatinisation has been studied by measurements of viscosity electrical conductivity and density.The variaCion of the viscosity with time depends very much on the concentration of the acetic acid. Below 3.22 mols. per litre the viscosity remains constant ; with increasing acetic acid concentration the rate of alteration of the viscosity with time increases attains a maximum at 7.01 mols. per litre and then decreases as the acid concentration is further increased. On the other hand the electrical conductivity does not change with time and the curves which represent the dependence of the con- ductivity on the acetic acid concentration are closely similar to the corresponding curves for acetic acid-water mixtures.Both curves exhibit a maximum a t about 3.2 mols. acid per litre. The change of viscosity with time is supposed to be due to an action of hydrogen ions on the particles of the colloid. I n agreement with this it is Found that the rate of gelatinisation is greater when the acetic acid is replaced by formic acid aud less when replaced by propionic acid.GENERAL AND PHYSlCAL CXEMISTRY. 131 Observations relating to the influence of calcium acetate indicate that the reaction is catalytically accelerated by calcium ions. The increase in viscosity takes place more rapidly at 25’ than at higher or lower temperatures when the other conditions are maintained c o ~ s tant. H. H. D. Hydration in Solution as the cause of certain Solubility Influences. C.S. HUDSON (Zeitsch. EZektrocham. 19OS 14 831-823 ; J. Amr. Chem. Soc. 1909 31 63-66).-The solubility of anhydrous sodium sulphate in water is diminished by the addition of carbamide whilst that of Glauber’s salt is increased. The author supposes that the solution contains molecules of the anhydrous salt and molecules of the hydrate ; in presence of the solid anhydride the concentration of the former is a that of the latter is h. The total solubility of the anhydrous salt is therefore s=cl+h. Tf p is the vapour pressure of the solution h/a=const. pn. The addition of a foreign substance to the solution diminishes p and therefore diminishes h also since a (in presence of the solid anhydrous salt) is constant. The solubility of the anhydrous salt is therefore diminished by the addition of a foreign substance to the solution.Precisely the same argument applied t o the hydrated salt shows that its solubility must be increased. T. E. Theory of Colloidal Solutions. LUIGT ROLLA (Atti R. Accad. Lincei 1908 [vJ 17 ii 650-654).-The author has carried out a series of experiments on metallic colloids with the object of determin- ing the charge of the granules and the relation between charge and mass making use of Stokes’s formula. The colloids examined were Eredig’s platinum and various preparations made by Zsigmondy ’s method. Using a P.D. of 13 volts between electrodes i cm. apart the time required to traverse uniformly a path of 0.125 mm. was found to be four seconds for the gold granules and 4.3 seconds for those of platinum.The mobility or velocity for a field of 1 volt per cm. is hence 26.0 x 10-5 crns. per sec. for gold and 24.0 x loe5 crns. per sec. for platinum. Burton’s measurements (Abstir 1906 ii 275) gave the values 21.6 x crns. per sec. for gold and platinum respectively. Electric transport measurements made on red violet and blue colloidal gold solutions prepared according to Zsigmondy’s method (Abstr. 1898 ii 522) show that the method of preparation does not influence the nature of the colloidal metallic solution obtained the charge of the granules remaining practically constant. The radii of the gold granules measured by means of a hmnato- meter were found to be red gold 192 x low5 crns. ; violet gold 1.7 x crns. ; blue gold 2.0 x cms. If the granules carrying a charge e move in an electric field of intensity + they are subjected to an electric force e+ and their velocity is given by k+ where k is their mobility.Owing to the very great dilution (0.00006 gram of gold per c.c.) the internal friction 7 will be sensibly thb same as if the granules moved in pure water. According to Stokes’s law the velocity of spheres of radius r iq 8 and 20.3 x132 ABSTRACTS OF CHEMICAL PAPERS. medium having the internal friction 7 under the influence of a force f=e+ is given by the expression v = e+/6nr)r and since v=k+ e = 6 ~ 7 & r . The experimental determinations give the value 7 = 0*01782/(1 + at). The charge of Bredig's gold granules is hence e= 12.19 x electrostatic units the values for the other colloids being Zsigmondy's red gold 9.75 x ; violet 12.19 x lo-'"; blue 16.2 x lo-''); Bredig's colloidal platinum 11.32 x 10-10. Tbe charges on the granules are hence of the same order of magnitude as the charges carried by the ions.T. H. P. Behaviour of Colloidal Suspensions with Immiscible Solvents. W. LASH MILLER and R. H. MCPHERSON (J. Physical Chem. 1908 12 706-71 6).-The experiments were undertaken to ascertain if colloidal suspensions distribute themselves between t w o immiscible solvents on shaking. No such distribution was observed in the case of two liquids ; the colloid usually coagulated on shaking (compare Winkelblech Abstr. 1907 ii 17). More definite results were obtained with ternary systems which form two layers in the neighbourhood of the " plait point )' (the point at which the layers become almost identical in composition).The binodal curve tie-lines and plait point have been determined directly at room temperature for a number of ternary systems such as water-chloroform-alcohol water-chloroform-acetone and water- alcohol-ether by a simple method. No distribution was observed with colloidal arsenious sulphide in the first two systems but in the latter systgm and in certain other systems distribution was observed in the neighbourhood of the plait point. It is however only for relatively clear solutions which approach true solutions in character that distribution has so far been obtained. G. S. Has the Crystallising Force any Influence on Properties in the Amorphous Condition. Latent Heat of Vaporisation of p-Toluidine. W. A . KURBATOFF (J.Buss. Phys. Chem. SOC. 1908 40 1487-1492).-The latent heat of vaporisation of o-toluidine m. p. - 40° b. p. 198" is 95.1 and Trouton's constant 21-6 (compare Luginin Abstr. 1903 ii 7). The author's measurements of the latent heat of vaporisation of p-toluidine m. p. 45O b. p 199*5O give the value 9 1-8 Trouton's constant being consequently 20.6 the normal value. p-Toluidine is hence non-associated and o-toluidine associated. The author regards this difference as due to the difference in the crystallising powers of the two compounds. The crystallising power hence seems to be a molecular force and to influence the properties of the compound in the amorphous condition. The values of the Ramsay-Shields constant are different for the two toluidines being 1.72 for the p-compound between 107' and 210*6O and for the o-compound 2.04 a t 8.1-108.4° and 2-06 at 108.4-208*5°.T. H. P. Forms of Matter. 11. P. P. VON WETMARN (Zeitsch. Cham. Ind. I1TbZZoide 1908 3 283-304).-An account is given of methods which have been used in the preparation of crystalliue substances in so-calledGENERAL AND PEYSICAL CHEMISTRY. 1.38 colloidal amorphous forms. According to the author’s theory (crystallisation theory of colloids) the amorphous condition has no real existence ; “ amorphous ’’ substances represent sponge-like forms- tions consisting of extremely minute crystals In a large number of cases it has been shown that crystalline substances can be obtained i n “ colloidal ” form and conversely “colloidal” substances i n crystalline form by suitable variation of the conditions under which separation from solution takes place.The character of the precipitate which separates from a solution as the result of a chemical change (for example the double decomposition of two salts) depends on the rate of formation and the solubility of the solid phase the degree of association of the components of the solution which react to form the insoluble substance and on the viscosity of the !iquid medium. The fact that the rate of formation of the solid and the association of the components of the solution both increase when the concentration of the solution increases enables the process of crystallisation to be regulated by varying the concentration of the solution. Starting out from solutions just saturated with respect to the slightly soluble substance and progressively increasing the con- centration of the reacting solutions it is possible to distinguish five concentration intervals according to the crystalline character of the the substance which separates out.The character of the barium sulphate precipitate which is obtained on mixing differently concentrated solutions of barium thiocyanate and manganous sulphate is described and illustrated by photographs. The following t intervals of concentration are distinguished. Between X/ZO,OOO and N/7000 no precipitation takes place even when the solution is left for years. Between N/7000 and N/600 well-developed crystals separate out whilst between N/600 and 0.75N the precipitate consists of star-shaped and needle-like aggregates.From 0*75N to 3N ‘‘ amorphous ” precipitates are obtained distinguishable under the microscope as spherical granules whilst between 3N and 7rV ‘* amorphous ” precipitate separate which cannot be differentiated either by the aid of the microscope or the ultra-microscope. It is shown that the ‘‘ amorphous ” forms obtained in the fourth and fifth concentration intervals are actually crystalline. The minuteness of the crystals which result from these concentrated solutions is probably due for the most part to the very high velocity of formation. The conditions for the preparation of a stable suspension of barium sulphate are considered and it is shown that such a stable suspension can be obtained by mixing alcoholic solutions (N/50O-N/lO) of barium thiocyanate and cobalt sulphate.This is due to the increase in the number of centres of crystallisation consequent upon the diminished solubility of the barium sulphate. H. M. D [Forms of Matter.] MAX M~NDEN (Zeitsch. Chem. Ind. Kolloide 1908 3 304-505).-A claim of priority in respect of P. P. von Weimarn’s paper (preceding abstract). The author points out that he has previously demonstrated by microscopic observations that all forms of matter organic and inorganic are fundamentally identical H. M. D.134 ABSTRACTS OF CHEMICAL PAPERS. [Form of Matter.] 9. P. VON WEIMARN (Zeitsch. Chsm. $ad. Xolloids 1908 3 305).-In reply to Munden (preceding abstract) the author states that the question of the identity of living and dead matter has not been considered by him.Conservation of Weight. CONSTANTIN ZENGELIS (Zeitsch. physikal. Chern. 1909 65 341-358. Compare Abstr. 1906 ii 831). -It is shown by a number of different methods that many gases and vapours of solids can pass through glass even at the ordinary temperature. I n one set of experiments substances such as stannic sulphide and iodic acid mere supported inside a glass beaker inverted on a glass plate the junction between plate and beaker being closed by para&n. On the outside of the beaker at the same height as the material inside tt piece of silver foil was fixed and the whole arrangement was surrounded by a large inverted beaker also closed air-tight with paraffin. After some days the silver foil showed evidence of the action of the solid which must therefore have passed in the form of vapour through the glass.I n another set of experiments chlorine bromine and iodine were sealed up in separate flasks on the outside of which were fixed strips of silver foil and the flasks were then enclosed in separate air-tight vessels. The silver outside the chlorine vessel showed signs of attack after fifty days that of the bromine vessel in about the same time but in the case of iodine there was distinct action in three days. The effect was much more rapid when the outer vessel was exhausted. The rate of action is not proportional to the volatility of the substance and in some cases at least is not markedly accelerated by a moderate rise of temperature. The effect is the more rapid the thinner the glass walls. The author considers that Landolt's experiments contrary to the latest views of Landolt himself (Abstr. 1908 ii 366) afford evidence of a real loss of weight in certain chemical reactions and that the loss of weight is due to the passage of vapours through the glass walls. The fact that there is no loss of weight when the inner surface of the vessel is coated with paraffin (Landolt) is in favour of this view. H. &I. D. G. S. Are the Stoicheiometric Laws Intelligible without the Atomic Hypothesis? FHANZ WALD (Chem. Zeit. 1908 32 1249-1250 1276-1279. Compare Abstr. 1908 ii 367).-Polemical. A furthsr reply to Kuhn (Abstr. 1908 ii S26). Combining Power of Metallic Atoms with Atoms of the Same Kind. LEOPOLD RUGHEIMER (Anlzalen 1908 364 5 1-631.- I n a previous paper (compare Abstr. 1905 ii 576) the author has pointed out that the tendency of atoms of metals to link together is very small even in non-ionised compounds ; the only definite exception is tin triethyl which according to Ladenburg has the formula Sn,Et (from vapour density determinations). The author has re- determined the molecular weight of this compound by the boiling-point method ethyl ether being used as solvent. I n the moat dilute solution W. H. G.INORGANIC CHEMISTRY 135 the value found is not much greater than that corresponding with the formula SnEt but it increases rapidly with the concentration so that the substance shows a considerable tendency t o associate. The remainder of the paper is occupied with a discussion on the nature of valency. G. 8. Physical and Chemical Properties as Functions of the Magnitude of the Qranules (Number of Molecules in the granule) of the Solid and Liquid Phases. P. P. VON WEIMARN (J. Izuss. Phys. Chem. ~ o c . 1908 40 1434-1447).-The author gives a rdaumd of the literature on this subject and bhows that some of Pawloff's conclusions (Abstr. 1908 ii 92'7) are in entire disagreement with the results of previous investigators (compare also Abstr. 1908 ii 90 263 1023). Method to Avoid Cracking Vacuum Vessels whilst Manipulating Liquid Air. ENRIQUE HAUSER (Anal. Pis. Quim. 1908 6 428-429).-8 tube of paper rolled several times on itself is introduced into the mouth of the vacuum vessel so as to fit it closely and to pass halfway to the bottom of the vessel and project an equal distance outside. The liquid air can then be poured out through this tube without undergoing violent ebullition in the neck and without risk of cracking the vacuum vessel. T. H. P. W. A. D.

ISSN:0368-1769    

DOI:10.1039/CA9099605105

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

125 Organic Chemistry. Chemical Action of the Electric Discharge at Low Tempera- tures. E. BRINEU and E. L. DURAND (J. Chim. Phys. 1909,7,1-30). -Most of the results described in this paper have been published already (Abstr. 1907 ii 759; 19OS ii 101 940). By the action of the electric spark on a mixture of nitrogen and ethane at -7S0 carbon hydrogen nitric acid ammonia and higher hydrocarbons ara obtained the latter being formed by polymerisation. I n siffiilar experiments with a mixture of nitrogen and acetylene similar products were obtained but in the latter case the proportion of hydrogen cyanide predominates over that of the ammonia. I n the action of the silent discharge on ethane alone at - 78O no carbon is liberated but there is considerable formation of higher hydrocarbons.Under similar conditions a mixture of equal volumes of nitrogen and ethane also gives a relatively high proportion of higher hydrocarbons and less hydrogen cyanide khan when the spark discharge is used. The effect of the electric discharge is very complicated and it appears that the laws of chemical stadcs are not applicable ; kinetic and atomic considerations afford a better guide to the phenomena. G. S. isoOctane [P-Methylheptane]. LATHAM CLARKE (J. Amer. Chern. Soc. 1909 31 107-116. Comparo Abstr. 1907 i 169).-/3-Methyl- heptane is the ninth hydrocarbon of the series C8H to be prepared. It may be easily obtaiued by either of the following processes (1) Me*CO*CH,*CO,Et -+ Me*CO*CH( CH,-CH,PrP)*CO,Et -+ Me*CO*[CH,],*PrP -+ CHMe(OH)-[CH,],*Pi P -+ CHMeI*[CH2]3-Prp -+ Me*[CH2],*PrS.CHPraI*CH,Prfl -+ h!fe*[CH,],*PrP. Methyl kohexyl ketone has b. p. 165'/764 mm.; Welt gives b. p. 167-168O (Abstr. 1895 i 202). It is reduced by sodium and ethyl alcohol to methylisohexylcarbinol b. p. 1 'i6'/765 mm. (compare Welt loc. cit.) and rnethylisohexylpinacme PI+*[CH,]~*CM~(OH)*CM~(OH)-[CH&*PI~ a liquid b. p. 293-295'/765 mm. by hydrogen iodide into +odo-/3(+?etramethyZdodecan-[-ol PrS*[CH,~,.CMe(OH)*CMeI.LCH,I,*PrP an unstable colourless oil (compare Clarke and Shreve Abstr. 1906 i 473). Methylisohexylcarbinol is converted by red phosphorus and iodine into l-iodo-P-rnethylheptane a colourless heavy oil which when reduced with a zinc-copper couple yields isooctam (/3-methylheptane) CH3*[CH2],*BrB a colourless liquid b.p. 116O/761 mm. Di 0.7035 fig 1.3944. The reduction may also be effected by acting on the iodo- octane with magnesium in dry ether and treating the organo-magnesium compound with water. (2) PraMgI + CH2Pr P*CHO -+ CHPra(OI-1) *CH,PrP -+ The latter compound is converted YOL. XCVI. i. k126 ABSTRACTS OF CHEMICAL PAPERS. Propyl magnesium iodide and isovaleraldehyde interact in dry ether forming an additive product which when treated with water yields P-met?~yZ-6-heptanoZ CH Pra(O€I)* CH,Pr~ a colourless liquid b. p. 164'/760 mm. If the reacting substances are not quite dry isoamyl alcohol and a glycol CH2Prfi*CH(OH)*CH(OH)*CH,Prf3 a colourless viscid oil b. p. 238-242"/760 mm. are formed. P-Methyl-8-heptanol is converted by red phosphorus and iodine into 6-iodo-/3-methyZheptane which is reduced by a zinc-copper comple to P-methylheptane.W. H. G . Production of Iodoform [from Carbon Dioxide]. GABRIEL QuPaIw (J. Pharm. Chim. 1909 [vi] 29 54-55).-Potassium hypo- chlorite added gradually to an aqueous solution containing ammonia potassium hydroxide 10% of potassium iodide and 5% of potassium carbonate forms nitrogen iodide which at first disappears on shaking. When the disappearance becomes slow a large excess of ammonia is added which causes an almost immediate precipitation of iodoform. G. B. Reactione between Iodoform and Silver Fluoride and Chloride. WILLIAM OECHSNER DE CONINCK (Bull. Xoc. chirn. 1909 [iv] 5 62-63. Compare Auger Abstr. 1908 i 494).-On gently heating silver chloride and iodoform in the correct proportions sus- pended in dilute alcohol the following interaction takes place 3AgCl+ C KI = 3AgI + CHCI,. No gas is evolved whereas if silver fluoride is taken (as Auger has shown) the products are carbon monoxide and hydrogen fluoride with a little carbon dioxide 3AgF + CHI + H20 = 3AgI + 3HF + CO.Preparation of Absolute Alcohol. M. EMMANUEL POZZI-ESCOT (BUZZ. Assoc. Chirn. sucr. dist. 1909 26 580).-Ninety to 95% alcohol is digested with aluminium foil in presence of mercuric chloride and then distilled. The product consists of absolute alcohol free from R. J. C. aldehydes and acetals. L. DE K. Butane-P-ol [Methylethylcarbinol] and its Tartrates. J. RICH^ (J. Pharm. Chirn. 1909 [vi] 20 57-60).-'l!his alcohol synthesised from acetaldehyde by Grignard's reaction could not be resolved into its optical antipodes by fractional esterification with tartaric acid.G. B. Pinacolyl Alcohols. MAURICE DELACRE (Bull. Xoc. chim. 1909 [iv] 5 109-1 13).-The author questions the accuracy of the follow- ing conclusions given in L. Henry's recent papers on pinacolyl alcohols (Abstr. 1907 i 374; 1908 i 881; this vol. i 79).- (1) That the haloid esters of sec.-pinacolyl alcohol (methy1tert.-butyl- carbinol) undergo isomerisation when heated yjelding haloid esters of tert.-pinacolyl alcohol (dimeth ylisopropylcarbinol) ; (2) that since on dehydration with acetic anhydride both pinacolyl alcohols yield a mixture of By-dimethyl-AS-butylene and By-dimethyl-ha-butylene in which the former largely preponderates it may be assumedORGANIC CHEMISTRY.127 gennera2Zy that the hydroxyl of a :C(OH)* group placed near a :CHo and a -CH,. Froup exhibits a marked but not exclusive preference for the H of the .CH* group and (3) that in the dehydration of dimethyliso- propylcarbinol by acetic anhydride containing aulphuric acid the anhydride acts by first forming dimethylisopropylcarbinyl acetate which is more readily dehydrated than the parent alcohol. The author contends that the first statement is refuted by the results given in his previous papers (Abstr. 1907 i 578; 1908 i 243) and that the second conclusion is inadmissible since the relative proportions of the two hydrocarbons formed vary with the conditions of the experiment. The validity of the third point he has examined by treating dimethylisopropylcarbinyl acetate with dilute sulphuric acid and finds that the acetate is scarcely dehydrated at all under conditions in which the alcohol undergoes complete dehydration (Abstr.1906 i 921). P. CLAESSENS (Bull. Soc. chim. 1909 [iv] 5 113-1 18).-$-Butylethylene (yy-dimethyl-ha-butylene CMe,*CH:CH,) described by Delacre (Abstr. 1902 i 79) furnishes a liquid dibromida b. p. 91-92'/14 mm. (approx.) 203'/762 mm. (decomp.) Do 1,616 which becomes coloured on keeping is readily soluble in organic solvents and when heated with potassium acetate and acetic acid in a closed tube at 200' is converted into bl.onto-yy-dimethyZ-A"-bztyZe~e b. p. 120-130° Do 1.165 which was not obtained pure. On oxidation with permanganate yy-dimethyl-ha-butylene yields trimethylacetic acid and is therefore an exception to Wagner's rule that on careful oxidation with permanganate ethylenic hydrocarbons yield the corresponding glycols (Abstr.1888 i 665). With iodine and yellow mercuric oxide the hydrocarbon yields the corresponding iodohydrin D 1.481 which decomposes at 1 loo but is volatile in steam. On treatment with potassium hydroxide solution this yields the corresponding gZyco2 CMe,*CH( OH)*CH,*OH D5O 0.940 b. p. 205-'206' m. p. 32-33' which is crystalline and hygroscopic. The glycol dissolves in hydrochloric acid from which it can be recovered unchanged. With acetyl chloride it yields apart from a small quantity of a chlorinated compound a dimetyl derivative b. p. 213-215O Do 1.014 which is a liquid of pleasant odour and readily soluble in water alcohol or ether.Couturier's hydrocarbon &di- methyl-ha-butylene (Abstr. 1893 i 244 and Delacre Abstr. 1902 i 79) can also be converted into the corresponding glycol through the iodohydrin. This glycol furnishes a chloroacetate on treatment with acetyl chloride and dissolves in hydrochloric acid yielding a chlorinated product which decomposes on distillation. T. A. H. +-Butylethylene Glycol. T. A. H. New Method for Preparation of Ethers. JEAN B. SENDEBENS (Compt. rend. 1909 148 227-229).-The author has recorded pre- viouslg the decomposition of alcohols into ethylenic hydrocarbons and water by the catalytic action of precipitated alumina at 300" (Abstr. 1908 i 494 495 ; ii 166). It is now found that this substance at a lower temperature can effect the quantitative dehydration of 11.2128 ABSTRACTS OF CHEMICAL PAPERS.alcohols with production of the corresponding ethers. Thus alcohol in the state of vapour is passed over alumina (prepared by acidifying a solution of sodium aluminate) at 240-260° and the products passed through a Y-tube cooled in ice. It is not necessary to use absolute alcohol. The products condense to a liquid which separates into two layers ; the upper layer consists of ethyl ether in :a state of greater purity than commercial ‘* rectified ether.” Methyl ethet and pr’opyl ether have been prepared in the same manner. W. 0. W. Action of Acids on Sodium Ethyl Thiosulphate. 111. AUGUST GUTMANN (Bey. 1909 42 228-232. Compare Abstr. 1907 i 671 ; 1908 i 497).-The action of alkalis on sodium ethyl thio- sulphate is represented thus NaEtS,O + KOH = NaKSO + EtSOH.Bunte (Bey. 1874 646) represents the corresponding acid hydrolysis in the following manner NaEtS,? + H,O = NaHSO + EtSH. The author finds that sulphurous acid is also produced whether the reaction is carried out in concentrated or dilute solution or in presence of much or little acid The other products are ethyl sulphide sulphuric acid and ethyl mercaptan. Probably the change in acid solution as in alkaline is a t first HEtS,O,+H,O=SO,+ H20 + EtS*OH. Subsequently in acid solution the sulphurous acid reacts with one or two molecules of thioethyl hydroperoxide thus EtS*OH + SO = EtSH + SO ; 2EtSoOH + SO = Et,S2 + H,SO,. That this explanation is correct is shown by the fact that if after alkaline hydrolysis a solution of sodium ethyl thiosulphate is rendered acid and kept sulphuric acid is formed.In view of these results thiosulphuric acid can no longer be given the constitution SO,<: ascribed to it by Bunte but it must exist as the two isomeric forms S 0 2 < ~ o E and S02<rr. O*SH . E. F. A. Acid Glycerophosphates. P. CARRS (Bull. SOC. chim. 1909 [iv] 5 109).-With reference to a paper by Self (Pharm. J. 1908 26 627) it is pointed out that the process described by that investi- gator for the preparation of barium hydrogen glyceryl phosphate namely the addition of sulphuric acid to barium glyceryl phosphate until the mixture is neutral to helianthin has been shown by the present author on a previous occasion to yield a mixture of the normal glyceryl phosphate and glyceryl dihydrogen phosphate (Abstr.1904 i 133 215 819). T. A. H. The Nitrogen of Lecithin and other Phosphatides. HUGH MACLEAN (Biochem. J. 1909,4 38-58).-The nitrogen of the com- mercial preparation of lecithin termed ‘‘ lecithol ” (Riedel Berlin) is probably all present as choline. I n the lecithin of heart-muscle there is probably another nitrogen- containing group in addition. The base of cuorin is probably not choline. W. D. H.ORGANIC CHEMISTRY. 129 Allylxanthic Acid. BERNARDO ODDO and GIOVANNI DEL Rosso (Gaxzetta 1909 39 i 11-23).-Study of allylxanthic acid and of its salts and other derivatives shows that in some ways the xanthic acids are comparable with hydrogen sulphide and with cyanic and thiocyanic acids. Potassium SK*CS*O*C,€I and sodium ccllylxccnthates SNa*CS*O*C,H obtained by the action of excess of carbon disulphide on a solution of potassium (or sodium) hydroxide in allyl alcohol at a low temperature form white gelatinous precipitates which dry in the form of faintly yellow silky needles.With copper sulphate these salts react accord- ing to the equations BSK*CS*O*C,H + CuSO = (C,H,*O*CS*S*),Cu + K2S0 and Z(C,H,*O*CS*S*),Cu = (C t3,*O°CS*S*)2Cu2 + C,H,=O*CS*S*S*CS*O*C,H (compare Ragg Ab;tr. 1908 i 604) the cupi*ous allylxantAate formed being insoluble. The allylxanthic radicle in the potassium and sodium salts may be estimated by titration with standard copper sulphate solution using s-diphenylcarbazide as indicator (compare Oddo Abstr. 1903 ii 758). The following salts of allylxanthic acid were also prepared silver C,H,OS,Ag zinc ( C,H,OS,),Zn lead (G4H2OSJ2P.b nickel (C4H50S2),Ni cobalt (C4H50S2)2C02 mercury cadmaurn tin bismuth iron platinum and gold.Allylmnthic acid SH*CS*O*CH2*CH:CH2 is obtained as a faintly ycllow unstable oil heavier than water and on distillation decom- poses into allyl alcohol and carbon disulphide. The methyl ester SMe*CS*O*C,H is a pale yellow oil b. p. 200-203° DZ4 1,1214 with an alliaceous odour and has the normal molecular weight in freezing benzene. The ethyl ester C,H,,OS is an oil b. p. 210-212° DB 1.0690 resembling the methyl derivative in odour and having the normal molecular weight in freezing benzene. The ally.! ester C,H,,OS is obtained as a brownish-yellow oil b. p. 231-253” having a very pungent garlic-like odour and exhibiting normal cryoscopic behaviour in benzene.T. H. P. Selenomercaptans and their Derivatives. LEO TSCEUGAEFF (Ber. 1909 42 49-54).-Ethyl propyl and butyl selenomercaptans have been prepared by heating on the water-bath a solution of sodium hydroselenide obtained by saturating a 10% alcoholic solution of sodium ethoxide with hydrogen selenide with about 5.h less than the calculated quantity of the alkyl iodide or bromide in an atmosphere of hydrogen. The selenomercaptans are heavy liquids with a foul persistent odour which are insoluble in water react in the usual way with mercuric oxide and yield coloured precipitates with the salts of heavy metals particularly of lead and thallium. Selenomercaptans are extremely autoxidisable in air yielding diselenides R-Se2*R.The hydrogen of the *SeH group reacts with magnesium methyl iodide methane being evolved quantitatively. Selenides R*Se*R” are obtained by treating an alcoholic solution of sodium ethoxide and the selenomercaptan with an alkyl iodide or bromide all in equal molecular quantities; in the absence of air the yield is nearly quantitative. Diselenides of the type R*Se*[CH,],,*Se*R result by the130 ABSTRACTS OF CEIXWCAL PAPERS. action of dihaloid hydrocarbons on the sodium selenomercaptides 2NaSeR + Br[CH,],Br = R*Se[CH,],*Se-R + 2NaBr. With ethylene dibromide however the main product is diethyl diselenide ethylene being evolved. R*Se* [CH,],*Se*R are colourless liquids somewhat stable in air whilst diselenides of the type R*Se,*R are yellowish-red liquids which distil undecom posed only in a vacuum.In the accompanying table the density refractive index and coefficient of expansion (a) are measured at the temperature 6O. The selenides and the diselenides of the type B. p. 1". D:. a. n,. EtSeH ........................ 53'5" 24 1.3954 0'0018 1.47715 PraSeH ........................ 84 20 1-3020 - 1.47560 BuaSeH ........................ 114 24-5 1'2352 0'0012 1-47446 MeSeEt ........................ 86 23 1'3134 - 1 -4820 MeSePra ..................... 114 20'4 1'2445 - 1-48121 MeSeBua 141 24'5 1'1875 - 1.47710 PraSePra ..................... 159 24-3 1'1427 0*00113 1-47494 PrclSe,'Pra ..................... 99/13 min. 22'2 1'4991 0.00127 1.55535 EtSe'{CH,],*SeEt ........... 135/15 mm. 24 1'4630 0*00129 154892 The atomic refraction of selenium in the selenomercaptans is 10.78 i n the selenides 10.91 and in dipropyldiselenide 11.33. C.S. Solidiflcation of Mixtures of Water and Soluble Fatty Acids. A. FAUCON (Compt. rend. 1909 148 3$-39).-The freezing-point curves of the systems water-formic acid water-acetic acid and water-propionic acid have been determined. The respective eutectic points and the molar composition of the eutectic mixtures are as follows H*CO,H + 1*14H,O - 48' ; Me*CO,H + 2*40H,O - 2'7" ; Et*CO,H + 0*57SH,O - 29.4'. In no case is there evidence of chemical combination. The system butyric acid and water is being further investigated. G. S. Behaviour of Fatty Acids in Arnold's Distillation Process. A. HEIDUSCHKA and K. PFIZENMAIER (Pharm. Zentr-h.1909 50 85-86).-With reference to the publications of Dons (Zsiteh. Ndw. Genussm. 1907 14 150) and Arnold (ibid. 1908 16 705) on the subject of the fatty acids of butter the author has investigated the behaviour of each of the acids formic acetic propionic butyric hexoic octoic decoic lauric myristic palmitic stearic oleic and linoleic when mixed with water and distilled. It was found that (1) the distillate may have a constant composition which has no relation to the composition of the mixture under distillation or (2) its composition may vary with that of the mixture under distillation or (3) it may exhibit a combination of (1) and (2) being of constant composition for a certain concentration of the mixture under distilla- tion and exhibiting a proportional composition for other concentrations.A table of experimental results is given in the original. ..................... T. A. H Total Asymmetric Syntheses. ALFRED BYK (Ber. 1909 42 141-242).-Mainly a criticism of Henle and Haakh's paper (this vol. i 6). J. J. S.ORGANIC CHEMISTRY. 131 General Method for the Preparation of Trialkylacetic Acide. ALBIN HALLER and ED. BAUER (Compt. rend. 1909 148 127-132. Compare Abstr. 1908 j 987; this vol. i 108).- Trialkylacetophenones of the type COPh-CRR'R are dissolved in benzene or toluene and boiled for five hours with sodamide. The ketone undergoes decomposition into benzene and an amide of the type C RRR"mCO*NH2 which is readily converted by nitrosyl sulphate into the corresponding acid CRRR'*CO,H. Attempts to bring about a similar reaction in the case of dialkylallylacetophenones however have not been successful.The following new compounds have been prepared in this way aa-dimethyl-n-bzctyramide CMe,Et-CU-N H m. p. 103-104' ; aa-dimethyl-n-valeramide CMe,Pra*CO*NH2 m. p. 95-96' ; aa-dimethyl-n-valeric acid CMe2Pra*C02H b. p. 10 1-102"/ 1 1 mm. 1 90-200' under ordinary pressure ; a-methyl-a-etl&yl-n-butyr- amide CMeEt,*CO*NH m. p. 78-79" ; aa-cliethyl-n-b~tyranzide CEt,*CONH m. p. 108' b. p. 148-149'/30 mm. ; aa-diethyl-n-butyric acid CEt,*CO,H m. p. 39.5' b. p. 119'/14 mm. 220-222' under ordinary pressure ; a-methyl-a-ethyl-n-valeramide CMeEtPra*CO*NH2 m. p. 464 b. p. 134-135"/12 mm. ; a-methyl-a-ethyl-n-valeric acid CMeEtPF*CO2€€ b. p. 215-220". w. 0. w. Further Applications of the General Method of Hydrogenation Bwed on the Use of Finely-divided Metds. PAUL SABATIER and ALPHONSE R~AILHE (Anlz.Chim. Phys. 1909 [viii] 16 70-107).-Mainly a resume of work already published (compare Abstr. 1905 i 571 635 ; 1906 i 561 ; 1907 i 458 488 490 587 747; 1908 i 36 278 529) but the following facts have not previorisly been recorded (1) unsatnrated acids of the aliphatic series yield the corresponding saturated acid when directly hydrogenated in the presence of nickel ; thus crotonic acid at 190' is reduced to butyric acid and oleic or elaidic acid at 280-300' is reduced to stearic acid to the extent of 90% of that required by theory; (2) unsaturated ketones are converted into the corresponding saturated ketone by direct hydrogenation in the presence of nickel ; thus mesityl oxide yields isopropylacetone (p-methylpentan-Bone) and phorone yields diiaobutyl ketone ; (3) when the ketonic acids are directly hydrogenated in the presence of nickel the ketonic group only is reduced; thus l=vulic acid yields valerolactone and ethyl acetoacetate undergoes (a) the normal reduction yielding ethyl butgrate; ( b ) scission of the molecule and subsequent reduction of the products yielding acetone isopropyl alcohol and propionic acid ; and (c) a molecular condensation yielding solid dehydracetic acid. Methyl tert.-butylamine has b.p. 54-56" and the oxalate has m. p. 166" (not 58-60" and 160' respectively as stated previously Abstr. 1907 i 490). M. A. W. Action of Ozone on Oleic Acid. CARL D. HARRIES [with WALTHER FRANK] (Bey. 1909 42 446-458.Ccmpare Molinari Abstr. 1908 i 849 and Harries ibid. 387).-01eic acid ozonide,132 ABSI'ICACTS OF CHEMICAL PAPERS. after washing with sodium hydrogen carbonate solution and water has the same composition whatever the concentration of the ozone used may be. The formation of hydrogen peroxide by the decomposition of the ozonide with water is confirmed. The decomposition with water yields products containing 9 and not 18 carbon atoms and the primary products are aldehydes or their peroxides which are trans- formed into acids by a secondary reaction. These products have been re-investigated (compare Abstr. 1907 i 10). Nonaldehyde peroxide CgHlRO2 crystallises from light petroleiim in glistening plates m. p. 73" and hasall the characteristic properties of a peroxide.Its b. p. under reduced pressure is higher than that of nonaldehyde but lower than that of pelargonic acid. When boiled with water it yields nonaldehyde and hydrogen peroxide. The other products isolated were pelargonic acid and the semi-aldehyde of azelaic acid all of which are obtained from the original ethereal extract. The aqueous solution when acidiced yields an ethereal extract from which the peroxide of the semi-aldehyde of azelaic acid C9H,,0 and azelaic acid have been isolated. The peroxide crystallises from acetone in needles m. p. 98" and is completely soliible in hot water but is partly converted into the semi-aldebyde and hydrogen peroxide and paitly isomwised t o azelaic acid. Semi-aldehyde of Succinic Acid [P-Aldehydopropionic Acid].-cARr D.HARRIES and ERNST ALEFELD (Ber. 1909 42 159-165. Compare Harries Abstr. 1898 i 232).+?-Aldehydo- propionic acid has been described by Perkin and Sprankling as a thick dark yellow oil which is readily oxidised by atmospheric oxygen to succinic acid (Trans. 1899 75 11). von Ungern-Sternberg prepared P-aldehydopropionic acid from aconic acid and describes it ae an oil solidifying to a white crystalline mass m. p. 147O b. p. 234-236",760 mm. which is very stable towards oxidising agents but nevertheless has the properties of an aldehydo-acid; thus i t yields n phenylhydrazide-phenylhydrazooe m. p. 182'. The conclusion drawn by this author was that Perkin and Sprankling were either not working with P-aldehydopropionic acid or else that their statement as to the readiness with which the acid underwent oxidation was incorrect (Diss.Konigsberg 1904). The present authors have prepared P-aldehydopropionic acid by decomposing allylacetic acid ozonide with water. They obtained it as an oil which was readily oxidised by atmospheric oxygen forming succinic acid. The oil when kept for a few days however solidified to a white crystalline mass m. p. 147" identical with the substaxIce described by von Ungern-Sternberg. MoLmt. determinations show that the oily acid is unimolecular wbereis the solid acid is bimolecular (compare following abstract). prepared by the action of ozone on a solution of allylacetic acid in carbon tetra- chloride is a colourless syrup Dii 1.289 Dti 1.297 nil 1.46552 n," 1.47359; it is decomposed by water yielding formic acid form- J.J. S . Allylacetic acid oxonide O,< CH2 I CH C H,* C H,* C 02H'ORGANIC CHEMISTRY. 133 aldehyde succinic acid and P-aldehydopropionic acid ; it is probable that the peroxide of the latter substance is formed at the same time. The nnimolecular P-aldehydopropionic acid is a colourless viscid liquid b. p. 134-136O/14 mm. DZ 1.2568 ng3 1.44873 nz 1.44571 1.45911 ; it follows from these physical constants and from the absence of a ferric chloride reaction that the substance is the aldehyde form of the acid. NII,-NH*CO*N CH* CH,*CH,* CO,H crystallises in small prisms or needles m. p. 177-1 78" (decomp.) ; the p-nitroplmzylhydrazone C10H1104N3 forms golden-yellow leaflets IU. p. 158'. P-Aldehydopropionic Acid.CARL D. HARRIES and ALFBED HJXMELXANN (Ber. 1909,42 166-167).-The crystalline P-aldehydo- propionic acid prepared from allylacetic acid (compare preceding abstract) or from aconic acid (compare von Ungern-Sternberg Dim. Konigsberg 1904) is shown to have the bimolecular formula (C,H,O,),. It yields the unimolecular variety when distilled at 134-136" under a pressure of 14 mm. The stability of the polymerised form towards oxidising agents shows that the cocdensation occurs between the two carbonyl groups thus The 8enaicai*bazone W. H. G. CO,H* CH2*CH,*CH<~>CH*CH2*CH2*C02H. W. H. G . Molecular Rearrangements in the Camphor Series. I. Hydroxylauronic Acid and isoCampholactone. WILLIAN A. NOYES and A. W. HOMBERGER (J. Amer. Chern. Soc. 1909 31 278-281).-1t has been shown (Abstr.1895 i 295) that amino- lauronic acid is converted by nitrous acid into y-lauronolic acid laurolene and isocampholactone. When ethyl aminolauronate is treated with nitrous acid it yields a mixture of ethyl y-lauronolate and ethyl hydroxylauronate. Ethyl y-lauronolute C,H,,-CO,Et b. p. 110-115°/25 mm. has Di0 0,9514 and [a12 + 56.6'. Ethyl hydroxylauronate OH*C8El,*C02Et b. p. 150°/30 mm. has Di0 1.100 and [a]:'' + 6-73' Evidence is given t o shorn that hydroxylauronic acid has the v CH2-FH2 C&le,*CH* OH' which is supported by the fact formula CO,H*CMe< that the acid is oxidised by k t r i c acid to active camphoronic acid. The method of formation of isocampholactone suggests that it should be represented by the annexed formula. CO*CMe<CH2-$!H2 I n this case the corresponding hydroxy-acid OH-C,H,,*CO,H must be a stereoisomeride of l I hydroxylauronic acid.In order t o obtain evi- dence on this point isocampholactone was sub- 0 mitted to oxidation with nitric acid. The productas obtained were a Zccctone CsH1204 an acid m. p. 228O probably camphononic acid and a compound m. p. 11l0 which is probably a lactone. The Znctone C,H,,O m. p. 122O b. p. 272O is the chief product of the oxidation and crystallises in needles. These results do not justify any conclusion with regard to the structure of isocampholactone. CMe2*CH E. G .134 ABSTRACTS OF CHEMICAL PAPERS. Ethyl Nitrososuccinate. JULIUS SCHMIDT and KARL TH. WIDMANN (Be?.. 1909 42 497-501).-A general method for the production of nitroso-compounds is to pass the nitrous gases from tbe action of nitric acid on arsenious oxide into acylcarboxylic esters.The method gives especially good results when the acyl group is attached to a tertiary carbon atom. Ethyl acetylsuccinate when treated with the gas at 0' in a long narrow tube then after two hours evacuated in a dark glass desic- cator forms ethyl nityososuccinate CO,Et*CH(NO)*CH;CO,Et an azure-blue liquid which cannot be distilled and is decomposed quickly by light. It is however pure ; in a ethylene dibromide solution it is unimolecular (found 185 and 194 calc. 203) DIE 1.20 n 1.4419. The compound gives Liebermann's reaction is stable in ethylene dibromide but in alcohol or ether the cold solution is slowly decolorised quickly when warm. This change may be due either to polymerisation or isomeric change to oximino-compounds. Potassium permanganate Caro's acid or hydrogen peroxide (10%) oxidise it to ethyl nitro- succinate C,H,,O,N? a yellow viscous oil which could not be distilled unchanged under diminished pressure and explodes when quickly heated.On reduction with zinc dust and acetic acid ethyl aspartate is formed b. p. 126-127'/10 mm. 150-152'/25 mm. (compare Fischer Abstr. 1901 i 193) ; the picrolonate C,Hl,O,N,CloHsO,N forms yellow crystals m. p. 290O. W. R. Products of Hydrolysis of Ethyl Dioxalylsuccinate. GoPyromucio Acid. EDMOND E. BLAISE and HENRI GAULT (Compt. rend. 1909 148 176-179. Compare Abstr. 1908 i 713).-The authors consider that their experiments on the production of iso- pyromucic acid by the removal of 1C0 from the product of hydrolysis of ethyl oxalylsuccinate furnish evidence against the constitutions ascribed by Wislicenus to the substances this author obtained by the action of alkalis on the ester (Abstr.1895 i 506). Thus the compound t o which Wislicenus gave the formula CO Et $' C( C02E t ) CO,Et*CO* CH-CO>' >O; the CO,E t Q=C( C0,Et) CO,Et e:C(OH)-CO should be represented as a &lactone substance obtained from this by hydrolysis mould then have the formula C02H* C( OH) :C(CO,Et) C( CO Et) C( OH)*CO,Et which agrees more closely with the properties of the compound than the ketonic structure put forward by Wislicenus. w. 0. w. Laevulinaldehyde. CARL D. HARRIES and MAX BOEGEMANN (Ber. 1909 42 439-446. Compare Abstr. 1906 i 364 ; 1906 i 833).- The aldehyde was prepared by the action of water on methylheptenone ozonide (Abstr. 1906 i 226).It dissolves readily in water and reduces cold Fehling's solution. I t s molecular weight as determined by the cryoscopic method in benzene solution proves it to be uni- molecular and its molecular dispersion agrees with the ketoaldoic constitution. Its dielectric constant as determined by Nernst'sORGANIC CHEMISTRY. 135 method is high namely 32 at lSO whereas the constant for succin- aldehyde is 28.5 at 20’. The dioxime has m. p. 7 6 O ; the disemicarbmone C7HI4O2N6 crystal- lises from methyl alcohol in colourless plates or prisms m. p. The diphenylhydrazone has not been obtained ; phenylhydrazine reacts with an acetic acid solution of the aldehyde yielding an oil which with hydrochloric acid forms phenylmethyldibydropyridazine.As this compound is sparingly soluble it can be made use of in estimating the aldehyde. The di-p-nitrophenylhydrazom Cl:HI,O,N crystallises in brown plates m. p. 106O. The aldehyde reacts with an alcoholic solution of pyruvic acid and 178-1 80’. P-naphthylamine yielding kstobutylnup~t?~acinc?~onic &d N==C*CH,-CH,COMe 9 c,oH6<C( C0,H 1 jlH which is sparingly soluble i’n ah ordinary solvents. Lavulinaldehyde differs from succinaldehyde which also contains carbonyl groups in the as-positions in the following points (1) it does not polgmerise; (2) i does not give Angeli’s reaction with benzsulph-hydroxamic acid Ttr. 1904 ii 330)’ and (3) it is not readily converted into acetals b When reduced with a large e .cess of aluminium amalgam and ether it yields y-amylene glycol and Lipp’s methyldihydrofuran (Abstr.1889 843). laisen’s method. J. J. S. Certain Numerical Relations in the Sugar Group. C. S . HUDSON ( J . Amer. Chem. Xoc. 1909 31 66-86).-0n the assumption that the known a- and p-forms of dextrose and the related mutarotating sugars are the partial stereoisomerides indicated by the lactonic formula of Tollens it is shown (1) that the difference between the molecular rotations of the a- and p-forms of all the aldehyde sugars and all their derivatives in which the added substance is not joined directly to the end asymmetric carbon atom is a nearly constant quantity; (2) that the a- and @-forms of those derivatives of any aldose sugar in which only the end carbon atom is affected (a.g.glucosides) have molecular rotations the sum of which is equal to the sum for the a- and p-forms of the aldose and it is shown from the available data that these deductions are valid. On this basis the following rules are proposed for the naming of the a- and p-forms of the sugars The names are to be so selected that for all sugars which are genetically related to &-glucose the subtraction of the rotation of the p-form from that of the a-form gives a positive difference and for all sugars genetically related t o I-glucose a negative difference. When the end carbon atom is affected the above rule is modified as follows The names of the a- and p-forms are t o be so selected that the difference of their molecular rotations is equal to aud of the same sign as the similar difference for the forms of the similar derivative of that glucose (d or I ) to which the first sugar is genetically related.136 ABSTRACTS OF CHEMICAL PAPERS.The equilibrium constant for the reversible reaction between the a- and /3-forms of the aldohexoses and allied disaccharides is approxi- mately constant and equal to 1.5 a rule which permits of the calcula- tion of the rotation of the unknown forms of certain sugars. From measurements of the " thermal lag " (compare Abstr. 1908 ii 665) it is shown that in all cases the a-form of the sugar is favoured by an increase in temperature. A formula is deduced which allows of the calculation of the rotatory power of the unknown forms of many of the natural and synthetic glucosides.The influence of t h e end groups of the gliicosides on the rotation of the carbon atom to which they are attached depends mainly on the weight of the group. G. S. Preparation and Properties of P-Glucoheptitol. L. H. PHILIPPE (Compt. rend. 1908 147 1481-1483).-The author has submitted Fischer's P-glucoheptose (Abstr. 1892 1164) to the prolonged action of sodium amalgam; he thus obtains P-gluco- heptitol OH*CH,*Y -$J-? -$J-y*CH2*OH. ?H ?H ?H H H H OH H OH This compound forms small rectangular tablets m. p. 130-131O on the Maquenne block ; [a] + 48' in aqueous solution. I t s rotatory power serves t o distinguish it from the isomeric a-glucoheptitol (loc. cit.). Acetic anhydride in presence of zinc chloride converts it into a resinous heptu-ucetyl derivative C,H,(OAc) m.p. about 50' ; [ a3E + 34.8'. The Aeptabenxoyl derivative C,H,(OBz) forms prismatic needles m. p. 183'. The tpibenzylidene derivative C7H1007( C7H& crystallises in very slender needles m. p. about 230O. Aformulacetal w. 0. w. derivative has also been prepared. Hydrolysis of Maltose by Citric Acid. JOSEPH PIERAERTS (Bull. Assoc. CAim. SUCT. dist. 1909 26 562-573).-Hydrated maltose may be converted completely into 2 mols. of dextrose by boiling 50 C.C. of a 290h solution with 10 C.C. of 20% citric acid for about thirty hours in a reflux apparatus. The time may be reduced to two hours and a-half by heating at a pressure of 14 atm. As soon as the maltose is converted into dextrose the liquid assumes a yellow colour which dnrkens on prolonged heating.L DE K. Formation of Hydrocelluloses by m e a n s of Sulphuric Acid. CARL G. SCHWALBE (Zeitsch. usagew. Chem. 1909 22 155-156. Compare Biittner and Neuman (this vol. i 86).-The author claims that elementary analyses are not sufliciently accurate t o serve for the clear diagnosis of different hydrocelluloses. The reducing powers are much more accurate criteria. Both acids and alkalis hydrolyse hydrocelluloses. J. J. S. Acid Haloid Salts. FELIX KAUFLEB and E. KUNZ (Ber. 1909 42 355-392. Compare Scholl and Escales. h b s t r 1898 i 182; Korczyriski this vol. i 123).-lt is shown that a large number ofORGANIC CHEMISTRY. 13'7 mono-amines combine with dry hydrogen chloride or bromide at the ordinary temperature forming dihydrochlorides and dihydrobromides.The stability of the dihydrochloride depends largely on t h e degree of alkylation ; thus tertiary and quaternary bases regularly form dihydrochlorides whilst of the secondary bases only dimethylamine forms a dihydrochloride. Dihydrochlorides of methylamine methyl- aniline aniline acetanilide methyl-o-toluidine diphenylamine and tribenzylamine could not be obtained at the ordinary temperature. When a compound contains several nitrogen atoms i t is found that each nitrogen atom reacts independently. The conclusion is drawn that the compounds are in all cases ammonium salts of perhalogen hydrides. This is supported by the fact that the change of p-nitrosodimethylaniline hydrochloride into the di- hydrochloride is not accompanied by a change of colour as in the forma- tion of the former from the base itself.The following formulation y X N -+ If N j G l - - + [; N4[Cl2H] shows that in the conversion of the hydrochloride into the dihydro- chloride 'only the colourless anion undergoes alteration whilst the ammonium part of the molecule which imparts the colour to the substance remains unchanged. The following salts were prepared by passing the dry halogen hydride over the base or its normal haloid salt. They are all hygro- scopic substances and readily part with hydrogen chloride or bromide. Dimethylamine dih ydrochloride is a white cryst d i n e subs tance. Tetrcumethylammonium chloride hydrochloride NMe,Cl,HCl forms a white crystalline mass. m-NitrodinLethylaniline dihydrochloride C,H,o0,N2,2HCl i ; a yellowish-white crystalline mass.p-Nitroso- dimethylaniline dihydvochloride is a yellow powder. Dimethyl-o- toluidine dihydrochloride was obtained as an oily liquid. Diethyl- aniline dihgdvochloride C,,H1,N,2HC1 forms colourless crystals which solidify at 47O. p-Nitrosodieth3/laniline dihydrochloride is a yellow powder. Pyridine dihydrochloride C5H,N,2HCl forms large white prisms m. p. 46.7O. Quinoline dihydrochloride C,H,N ,2HC1 is a crystalline mass having the same freezing point as the pyridine compound. Tetramethgldiarninodiphenylmethane tetrahydrocidoride C17H22N,,4HCI is a brown solid. ~etramethyldiami~nodip~r~yZ ketone tetrahpdrochhide is obtained only at Oo. pAzotoluene dihydro- chloride C,,H1,N2,2HCl is a chocolate-brown solrd. Diethylamino- axobenxene dihydrochlorida has the same red colour as the mono- hydrochloride Dieth~lamiwaxobenzene-P-naphthdene psntahydro- chloride resembles potassium permanganate in colour. Pyridina dihydro bromide C H,N 2H Br .pinoline dih ydro bromide and diethylccminoaxobenxene pentahydvobromade were also prepared. W. H. G d-Propylenediemine and Derivatives of the Optically Active Propylenediamines. LEO TSCHUCIAEFF and W. SOEOLOFF (Ber. 1909 42 55-58. Compare Xbstr. 1907 i 896).-The data138 ABSTRACTS OF CHEMICAL PAPERS. previously given for I-propylenediamine are to be corrected to Cobalt-tri-1-propylenediamine iodide [ CoPn,]I prepared in a similar manner to the racemic iodide (Pfeiffer and Gassmann Abstr. 1906 ii 614) separates from hot water in brownish-yellow needles contain- ing 2H,O is much more soluble than the racemic iodide and for a sample dried a t 100" shows [.ID + 23.63' for p 3.38 and DT 1.0156.d-Propylenediamine separated from the racemic base or from the non-crystalii*able syrup remaining after the preparation of the I-isomeride (Zoc. cit.) by means of the d-propylenediamine hydrogen Ltartrate has b. p. 120*5" Di5 0.8584 and [.ID + 29*78" and yields like the I-isotneride (loc. cit ) a platinum di-d-~opylenediarrLi~e chloride [PtPn,]Cl which has [ u J D - 46-45' for p 8.27 and Df" 1.0445 from which the nitrate [PtPn,](NO,) is obtained having [.ID - 40 55" for Degradation of a-Amino-acids to Aliphatic Aldehydes by means of Sodium Hypochlorite. KURT LANQHELD (Ber. 1909 42 392-393).-Raschig has shown (Abstr. 19OS ii 30) that chloro- amine is formed by the interaction of sodium hypochlorite and ammonia.A similar reaction appears to take place between sodium hypochlorite and a-amino-acids ; an intermediate product is formed which does not colour aqueous aniline and decomposes when the solution is warwed at 40-50" yielding ammonia carbon dioxide and an aliphatic aldehyde containing one carbon atom less than the acid. The reaction probably takes place thus R*CH(NQ,)*CQ,H + NaOCl -+ K*CH(NHCl)*CO,H -+ DF 0.8612 and [ a ] D -29.65". p 8-36 and Di6 1.0465. c. s. &KJ R*CH:NH + CO + HC1-+ R*CHO + NH,. Internally Complex Salts. HEINRICH LEY (Ber. 1909 42 354-376).-1n the internally complex copper salts of a-amino-acids the union of the metal to oxygen by a principal and to nitrogen by a supplementary valency linking (Abstr.1905 i 175) causes the properties especially the colour and the dissociation of these complex salts to differ from those of ordinary salts. The electrolytic and the hydrolytic dissociation of copper glycine and of copper a-alanine are very small ; the solutions can be boiled without deposition of copper hydroxide. Such stability is not shown by the copper salts of all a-amino-acids those of piperidinoacetic or diethylaminoacetic acid (of the type NR,*CH,*C02H) being slightly electrolytically but considerably hydrolytically dissociated ; a complex nickel piperidinoacetate cannot be prepared by reason of its great hydrolytic dissociation. The complex copper salts of 6-amino-acids are moderately hydrolytically dissociated and in dilute solutions precipitation of copper hydroxide occurs.Complex copper salts of 6-amino-acids the formation of which would require the production of W. H. G. a seven-membered ring CH2<gZ%S!>Cu cannot be obtained (compare Tschugaeff Abstr. 1907 i,&392)f The fact that glycine can displace the metal from salts of strongerORGANIC CHEMISTRY. 139 (NH,*R*CO,),M + 2HX where M = Cu Ni Go or Zn proceeding almost entirely from left to right in consequence of the very slight electrolytic dissociation of the complex salt. (The equation only partly represents what occurs; in addition the acid HX forms a salt with the amino-acid. Since the salt formation is very small with acetic acid the author uses acetates in the following experiments.) Conductivity measurements give bome idea of what is happening i n the reaction.The difference A between the conductivities of the metallic acetate before and after the addition of the amino-acid is approximately a measure of the complex salt formation because if (NH,-R*CO,),M is largely formed the conductivity of the solution will approach that of acetic acid whilst the conductivity mill be mainly due to the metallic acetate if complex salt formation is only small. In this way it is shown that barium manganese and cadmium have little tendency to form complex salts and copper and nickel have a great tendency; the tendencies of cobalt and zinc are about the same and much smaller than that of nickel. With nickel acetate and different amino-acids the formation of internally complex salts decreases from glycine through a- and P-aminopropionic acids to piperidinoacetic acid ; with copper acetate and y-aminobutyric acid negative values of A that is an increase of the conductivity are observed which is explained by the fact that a partial formation of basic copper acetate occurs in consequence of the large basic k value of the amphoteric electrolyte.The abnormal colour of complex salts has been examined spectro- metrically. The complex copper salts of glycine P-aminopropionic acid methylglycine benzylglycine aa-dimethylglycine a-phenyl- glycine diethylglycine and piperidinoacetic acid are all blue in the solid state and violet-blue in solution. The substitution of methylene hydrogen by phenyl does not produce any essential colour change. The replacement of aminic hydrogen by an aromatic group causes a great change in the absorption internally complex coppzr anilino- acetate and its homologues being intensely green in the solid and the dissolved states. The addition of ammonlum hydroxide to copper anilinoacetate causes a colour change from green to blue probably by reason of the conversion of the internally complex salt into an ordinary complex salt ; a similclr conversion occurs with ammonium hydroxide and copper glycine although here no essential colour change is observed O*CO* H2 O*CO*CH,*NH I cu e:c<NHz + 2NH = H,N..-,du 0. COO CH H,N*’* I 0.CO C H,*NH I T H 2 The decomposition of metallic acetates by amino-acids is accom- panied by colour change when internally complex salts are formed; nickel acetate become3 distinctly blue by the addition of glycine or a- or P-aminopropionic acid.It is noteworthy that the colour of cobalt acetate is unchanged by the addition of glycine and also that solid cobalt anilinoacetate has the normal red colour. It is well known that the strengths of amino-acids are increased by140 ABSTRACTS OF CHEMICAL PAPERS. the introduction of acyl groups. The metallic salts of aceturic acid (acetylglycine) are strongly dissociated and do not behave as internally complex salts copper aceturate and nickel aceturate having the normal blue and green colours respectively. The ultraviolet absorption spectra of aqueous copper acetate in the presence of increasing amounts of ammonia indicate that Cu( NH,),(C2H,02)2 and Cu( NH,),(C2H,0,) respectively are present according as the concen- tration of the ammonia is small or large thus confirming the results of the partition experiments previously described (loc.cit.). The paper concludes with some remarks on the migration of cations Some Derivatives of 6-Aminocaproic [Hexoic] Acid. AUGUST ALBERT (Ber. 1909 42 556-558).-Ethyl 6-phthaliminobutyl- malonate (Abstr. 1899 i 595) which crystallises from petroleum in needles m. p. 4 6 O is converted into the acid C,H402:N*[CH2]4*CH(C02H)2 by warming for a short time with hydriodic acid; it crystallises from a mixture of ethyl acetate and benzene in needles m. p. 127O decomposing into r-phthaliminohexoic acid (Abstr. 1908 i 649). As the yield of the latter was only 16% another method for its preparation was devised.r-Chlorohexonitriles is obtained in 32% yield by heating pentamethylene chloride and potassium cyanide in aqueous alcohol solution for seven hours (compare von Braun and Steindorff Abstr. 1905 i 206). The portion b. p. 242-250° when heated with potassium phthalimide at 210° is converted into crude r-phthaliminohsxonitrile. This oil when heated with double its volume of sulphuric acid for ten minutes at looo yields a mixture of c-phthaliminohexoamide C,H,O :No[ CH,] 430 NH which crystallises from alcohol in leaflets m. p. 1 5 8 O and the corresponding acid. The yield from the pentamethylene chloride is 12%. Red phosphorus and bromine convert phthaliminohexoic acid into a- bromo-r-phthaliminohexoic acid C,H,O,:N* [C R2],=CHBr*C02H which forms crystals m.p. 153-153P. An attempt to prepare a€-diaminohexoic acid from this failed through lack of material. of type CO,H*R*NH,. c. s. W. R. The Nature of Hofmann’s Bromoacetamide. MAURICE FRAN~OIS (Compt. rend. 1909 148 173-176 ; J. Phamn. Chim. 1909 [vi] 29 145-151. Compare this vol. i 13).-The substance t o which Hofmann (Abstr. 1882 950) ascribed the constitution CH3*CO*NHBr,H20 has been prepared by evaporating below 30° an aqueous solution of acetamide and pure hypobromous acid. The con- clusion is drawn that the compound is acetamide hypobromite CH,* CO NH,,HOBr and that Hofmann’s bromoacetamide which arises from this bv dehydration should be regarded as a secondary amide of hypobrornois acid. w. 0. w. Action of Nitrogen on Commercial Barium Carbide. OTTO E~HLINCI and 0.BERKOLD (Zeitsch. angew. Chem. 1909 22? 193-1 97).-The influence of barium chloride on the absorption ofORGANIC CHEMISTRY. 141 nitrogen by a heated mixture of barium carbonate and charcoal has already been determined (Abstr. 1908 i 143) and the investigation has been extended to barium carbide. Moissan (Abstr. 1894 i 314) has already shown that this compound only combines with traces of nitrogen at 1200" but the effect of other substances was not ascertained. The barium carbide used in the experiments had the following composition Ba 49.86; Ca 17.11 ; Fe+Al 2.62; '' carbide " carbon 7.62 ; Na 0 85 ; C1 0.18 ; insoluble matter 9.76 ; P S 0 and CO 12.00% (by difference) and the material therefore probably contains both calcium and barium carbides as well as their oxides. The absorption of nitrogen with this material begins at 500-600° and there is an increase in the nitrogen absorbed as the temperature rises to 920-930° when the maximum amount is absorbed the percentage of cyanide formed at 920-930' being 18.4 that of cyanamide 19.4.With 10% barium chloride the maximum absorption is attained at this temperature also but with 20 and 30% of added chloride the maximum had not been reached at 1120-1130°. With the larger amount of chloride a t the latter temperature the yield of cyanide was somewhat greater (21*6%) the yield of cyanamide some- what less (17.9%). W. R. Preparation of Cyanuric Acid from Carbamide. REINHOLD VON WALTHEB (J. p . Chem. 1909 [ii] 79 126-128).-Cyanuric acid is obtained in 62% yield by heating carbamide with twice its weight of anhydrous zinc chloride at 220° decomposing the cold product with hydrochloric acid and recrystallising the precipitate from hot water.c. s. Molybdenum Hexathiocyanate Saltrs. ARTHUR ROSENHEIM (Ber. 1909 42 149-152).-Largely polemical A reply to Maas and Sand (Abstr. 1908 i 961 ; compare also ibid. i 397 513 614). It is suggested t h a t many of the thiocyanate values obtained by Sand and Maas are low owing to the oxidising action of the nitric acid used. When a thiocyanate is boiled with sodium hydroxide solution a small amount of ammonia is liberated but the amount is so small that the error introduced into the estimation of ammonia would scarcely affect the formula deduced from the experimental data. The sodium salt Na3Mo(SCN),,12H,O forms golden-yellow crystals and agrees in composition with the sodium salts of other complex thiocyanates.J. J. S. CARL W. H~~BNER (J. pr. Chem. 1909 [ii] 79 66-71).-This investigation was carried out with the object of filling some gaps in the chemistry of the dinitriles. Only one of the three condensation products obtained by von Meyer (Abstr. 1895 i 582) by the action of phenylcarbimide on diacetonitrile LP-imino- butyronitrile] in benzene namely that having m. p. 148O (von Meyer gives m. p. I5Oo) is formed when ether is employed as the solvent. Bsnzacetodinitrile [P-iminophenylpropionitrile J and phenylcar bimide Dimolecular Nitriles. VOL. XCVI. i. I142 ABSTRACTS OF CHEMICAL PAPERS also interact at the ordinary temperature in ethereal solution yielding the analogous additive product m.p. 190' (compare von Meyer Zoc. Phenylthiocarbimide reacts in a similar manner with P-iminobutyro- cit.). nitrile at 140-150° yielding the additive product which crystalliees in small orange-yellow needles m. p. 1 9 2 O . P-Imino- phenylpropionitrile yields the analogous additive product CN*CH,* CPh:N* CS*NHPh small lemon-yellow needlos m. p. 166' which when heated under pressure at 140-150O with alcoholic ammonia and lead oxide yields the guanidine derivative C,,H,,!,:NH white leaflets m. p. 1 7 8 O and when treated with nitrous acid yields the nitroso-derivative CN*CH,*CPh:N*CS*NPh-NO lemon-yellow needles m. p. 231'. The additive product obtained by heating P-iminobutyronitrile with dicyanodiamide a t 150' (compare von Meyer Zoc.cit.) has the formula C6HqON,. ; it f orrns a platinichloride (C,H,ON,),,H,PtCI which crystallises in golden-yellow needles m. p. 240' (decornp.). CN.CH,*CMe:N*CS*NHPh W. H. G. Action of Cyanogen on Sulphurous Acid. DANIEL VORLA~DER (Verh. Ges. deut. ATaturforsch. Aerxte. 1907 ii 92).-The action of cyanogen on sulphurous acid is similar to t h a t of the halogens but occurs more slowly C,N + H,SO + H,O = 2HCN + H,SO,. IVith equivalent quantities in 0.1 to 0.2% solution the amounts of cyanogen reduced and of sulphurous acid oxidised are initially equivalent. With a large excess of cyanogen 94% of the sulphurous acid is oxidised after four t o five days but when the acid is in excess only 23% of the cyanogen is reduced in seven to eight days.c. 8. Production of White Ferrous Ferrocyanide. ROBERT L. TAYLOR (Mem. Manchester Phil. Xoc. 1908-09 53 vi).-A creamy- white precipitate is obtained on adding potassium ferrocyanide t o a solution of a ferrous salt which has been thoroughly reduced by hypo- sulphurous acid or sodium hyposul phite Na,S,O,. Hyposulphurous acid will even reduce [precipitated Prussian blue to the white ferrous compound. R. J. C. Prussian Blue and Turnbull's Blue. I. ERICH M~~LLER and THEOPHIL STANISCH (J. pr. Chem. 1909 [i$ 79 81-102).-1n a solution containing ferric and ferrocyanogen ions or ferrous and ferri- cyanogen ions the value of the equilibrium constant K(= [Fe"'] [FeCy,""]/[Fe"].[FeCy,"']) calculated from electrochemical data (Abegg Abstr. 1903 ii 628 ; Schaum Abstr. 1900 ii 2) is about and therefore either solu- tion will contain practically only ferrous and ferricyanogen ions.Consequently the precipitates obtained from ferric chloride and potassium ferrocyanide or from ferrous chloride and potassium ferri- cyanide should be identical. The preceding reasoning however is inaccurate since it assumes that all the ions remain in solution TheORGANIC CHEMISTRY. 143 authors agree with Hofmann (Abstr. 1905 i 38) that the preceding precipitates are ferrocyanides but deny that soluble and insoluble Prussian blue are identical respectively with soluble and insoluble Turnbull's blue. They object that Hofmann actually isolated the pre- cipitates which probably changed during the process and only deter- mined the iron and cyanogen or the ratio Fe CN which-cannot give accurate information as to the composition of these complex and very similar blue ferrocyanogen compounds (compare Illessner Abstr.1895 i 486). The authors determine the compositions by a method which does not involve the separation of the precipitates from the mother liquor and also estimate the ratio of ferrous to ferric iron and of ionised and non-ionised iron. I n definite volumes of for example standard ferric chloride and standard potassium ferrocyanide the amounts of Fe"' and of (FeCyJ"" are estimated by standard potassium permanganate before and after mixing 0.1-molecular solutions being used to minimise the error due to any volume change on mixing. The decrease in the concentration of the ions represents the amounts which have disappeared from the solution to form the precipitate but in consequence of the reaction Fe"' + (FeCy,)"" Fe" + (FeCy,)"' it is not allowable to assume that the for example ferric iron whici has disappeared from the solution occurs as such in the precipitate.However the ratio of ferrous to ferric iron and of ioriised to non- ionised iron can be estimated in the precipitate and hence conclusions drawn as to its constitution. The authors find that ferric chloride and potassium ferrocyanide in proportions exceeding 4 3 give insoluble Prussian blue Fe1114( Fe11Cy6)8 whilst in proportions less than 1 1 the precipitate is a mixture of KFelll(FellCy,) + K,Fel'(Fel'Cy,) ; ferrous chloride and potassium ferricyanide in proportions exceeding 4 3 yield insoluble Turnbull's blue KFe11EIe1rr3(Fer'Cy,)3 whilst in proportions less than 1 1 I(Fe1'I(Fe1'Cy6) is formed.The Roman numerals denote the valency of the iron. c. s. cycZoPropane. ALFRED PARTHEIL ( Verh. Ges. deut. Naturforsch. Aerxte. 1907 ii 159).-cycZoPropane can be prepared by heating together finely-divided zinc arnyl alcohol and trimethylene bromide. c. s. Introduction of Iodine into the Benzene Ring. ADOLF OSWALD (Zeitsch. physiol. Chem. 1908 58 290-294. Compare Abstr. 1903 i 450 ; Messinger and Vortmann 1889,1150 ; Wheeler and Jamieson 1905 i 35O).-Fiirth and Schwarz's statement (P'liiger's Archiu 1908 124 113) that phenylalanine can yield an iodo-derivative when treated by Messinger and Vortmann's method is refuted. Unaltered phenylalanine alone was recovered.Phenyl- acetic and phenylpropionic acids behave in a similar manner. The formation of iodo-derivatives only occurs when the benzene nucleus contains one or more hydroxyl groups. I n certain reactions the pyrrole ring behaves as a phenol for example yields a tetraiodo- 2 2I44 ABSTRACTS OF CHEMICAL PAPERS. derivative and it is possible that the re-activity of tryptophan to iodine is due to the presence of the pyrrole group. J. J. S. [Nitronitrosotetramethyldiaminophenylbenzylsulphone.] ARTHUR I ~ N Z (Ber. 1909 42 385).-The formula NMe,*C,H,(NO,)*CH,*SO,*C,H,(NO)~NMe or a similar one in which the positions of the nitroso- and the nitro- groups are interchanged is in better agreement with the analytical data for the nitroso-derivative obtained from tetramethyldiamino- benzylphenylsulphone than that originally given (A bstr.1908 i 940). c. 8. The Action of Arsenites on Toluenesulphonyl Chloride. AUGUST rGUTMANN (Rev. 1909 42 480-483).-An aqueous solution of trisodium arsenite reacts with p-toluenesulphonyl chloride yielding sodium toluenesulphinate and trisodium arsenate. It is suggested that the chloride first reacts with the alkali yielding sodium hydro- peroxide NaO*OH which then oxidises the arsenite to arsenate. The formula R*SO*OCl for the sulphonyl chloride is accepted. Sodium arsenite has no action on sodium p-toluenesulphonate. An alkaline solution of sodium sulphite reacts with the sulphonyl chloride in much the same manner as the arsenite and is oxidised t o sulphate. J. J. S. p-Tolueneaulphinic Acid. A.HEIDUSCHKA (Verh. Ges. deut. Naturforsch. Aerzte. 1907 ii 170-172).-When ammonia is passed into an alcoholic or ethereal solution of p-toluenesulphinic acid the corresponding ammonium salt is formed whilst in benzene the reaction yields p-tolyl disulphoxide p-toluenesulphonic acid and water It is suggested that the ammonia acts as a base in the former more concentrated solutions whilst in the dilute solution in benzene it acts as a catalyst. Primary amines show a similar behaviour ; in equal molecular quantities they react with p-toluenesulphinic acid t o form salts whilst if the amine is present in less than equal molecular quantity the acid decomposes in accordance with the preceding equation. p-Toluenesulphinic acid decomposes in the same way in boiling water or by melting.The decomposition may throw some light on the nature of the highly-coloured products which are obtained by fusing amine toluenesulphinates (compare Meyer Abstr. 1901 i 3C,K,*SO,H = C7H7*S02*S*C,H7 + C,H,*SO,H + H20. 264). c. s. Triphenylmethyl. XVIII. Tautomerism in the Triphenyl- methane Series. MOSES GOMBERG (Ber. 1909 42 406-417).-1t was stated previously that triphenylmethyl chloride and its analogues exist [in a benzenoid form and a quinonoid form (compare Abstr. 1907 i 504). This statement has been combated however by von Baeyer (Abstr. 1907 i 691) and by Tschitschibabin (Abstr. 1907 i 1022). Evidence is brought forward in the present communication in support of the author’s view. A solution of tri-p-bromotriphenyl- methyl chloride in liquid sulphur dioxide which has been kept forORGANIC CHEMISTRY.145 some time at 45-55' and then cooled deposits colourless crystals which analyses show to be composed of a mixture of tri-p-bromo- triphenylmethyl chloride and 4-chloro-4' 4"-dibromotriphenylmethyl bromide In one experiment the isomorphous mixture contained about ,85% of the latter substance. There is little doubt that the transformation of the carbinyl chloride into the isomeric carbinyl bromide takes place owing to the intermediate formation of the quinonoid modification thus C(C,H,Br),Cl C(cGH,Br),:cGH4<~~ C(C6H4Br)2<~~H4ul. Attempts t o separate the pure carbinyl bromide by repeated crys tallisa tion of the mixture were unsuccessful. The action of liquid sulphur dioxide on 4-bromotriphenylmethyl chloride 4 4'-dibromotriphenylmethyl chloride 4-chloro-4' 4"-di- bromotriphenylmethyl chloride and 4 4'-dichloro-4"-bromotriphenyl- methyl chloride has also been studied.It is found in each case that a certain amount of the carbinyl chloride is converted into the isomeric carbinyl bromide from which it follows that (1) part of the chlorine changes place with the bromine through the intermediate quinonoid form ; (2) when the compound contains a brominated and a chlorinated benzene nucleus it is the former which primarily changes into the quinonoid form under the influence of sulphur dioxide. 4-Chloro-4' 4"-dibromotriphenylmet?q/l bromide forms colourless crystals m. p. 174'. W. H. G. Action of Nitrosobeneene on Secondary Aminea. PAUL FREUNDLER and JUILLARD (Compt.rend. 1909 148 289-290. Com- pare Bamberger Abstr. 1896 i 222).-Nitrosobenzene and secondary amines readily react to give azobenzene together with smaller quantities of nitrobenzene aniline and possibly azoxybenzene. The greater part of the amine remains unaltered but a portion is converted into the corresponding secondary hydroxylamine RR'N*OH. This reaction may be applied t o differentiate between primary secondary and tertiary aliphatic amines. About 0.5 gram of the amine is mixed with nitroso- benzene and when a red coloration appears the product is distilled below 150' in a vacuum if necessary. I n the case of secondary amines the distillate reduces silver nitrate solution in the cold whilst with primary or tertiary amines no reducing agent is formed.A secondary hydroxylamine however appears to be formed when nitrosobenzene is heated for a long time with a tertiary amine. w. 0. w. Preparation of Esters of the Cyclic Series. AUGUSTE BIHAL (Compt. rend. 1908 147 1478-148 I).-Cyclic halogen derivatives react with organic acids liberating hydrogen chloride and giving rise to a cyclic ester. Thus for example benzyl chloride is converted into benzyl acetate when boiled for several hours with glacial acetic acid. The reaction proceeds more rapidly in presence of certain chlorides notably those of antimony bismuth manganese copper and cobalt. The chlorides of iron zinc and tin have a similar action but altjo146 ABSTRACTS OF CHEMICAL PAPERS. bring about the formation of res,inous condensation products.The chlorides of magnesium nickel cadmium mercury chromium barium and strontium have no action or else exercise a retarding effect. Curves are given showing the influence of varying amounts of bismuth chloride and of acetic acid on the velocity of the reaction. w. 0. w. Formation of Hydrogen Cyanide in the Action of Nitric Acid on Phenols and Quinones. ALPHONSE SEYEWETZ and L. POIZAT (Compt.rend. 1909,148 286-288).-Phenols and quinones containing an unsubstituted ortbo- or para-position yield hydrogen cyanide when boiled with nitric acid (20%). With the exception of dimethylaniline and diethylanilhe no other aromatic compounds have been found to give the reaction which is probably due to nitrous acid since in preseiice of carbamide or aniline no hydrogen cyanide is evolved.A theoretical explanation of the reaction based on this fact is suggested. w. 0. w. 1-Methylcyclohexan-2-01 and its Derivatives. MURAT (Ann. Chirn. Phys. 1909 [viii] 16 lOS-l26).-A detailed account of the preparation and properties of certain esters ethers tertiary alcohols and ethylenic hydrocarbons obtained from 1-methylcyclohexan-2-01 (Sabatier and Mailhe Abstr. 1905 i 275). The hydrobromide is less stable than the corresponding hydro- chloride (Sabatier and Mailhe Zoc. cit.) and has b. p. 118-120°/35 mm. and Do 1.240 ; the bccrium salt of the sulphate (C,HloMeO*SO,),Ba has m. p. 120'; the propionate has b. p. 189-190° D20 0.9225 n 1.443 ; the butyrute has b. p. 104'/20 mm. Do 0.941 D20 0.930 nz 1.55; the isobutyrate has b. p. 10Z0/20 mm. Do 0.940 DZo 0.926 ng 1.441 ; the valerate has b.p. 112-113O/24 mm. Do 0.93'3 D20 0.926 n 1.448 ; the isovulerate has b. p. 110-112°/20 mm. Do 0.9375 9 2 1 0.926 mg 1.447; and the belnxoute has b. p. 200°/55 mm. Do 1.0325 Dl* 1,047 m'," 1.521. The ethers are readily obtained by the action of the alkyl iodide on the sodium derivative of che alcohol and the following compounds were prepared 2-ethoxy-l-methyZcyclohezune b. p. 156-158"/760 mm. Do 0.9221 D20 0.912 nz 1.470 ; 2-arnyZoxy-l-methylcyclohexu~ze b. p. 177" Do 0,936. When l -methylcycZohexan-Z-one is heated with acetic anhydride during several days it yields the ucetyl derivative of a tetrahydro- cresol CH2<2zH,$&>COAc b. p. 178" ; the tetrubromo- derivative of the ketone C,H,MeBr,:O crystallises in needles and has m.p. 76'. By the action of organo-magnesium derivatives on 1-methyl- cyclohexan-2-01 the following tertiary alcohols were prepared 1-methyl-2-ethylcyclohexan-3 01 C H 2 < ~ ~ ~ ~ ~ ~ ~ > C E t * O H b. p. 181-182"'745 mm. Yo 0 9356 D20 0,9235 w 1.458 forms an ucetylORGANIC CHEMISTRY. I47 derivative which has b. p. 196-198' DO 0.946 and on dehydration by means of zinc chloride yields R mixture of methylethylcyclohexenes b. p. 149-153' Do 0.829 D12 0.821 which is reduced by direct hydrogenation in the presence of nickel at 200° yielding the methyl- ethylcyclohexane b. p. 151° DO 0.7945 D20 0.784 % 1.432; 1 -methyl- 2-pop y Zc y clo hexan - 2 -oZ C H2< CH2*CHMe>CPr*OH CH2-CH2 b. p. 97-98'/34 mm. DO 0.9276 D20 0919 ng 1.48 forms an acetyl derivative b.p. 107-110'/30 mm. DO 0.9650 D20 0.956 n 1.465 and on dehydration yields a mixture of ethylenic hydrocarbons b. p. 167-170' Do 0.861 1 D20 0.848 n 1.469 ; l-metl~yl-2-tert.-butyZcgclo- >C(OH)*CMe b. p. 93-96'/25 mm. Do 0.9218 D26 0.908 ng 1.465 yields on dehydration a mixture of ethylenic hydrocarbons b. p. 183-lS6'/750 mm. DO 0.864 D27 0,836 nz 1 -46 2 ; 1 -methyl- 2 -isoam$c yclohexan-2-0 2 C H,. C HMe 7Mxan-2-01> CH2<(TH,-CH b. p. 118-120°/22 mm. D O 0.913 D17 0.902 n z 1.462 yields on dehydration one or more ethylenic hydrocarbons b. p. 205-208' DO0.85LY D17 0.845 n" 1.471 which on direct hydrogenation in the presence of nickel at 230-250' is converted into a methylisoamylcyclo- hexaae,b. p. 204' Do 0.825 D17 0.812 ng 1.454 ; 2-cyclohexyZ-1-methyZ- cyclohexan-2-ol CH2<~~2*CHMe>C(OH)*C,FIl b.p. 146-147'/ 30 mm. with decomposition DO 0.978 D1* 0.969 ng 1.501 is converted by the action of zinc chloride into an ethylenic hydrocarbon b. p. 113-116'. Attempts to prepare corresponding tertiary alcohols by the action of 1 -methylcycZohexan-2-01 on phenyl- benzyl- or tolyl- magnesium iodide were unsuccessful the ethylenic hydrocarbon being the only product isolated 2-phenyl-1 -methyl-A2-cgclohexene 2-CH2 C"2<CH2--CH CH2*C=Me>Cpll b. p. 1 28'16 mm. ; 2-6enzyl-l-meIhyl-A2-cyclohexene b. p. 170'142 mm. DO 0.99 Dls 0.981 nz 1.453; 2-o-toZyZ-1-methyl- A2-cyclohexene C H < ~ ~ ~ ~ H ~ ~ > C * C 7 H f b. p. 158-160"/12 mm. DO 0.985 D20 0.961 nto 1.541. The following derivatives of l-methyl-A2-cyclohexene are described the dichloro-derivative obtained by direct chlorination has b.p. 123-125'/20 mm. DO 1.2300 ; the dibromo-derivative similarly pre- pared b. p. 128'/35 mm. Do 1.905 ; Knoevenagel has described a dibromo-derivative of hexahydrotoluene b. p. 1 lSo/20 mm. (Abstr. 1897 i 608) ; the nitrosate C H 2 < ~ ~ ~ ~ ~ ~ ~ > C = * O N 0 2 ; forms brilliant prisms m. p. 104' ; the nnitrosiie '148 ABSTRACTS OF CHEMICAL PAPERS. forms small yellow plates m. p. 103' ; the nitrosochloride CH,-CHMe>(YRCI CH2<CH_-C*(NO) is unstable. 1 -Methyl-Al-cyclohexene yields a dichloro- derivative b p. 1 20°/ 20 mm. DO 1.240; an unstable dibromo-derivative b. p. 126-130"/ 28 mm. ; a nitrosate m. p. 104' ; a nitrosite m. p. 102O and a liquid nitrosoch loride.2-Chloro-1-methylcyclohexane reacts with magnesium and the product condenses with acetaldehyde to form a secondary alcohol which on hydration yields the ethylenic hydrocarbon CH2<C CH2*CHMe>C:CHRle €3,-CH b. p. 158"/760 mm. DO 0.S23 D20 0.81 ng 1.47. ni. A. w. Chromo-isomeric Salts of o-Nitrophenols. ANTONI KORCZY~~~SKI (Bev. 1909 42 167-177).-Hantzsch has shown (Abstr. 1907 i 207 500) that the alkali salts of nitrophenols can be obtained in yellow orange and red modifications; the yellow and red salts are probably true isomerides whereas the orange salts are solid solutions of the red and yellow varieties; however the number of such isomeric salts prepared hitherto has been small. It is shown by the present investigation that the number of yellow salts of o-nitrophenols is quite as large as that of the red salts.The salts with amines are as a rule yellow and do not differ appreciably from one another in shade; on the contrary the red salts exhibit various shades of colour depending on the nature of the alkali metal. Hantzsch has shown recently that the colour of the anion is not altered by union with an alkali metal in salt-formation; consequently the yellow salts which have precisely the same colour must be chemically homogeneous whereas the majority of the red salts of variable colour must be solid solutions of the red isomeride with small quantities of the yellow isomeride. It has been found possible by careful crystallisation from water or dilute alcohol t o separate the orange lithium salt of 2 4-dinitronaphthol into its red and yellow components. The red and yellow salts are undoubtedly structurally identical having the formula C,H,<O->M ; they are '' chromo-isomerides," the exact nature of the isomerism being still unknown.The rubidium (8 H,O) and litihm (&H,O) salts of o-nitrophenol are orange ; the anhydrous salts are red. PhO,N*NH prepared by passing ammonia into the molten substance is red and quickly passes into the orange salt which is also obtained by the absorption of ammonia in Ley and Wiegner's apparatus (Abstr. 1905 i 749) at the ordinary temperature ; a t - 20° the yellow salt PhO,N*NH,,NH is obtained. The methylamine dimethylamine trimethylumine ethylumine dipopplunaine and benzylarnine salts precipitated from ethereal solution all have the same yellow colour ; NO2 The ammonium salt,ORGANIC CHEMISTRY.149 the pipmidine salt forms yellow leaflets ; the pipeyazine salt crystallises in yellow needles m. p. 74-75O. The anhydrous lithium sodium potassium rubidium and silver salts of p-bromo-o-nitrophenol are red ; the lithium salt containing H20 is orange and the sodium salt ($H,O) is yellow when first precipitated ; ammonium salts similar to those of o-nitrophenol were prepared. The salts with the organic bases mentioned above with the exception of trimethylamine have the same yellow colour ; the trimethylumine salt is orange. The alkali salts of 2 4-dibromo-o-nitrophenol are of a brighter red colour than the corresponding salts of p-bromo-o-nitrophenol ; the piperidine and methylcmine salts are yellow; the ammonium trimethylamine dimethylamime ethylamine dipropylamine and benzyl- amine salts are orange ; the piperaxine salt C6H,0,NBr2,C4H1,,N2 m.p. 160° is orange ; the piperaxhe salt (C6H,o,NBr2),,C,H1,N2 m. p. 185O is scarlet. The lithium and sodium salts of o-nitro-p-cresol when prepared a t - 203 are orange ; the potassium ($H20) rubidium and ccesium (IH20) salts are red as is also the sodiuin salt when prepared at the ordinary temperature ; the thallium and ummonium salts are orange ; the salts with organic bases are yellow. The lithium (2H,O) and potassium (1H,O) salts of bromo-o-nitro-p- cresol are blood-red; the anhydrous lithium salt is yellow ; the sodium benzylamine piperazine and ethylamine salts are orange ; the methylamine dimethylamine trimethylamine and piperidine salts are yellow.The lithium salt of p-chloro-0-nitrophenol is orange but the sodium (1 H20) salt is red ; the methyZamine dimethylamine trimethykamane ethylamine piperidine and piperazine salts are yellow. The sodium salt of a-nitro-/3-naphthol precipitated a t low tem- peratures is yellow but quickly changes into the stable orange form. The dimethylamine ethylamine and bemylamine salts are yellow. The lithium (1H20) and sodium salts of 3 :d-dinitro-p-cresol are orange ; the anhydrous potasrrium rubidium and ccesium salts are red. The ammonium methylamine ethylamine benzylamine dimethylamine and trimethylamine salts of 2 4-dinitronaphthol are yellow ; the pipwaxine salt crystallises .in large orange prisms but the powdered substance is yellow ; the sodium potassium rubidium ccegium and thallium salts are ‘orange; the lithium salt (1H20) is orange and loses its water at 160° without changing colour; the anhydrous salt absorbs lH20 from the air and becomes carmine-red.When a solution of the salt in dilute alcohol is cautiously concentrated at 70° it deposits at first a carmine salt lH20 as microscopic leaflets or needles after which a yellow salt lH,O crystallises out in needles; both salts when dehydrated pass into the orange variety ; the yellow modification generally passes spontaneously into the red form. Equivalent solutions of the two salts have the same colour and are equally intense. W. H. G.150 ABSTRACTS OF CHEMICAL PAPERS. Derivatives of 2 3 4-Trinitrortnisole.JAN J. BLANKSMA (Chem. Weekblad 1909 €3 85-88. Compare Abstr. 19@8 i 978 ; Meldola Trans. 1902 81,993).-Derivatives of 2 3 4-trinitroanisole are described. The parent substance was prepared by treating 2 %di- nitroanisole with a mixture of sulphuric acid and fuming nitric acid. Crystsllised from alcohol it has m. p. 155". Its constitution was determined by conversion into 2 4-dinitro-m-anisidine by heating in alcoholic solution with the equivaIent quantity of ammonia in a sealed tube in the water-bath. It separates from alcohol in yellow crystals m. p. 16'7". When this compound is diazotised in sulphuric acid solution and the diazo-solution poured into boiling alcohol 2 4-dinitroanisole is obtained proving that the parent substance is 2 3 4-dinitroanisole.With methylamine in alcoholic solution 2 3 4-trinitroanisole yields 2 4-dinitro- 3 -meth ylanainoanisole OMe C,H,( NHMe)( NO,) 2 which separates from alcohol in yellow crystals m. p. 130". When this compound is dissolved in a mixture of nitric and sulphuric acids and the solution poured into water 3-nitromethylamino-2 4 6-tri- nitroanisole OMe-C,H(NMe*NO,)(NO,) separates as a sticky mass which crystallises from methyl alcohol in colourless crystals rn. p. 99O (Romburgh Abstr. 1889 971). When 2 3 4-trinitroanisole in alcoholic solution is boiled with the equivalent quantity of aniline 2 4-dinitro-3-aniZinoanisoZe OMe*C,H,(NHPh)(NO,) is formed. It crystallises from alcohol in reddish-brown cryi;ta,ls m. p. 152". When 2 3 4-trinitroanisole is heated with aqueous sodium car- bonate the nitro-group at 3 is replaced by hydroxyl yielding the monomethyl ether of 2 4-dinitroi.esorcino2 OMe*C,H,(NO,),*OH which separates from water in light yellow crystals m.p. 108". The nitro-group a t 3 in 2 3 4-trinitroanisole is replaced by methoxyl by heating with sodium methoxide in methyl alcohol solution with formation of theIdimethy1 ether of 3 4-dinitroresorcinol identical with that obtained by Kauffmann and Franck (Abstr. 1907 i 1092). When freshly prepared it is colourless but direct sunlight turns it reddish-brown. Treatment of 2 3 4-trinitroanisole with sodium ethoxide with a view to replacing the nitro-group at 3 by ethoxyl resulted in a complex reaction which is under investigation. OMe*C,H,(NH,)(NO,) Crystallised from alcohol i t has m. p.73". A. J. W. Derivatives of 8-Amino- P-naphtbol. FRIEDRICH KEHRMANN and E. F. ENGELHE (Bey. 1909 42 350-353).-During the course of unsuccessful attempts to prepare 8-ncetylamino-$-naphthaquinone the following new compounds have been obtained. 8-Acetylurnino-P- naphthol OH*C,,H,*NHhc m. p. 164-165" obtained from the aminonaphthol and acetic anhydride is converted by sodium nitrite and dilute sulphuric acid into 1 -nit~oso-8-acety2amino-~-na$thol m. p. 133-134" (decornp.) which separates from boiling water in golden-yellow needles. The nitroso-compound by treatment with 8 parts of stannous chloride in 20% hydrochloric acid for twelveORGANIC CHEMISTRY. 151 hours yields yellow crystals of the hydvochloride of 9-hydroxy-2-methylperimidine {formula I ; compare Sachs Chem.Zeit. 1908 30 IX for nomenclature). Oxidation of an aqueous solution of the salt by sulphuric and chromic acids at Oo yields a substance C,,H,ON m. p. 175' {decomp.) (1.1 which crystallises in orange-yellow prisms is re-converted by reducing agents into the original salt and is probably 9-quino-2-methplperimidine (formula 11). Me \/\/ c. 8. N-P\ -\ / Substitution of Zinc by Magnesium in the Synthesis of Unsaturated Alcohols. \-/ W. JAWORSKY (Ber. 1909,- 435-438. Com- pare Abstr. 1908 i 753).-It is found that much better yields are obtained by substituting mag- (11.) nesium for zinc in the preparation of unsaturated alcohols by Saytzeff's method. A mixture of allyl bromide and the ketone in equivalent proportions is slowly added to magnesium ribbon (which has previously been treated for a short time with an ethereal solution of allyl bromide) immersed in absolute ether.The reaction product is subsequently treated with dilute acid and the alcohol dried and fractionally distilled. DipAenyZcclZyZcar6inoZ C ,H1,O prepared from benzophenone allyl bromide and magnesium is a colourless liquid b. p. 182-183'/32 mm. The following substances were also prepared a viscid yellow oil b. p. 169'/27 mm. from piperonaldehyde; an oil b. p. 266-272"/ 760 mm. from furfuraldehyde; a limpid liquid b. p. 168-170"/760 mm. (decomp.) from mesityl oxide; a yellow oil b. p. 165'/760 mm. (decomp.) from benzylideneacetone ; a viscid yellow oil decomposing when boiled under 22 mm. pressure from benzil. - W. H. G.Action of Magnesium on a Mixture of p-Tolyl Methyl Ketone and Ally1 Iodide. E. GRISHKEWITSCH-TROCHIMOWSHY (J. Buss. Phys. Chem. SOC. 1908 40 16S5-1691).-p-Z'oZyZmethyZalZyZ- carbinol C,H,Me-CMe{C,H,)*OH obtained together with a small proportion of diallyl by the action of magnesium on a mixture of p-tolyl methyl ketone with allyl iodide or bromide is a viscous colourless liquid with a camphor-like odour and an intensely bitter taste b. p. 128'/15 mm. 132.5-133'/30 mm 237-240°/760 mm. DY 0.9807 Di4 0.9832 ng 1.5236. The alcohol readily unites with bromine (2 atoms) giving a syrupy compound which rapidly decomposes with evolution of hydrogen bromide. p-p-ToZyZpentame-p&-trioZ C,H,Me*CBle(OH)*CH,*CH(OH).CH,. prepared by oxidising p-tolylmethylallylcarbinol by 1 ns of 1% potassium permanganate solution crystallises from a mixb of ether and light petroleum in colourless needles m.p. 101-103°. p-p- ToZyZ-p-meth yZh ydyacrylic acid C,H,Me*C~~e( OH)-CH,. d2H obtained by oxidising p-tolylmethylallylcarbinol by means of 4% potassium permanganate solution forms acicular crystals m. p.152 ABSTRACTS 102-104°. The silver salt and the colcium and barium ( OF CHEMICAL PAPERS. which is readily solrible in + 2H,O) salts were prepared. hot water T. H. P. Distribution of Cholesterol and its Allies. CHARLES DORJ~E (Bio-Chent. J. 1909 4 72-106).-Cholestorol is widely distributed in the animal kingdom being found in representatives of all classes examined. In one or two cases analogous substances take its place spongosterol in sponges and so forth.The amount present varies and the results are stated quantitatively. The same wide distribution of the phytosterols is found in the vegetable world and these sub- stances are probably the source of cholesterol in animals. The whole group consists of isomeric or closely related substances exhibiting the unsaturated linking and the hydroxyl group which are necescary for their antitoxic action. W. D. H. Fatty Acid Combinations with Cholesterol. CHARLES P. WHITE (Proc. Physiol. SOC. 1908 vi ; J. Physiol. 38).-Cholesterol forms loose combinations with fatty acids which differ from true esters. Those with the fatty acids higher than hexoic can be obtained as fluid crystals and give '' myelin forms " and,finally an emulsion of anisotropic globules on the addition of water.Similar combinations are formed by cholesterol with lecithin cetyl alcohol glycerol mono- and di-palmitin but not with triglycerides. The globules found in certain tissues (adrenal cortex) are of similar nature. Cholesterol may thus assist in the emulsification absorption and transference of fats. W. D. H. Agrosterol a Cholesterol Substance in Soils. OSWALD SCHHEINEB and EDMUND C. SHOREY (J. Amer. Chern. SOC. 1909 31 11 6-1 1 S).-The authors have isolated a cholesterol substance from Marshall clay (a soil containing 10.6% of organic matter and 0.51% of nitrogen) cbtained from North Dakota by extraction with alcohol and suitable treatment of the extract with ether and alcohol. The substance crystallises from ether in colourless needles m. p.237O and from 80% alcohol in flat plates containing water of crystallisation. It is proposed to name t h i s substance agrosterol since it gives Lieber- mann's cholesterol reaction and has the formula C2,H,,0. W. H. G. New Synthesis of Adrenaline and Allied Compounds. KARL BOTTCHER (Ber. 1909 42 253-266).-Barger and Jowett (Trans. 1905 87 970) were unable to convert up-dibromo-3 4- methylenedioxyphenylet hane by means of phosphorus pentachloride into a chlorinated compound which could be decomposed to a dihydroxy-compound on hydrolysis with water ; they obtained in addition to P-bromo-a-hydroxy-3 4-methylenedioxyphenylethane a dibromohydriu m. p. 158'. When however 24 to 3 mols. of phosphorus pentachloride are allowed to act on the dibromide for a considerable time at 105" a chlorinated product is obtained which is decomposed by water intoORGANIC CHEMISTRY.153 P-bromo-a-3 4-trihydroxyphenylethane. The halogen in this compound may be replaced by the NHMe-group forming adrenaline. By a similar series of reactions $-safrole CH2:O,:c6H,*CMe:CH and isosafrole CH,:O,:C,H,*CH:CHMe or their dichlorides or chloro- hgdrins can be converted into methyladrenaline. A monobromo- adrenaline is obtained from the dibromohydrin m. p. 158'. Thesg three substituted adrenalinee exhibit no pharmacological activity. P-Cldoro-a-hydro-3 4-methyylenedioxyphenyylethne CH,:O,:C,H,*CH( OH)*CH,CI crystallises in long needles m. p. 95'; it is prepared by acting with chlorine on a cooled solution of vinylcatechol methylene ether in carbon tetrachloride whereby the ap-dichloroethane is first obtained as a reddish-coloured oil and this is subsequently hydrolysed by means of a mixture of acetone and water. /3-Chlos.o- a-3 4- trih ydroxgphen y Zethane C,H,( 0 H) ,* C H( 0 H) CH,CI is prepared from the methylene ether by prolonged heating with a large excess of phosphorus pentachloride and subsequent hydrolysis with a mixture of acetone and water.It forms needles which decompose about loo" gives an intense green coloration with ferric chloride and soon decomposes when kept exposed t o the action of light. The carbonic ester C0:O2:C6H,*CHCl*CH,C1 formed as an intermediate product in its preparation may be isolated as an oil b. p. 190°/13 mm. P-Bromo-a-3 4-trihydroxyphenyylethane is prepared from the corre- sponding methylene ether in an analogous manner.It crystallises in clusters of small needles m. p. 92-93O decomposing to a dark violet substance shows the same intense green coloration with ferric chloride and decomposes even more easily than the chloro-compound. Either compound when dissolved in alcohol and shaken with a large excess of aqueous methy lamine is converted into adrenaline. Although the compound prepared in this manner has not yet been obtained in the form of crystalline salts it is very active physiologically. Chloro- P- b~orno-a-hydroxy-3 4methyylenedioxyphen ylet hane C H , 0, C H,C1* CH( OH) CH,Br prepared by the action of sulphuryl chloride on bromohydroxy- methylenedioxyphenylethane crystallises in well-formed long needles m. p. 128-129O.The halogen cannot be removed by heating with aqueous acetone. The acetate forms crystals m. p. 89". C H, 0, C,H,C1*CH(OH)*CH2Cl obtained by the action of sulphuryl chloride on chlorohydroxy- methylenedioxyphenylethane separates in needles m. p. 126-137". A tetrabromo-compound prepared by the action of bromine vapour on a/3-dibromomethylenedioxyphenylethane forms tiny crystals m. p. $r-Safrole ciiloroh ydrin CH, O,:C,H,*CMe( 0 €3) CH,Cl prepared by the action of chlorine on $-safrole is a faintly yellow-coloured oil. It is converted by treatment with phosphorus pentachloride and subsequent hydrolysis with water into di?LydroxyphenyLJI-alZylchloro- hydrin C6H3(0H)2*CMe(OH)*CH2Cl a thin oil from which a-methyl adrenaline is obtained as a bright golden-brown powder.The corresponding dichloro-compound 14 1 - 1 43".154 ABSTRACTS OF CHEMICAL PAPERS. isoSafrole dichloride CH,:O,:C,H,*CHCl*CHMeCl (Hoering Abstr. 1905 i 903) is an oil b. p. 164-166’/11 mm. 270°/760 mm. with much decomposition. P- Ch Zoro - a-h yd~ox y -a-( 3 4-)dioxyphen y Zpropane C,H,(HO),*CH(OH)*CHMeCI forms needles m. p. 104-105’ (decomp.) and when shaken with methylamine gives rise to P-methyladrenaline a bright yellow powder. P-Bromo-a-hydroxy-3 4-dioxybromophenylethane m. p. 157-158O is conveniently prepared by the action of bromine on a solution of vinylcatechol methylene ether in carbon tetrachloride. The acetate has m. p. 1OO-10lo. Oxidation with permanganate forms mono- bromopiperonylic acid m. p. 201-202’. P-Brorno-a-hydroxy-3 4-cc~~6onatobromopht?nyZethane CO:0,:C,H,Br*CH(OH)*CH2Br forms glistening plates m.p. 107O and is converted when left in contact with acetone and water into /?-homo-a-3 4-tdydroxybromo- phenylethane C6H2Br(OH),*CH( OH)*CH2Br which crystallises i n lancet-like needles m. p. 121-123’ and gives a green coloration with ferric chloride in aqueous solution. a-3 4-Trihydroxy-/?-methyZamiraob~omophenyEethnne C,H,Br( OH),. CH(0H) C€€,*NHMe is obtained by the action of methylamine on the above as a light brown powder. E. F. A. New Syntheses of Adrenaline and Allied Compounds. HERMANN PAULY (Ber. 1909 42 484-4S5).-It is claimed that Bijttcher (preceding abstract) had not proved that the product obtained by him is adrenaline. K. W. CHARITSCHKOFF (J. Buss. Phys. Chern. Xoc. 1908 40 1757-1774).-Oxidation by means of air in presence of alkali serves as a means of characterising hydrocarbons and of estimating them in mixtures such as naphtha and its fractional distillates.Under the above conditions saturated hydrocarbons give a negligible quantity of liquid oxidation products whilst naphthenes give polynaphthenic or asphaltogenic acids which are syrupy liquids D 1.2 incapable of cryatallising and are not reduced to more highly hydrogenated compounds by means of sodium amalgam. These acids give the red coloration yielded by ketones with sodium nitroprusside reduce ammoniacal silver nitrate solution and Fehling’s solution and decompose on distillation even under greatly reduced pressure. They are soluble in alcohol benzene chloroform ether and carbon disulphide.Oxidation of the fraction of “Meteor” kerosine b. p. 169-171° consisting of one of [the isomeric decanaphthenes yielded a dibasic acid which on analysis and on determination of the molecular weight cryoscopically and ebullioscopicnlly mas found t o have the formula C2oH2504. T. H. P. 1-Acetyl-Al-cyctopentene as an Oxidation Product of A1-cyclo- Hexeneacetic Acid. WILLIAM H. PERKIN jun. and OTTO WALLACR (Bey. 1909 42 145-149. Compare Wallach Abstr. 1906 i 176; 1907 i 616; 1908 i 426).-The ketone C,H1,O (Harding Haworth J. J. S. Polynaphthenic Acids,ORGANIC CHEMISTRY. 155 and Perkin Trans. 1908 93 1946) has been definitely proved to be acety lcyclopentene. The fact that both Al-cyclohexeneacetic acid and methyl-Al-cyclo- hexene yield acetylcyclopentene when oxidised at 0" with perman- ganate proves that in this reaction a rupture of the six-membered ring occurs and is followed by a closing of the ring to give a cyclo- pentene derivative The possibility of such a reaction must be borne in mind when the constitution of a cyclic compound is based on an examination of the products of oxidation with permanganate. J.J. S. Isomeric Cinnamic Acids. EINAR BIILMANN (Ber. 1909 42 182-188. Compare Liebermann Abstr. 1903 i 255 ; Erlenmeyer jun. Abstr. 1906 i 429).-It is shown that allocinnamic acid m. p. 68O isocinnamic acid m. p. 57" (compare Liebermann Abstr. 1890 1417) and isocinnamic acid m. p. 38-46' (Erlenmeyer sen. Abstr. 1891 200) are chemically identical and are not chemical isomerides. The three substances are trimorphous and may be converted one into the other by simply melting the solid substance cooling the fused mass and inoculating with the acid required Thus the isocinnamic acid m.p. 41° may be obtained from allocinnamic acid by melting this acid in a tube closed with a cotton-wool plug and subsequently cooling the fused mass in a freezing mixture ; if this is heated to about 44' and inoculated with the isocinnamic acid m. p. 58" the whole mass solidifies and melts then at 58". rcZloCinnamic acid may be obtained from this in the same manner. Special precautions must be taken in crystallising isocinnamic acid m. p. 58' in order to prevent inoculation with allocinnamic acid. Thus in order to crystallise the former in a room "infected " with the latter it must be dissolved and the solution boiled after closing the vessel with a cotton-wool plug.This probably explains why Liebermann having once obtained o2locinnamic acid could not again obtain isocinnamic acid m. p. 58O. The isocinnamic acid m. p. 419 when treated with light petroleum appears at first to dissolve but in a few seconds the acid m. p. 58" crystallises out from the solution W. H. G. Remark on Biilmann's Discussion of the Isomeric Cinnarnic Acids. EMIL ERLENMEYER jun. (Ber. 1909 42 521-522. Compare Biilmann preceding abstract).-Polemical. Biilmann's observations are not wholly in accord with those of Liebermann and the author on the three acids from allocinnamic acid the fact that allocinnamic acid can be separated from the iso-acid is held to be against the idea of polymorphism.W. R.156 ABSTRACTS OF CHEMICAL PAPERS. Separation of Synthetic Cinnamic Acid into its Isomeric Components and their Re-combination into the Synthetic Acid. EMIL ERLENMEYER jun. [with 0. HERz] (Ber. 1909 42 502-513. Compare Abstr. 1906 i 21 176; 1907 i 318).-It has already been shown that the synthetic acid is a mixture of storax- cinnamic acid and another acid of m. p. 128'. It has now been demonstrated that this admixed acid is not benzoic thienylacrylic or an alkyl- or methoxy-cinnamic acid. Fractional crystallisation is not a suitable method for obtaining this acid but it may be obtained by fractional distillation of the ethyl esters. Ethyl storax-cinnamate has b. p. 148-151'/20 mm. whereas the ethyl ester of the synthesised acid has b.p. 152-165O/20 mm. and leaves in addition a considerable residue (10-20%). This distillate on careful refractionation gave a separation ; the fraction of lowest b. p. on hydrolysis yielded " storax " acid that of highest b. p. gave the acid m. p. 1289 heterocinnnarnic acid. Moreover this hetero-acid like the cinnamic acid from storax exists in two forms. The residue just mentioned distils at 269-271° and on hydrolysis with cold 20% alcoholic potassium hydroxide a salt separates which yields hetero-p-cinnnarnic acid as an amorphous pre- cipitate m. p. 128'. It exhibits all the chemical properties of a cinnamic acid and i t separates from ethereal solution in a characteristic chalky form. It dissolves in '7-7.30 parts of 75% alcohol whereas storax-a-cinnamic acid dissolves in 16.67 parts and storax-P-acid in 11.31.The hetero-/?-cinnamic acid on repeated dissolution in petroleum is converted into the a-modification which crystallises in glistening thin leaflets m. p. 130-131'. It dissolves in 9.40-9.54 parts of 75% alcohol and by re-solution in water or alcohol it is converted into the chalky isomeride. When storax-a- and hetero-a-acids are mixed in equal proportions and crystallised from ether the synthetic acid is reformed also the two a-acids form mixed crystals. The hetero-/?-cinnamic acid does not give a single substance ; on the bottom of theAvessel the &acid is seen and glistening leaflets on the sides. W. R. Salt Formation and Addition Reactions of the Isomeric Acids obtained from Synthetic Cinnamic Acid and Demonstra- tion of their Different Chemical Behaviour.EMIL ERLENMEYER jun. [with 0. HERZ and G. HILGEKDORFF]l (Ber. 1909 42 513-521. Compare preceding abstract).-The salts of storax-a- and hetero-P- cinnamic acid exhibit strong resemblancea yet the original acids are recovered from them unchanged; thus the diphenyloxyethylamine salt of storax-a-acid crystallises in slender needles m. p. 177'; the salt of the hetero-P-acid crystallises similarly m. p. 172'. Brucine forms an acid and a normal salt with the hetero-/?-acid which are very similar to those of the storax acid ; they are however somewhat more soluble and differ slightly in optical rotatory power (20'). A non-crystallisable syrup was obtained by mixing the two acids and attempting to prepare a solid brucine salt.A potassium hydrogen storax-a-cinnamate C18Hlb04K is obtained from 2 mols. acid and 4 mol. potassium carbonate whlch is acid t o testORGANIC CREMISTRY. 157 paper and stable ; it crystallises from alcohol (75%) in long crystals ; the potassium hydrogen salt from the synthetic acid forms leaflets and the similar salt from the hetero-@acid is amorphous. Benzoic acid also forms a potassium hydrogen snlt. The properties described hitherto as descriptive of the different isomerides have all been physical. However chemical differences also exist; the dibromide from storax-a-acid is formed more readily than that from hetero-@-acid; the ester of storax-a-acid is more rapidly hydrolysed than the hetero-/3-ester and these acids may be separated by taking advantage of the fact that hypochlorous acid forms an additive compound much more slowly with the hetero- than with the storax-acid.The storax acid dibromide crystallises in stout crystals m.. p. 205-206° ; the hetero-dibromide forms thin leaflets m. p. 204' whilst the dibromide from the synthetic acid is intermediate in crystalline character. By Liebermann's method' all these dibromides give the original acids. Synthetic cinnamic acid when fractionally precipitated from its aqueous sodium salt solution is separated into hetero-a- and -p- and storax-a-acids which shows that these acids differ in strength also. The nature of the isomerism is discussed shortly and the opinion expressed that these isomeric phenomena are due to differences in the benzene nucleus.W. R. Action of Ammonia and Amines on Tetrahydrosalicylic Esters. ARTHUR KOTZ and B. MERKEL (J. pr. Chern. 1909 [ii] 79 102-125).-Ethyl 3-amino-1-methylcycZohexane-4-carboxylate (Abstr. 1906 i 88) which does not react with aqueous or methyl alcoholic ammonia vields with boiling aniline alcohol and the v m. p. 261' (decomp.) and by heating ~ H M ~ ~ H $ - ~ H substance CH,-CH;C*CO ' alone at 28d' for&s alcohol and the bimolecular compound CIGH2,O2N2 m. p. above 300'. Ethyl l-methylcyclohexan-3-one-4-carboxylate when heated with aminocyclohexane yields a substance C,H,,0N2 m. p. 264' which appears to be identical with the preceding. With boiling aniline ?HMe*CH,-fi*N€€Ph (1 mol.) the ester yields the ccnilinoanilide CH,-CH,*C*CO NHPh' m. p. 130° whilst with benzylamine at the ordinary temperature with or without methyl alcohol it yields the substance yHMe*CH,-F:N*CH,Ph CH,-CH,*CH-CO,E t ' m.p. 61° into which the attempt to introduce a second N*CH,Ph group was unsuccessful. Ethyl l-methylcycZohexan-3-one-4-carb- oxylate reacts ( a ) with the calculated amount of piperidine at the b. p. t o form ethyl 3-piperidino- 1 methyl-A3-cyclohexene-4-carboxylate FHMe*CH,* fi*C,NH CH,-CH,*C* C0,Et ' m. p. 123O ; (b) with carbamide in warm dilute sodium ethoxide solution VOL. XCVI. i. m158 ABSTRACTS OF CHEMICAL PAPERS. . ( c ) with methyl- yHMe*CH,*fi*NH*y 0 CH,--CH,*C*CO*NH ' t o form the substance alcoholic benzenylamidine to form the quinazoline derivatiue yHMe*CH,*$!:N-gPh CH2-CH,* C:C(OH)* N ' m. p. 227' and (d) with piperazine at 150° to form the substance CH2<@!&3>C* C,N,H *c<gfoy;:E>cH m.p. 21 6'. Ethyl cyclohexan-2-one-1 -carboxylate when heated with aniline yields m. p. 7 H CH N HPh CH,*CH,*C*CO,Et ' ethyl- 2-anilino- A h y clohexene-l -carboxykate 2 9 O and reacts with piperazine in a sealed tub; at $50'' firming the CH,* CH,*C-N c. s. II A C H C H m. p. %O0. II v 4' subst ance I I CH,*CH,*C*CO*N Synthesis of P-Hydroxy-P-phenylpropionic Acid. W. N. ANDRIEWSKY (J. Russ. Phys. Chem. SOC. 1908 40 1635-1 638).-In presence of zinc benzaldehjde and ethyl bromoacetate react giving ethyl P-hydroxy-P-phenylpropionate (compare Dai'n J. Russ. Phys. Chem. SOC. 1890 22 44) the changes being represented by the following equations (1) CH,Br*CO,Et + Zn = ZnBr*CH,*CO,Et ; (2) ZnBr*CH,*CO,Et + Ph-CHO = ZnBr*O*CHPh*CH,*CO,Et ; (3) ZnBr*O*CHPh*CH,*CO,Et + H20 = OH*CHPh*CH,*CO,Et + ZnBr *OH.T. H. P. Condensation of Mesoxalic Esters with Aromatic Tertiary Amines. ALFRED GUYOT and EDMOND MICHEL (Compt. rend. 1909 148 229-232).-Ethyl mesoxalate readily undergoes condensation with aromatic tertiary amines. Ethyl dimethyl-p-amimophmyl- tartronate NMe,*C,H,*C(OH)(CO,Et) prepared by heating an acetic acid solution of dimethylaniline with ethyl mesoxalate for thirty minutes forms colourless leaflets m. p. 76.5'. The following corn- pounds have also been prepared Methyl p-dimethylaminophenyl- turtronute prisms m. p. 1 15" ; ethyl p-dz'ethylanzinophenyltartronate NEt,*C,H,*C(OH)(CO,Et) prisms m. p. 45' ; the methyl ester needles m. p. 103".On hydrolysis with aqueous potassium hydroxide these substances form the corresponding acids which are unstable and have been converted into aldehydes and also into glyoxylic acids of the type R*CO*CO,H and glycollic acids of the type R*CH(OH)*CO,H. Under the influence of phosphoryl chloride the foregoing esters undergo further condensation with aromatic tertiary amines. Thus ethyl p-dimethylaminophenyltartronate and dimethylaniline yield ethyl tetra~th?/ldianziizodiphen ylmnalonate C( C,H,*NMe,),( CO Et) white leaflets m. p. 93'. The following compounds have been pre- pared in the same way Etlu~l dii,zethyZantinodiet~~yZu~~inodipheny~-ORGANIC CHEMISTRY. 159 NMe2*c6H4>C(C0,Et)2 m. p. 83" ; NEt,*C H ethyl tetraethyl- nralonate d~minodiphsi~ylmalonute prisms m.p. 82.5" ; the methyl ester prisms m. p. 08O ; methyl tetrametf~ylc2iccmino~lilenylmatonale leaflets m. p. I 66" ; methyl dimeth ylaminodieth ylamin odiphenylma Zonate NNe2*c'3H4>C( NEt2*C,H4 C0,Me)2 needles rn. p. 121O. Alcoholic potassium hydroxide converts these esters into the corresponding tetra-alkyldiaminodiphenylacetic acids which are unstable and have no definite m. p. (compare Weil Abstr. 1894 i 419). w. 0. w. m-Toluic Acid. ERTCH M~LLER (Ber. 1909 42 423-434).-A continuation of the iuvestigations of Findeklee (Abstr. 1906 i 42) and Jurgens (Abstr. 1907 i 1036). The present communication deals principally with an improved method of converting m-toluic acid into 3-methylphthalic acid and OF various condensation products derived from the latter substance.Experiments have also been made with the object of definitely establishing the constitutions of the four possible nitro-nz-toluic acids. I. 3-kfethylphthalic Acid.-3-Methylphthalic anhydride when heated with phenylacetic acid in the presence of sodium acetate at 2 3 6 O y ields benxy liclene-3-methylphthalide gH*CMe:y*CO*Y CH-CH=C--C:C H Ph' which crystallises in small leaflets m. p. 151° and is converted by a 10% aqueous solution of potassium hydroxide i n to 3-methyldeoxy- benxoin-2-carboxylic acid flH CMe:?oCo2 crystallising with CH*CH=C*CO* CH,Ph' 1H,O in gypsum-like crystals m. p. 77-79'. The latter when reduced with sodium amalgam yields a salt of a y-hydroxy-acid which when treated with hydrochloric acid yields benxyl-Y-methylphthcclide L which crystsllises in groups OF needles m.p. 87-92'. If the salt of the y-hydroxy-acid is heated a t 21Z3 for four hours and then treated with dilute hydrochloric acid i t yields an oil which is undoubtedly J-met?~ylstilbenc9-2-carbo~y~~c acid for it is converted on red uc tion into 3 -met?& y Zdibanxy I - 2 - carboxy Zic acid H -CMe:?*CO,H CH*CH=C*CH,*CH,Ph' crystallising in nodular aggregates of rhombic prisms m. p. 125-126O. It was shown that the acid has the given formula and not gH*CMe $l*CH,* CH,Ph CH*CH=-C*CO,H 9 by V. Meyer's lam of esterification (Abstr. 1895 i 228; 1896 i Although 3-methylphthalylglycine ethyl ester cannot be converted by Gabriel and Colman's method into an isoquinoline derivative 547). n a 2160 ABSTRACTS OF CHEMICAL PAPERS. (compare Jiirgens Zoc.cit.) the latter may be obtained from 3-methyl- phthalic acid by the following method. Benzylidene-3-methylphthalide is converted by gaseous nitrous acid into nitro benz ylidem- 3met?~ylphthalide C,H,Me<-b CPh. 02 which crystallises in yellow leaflets m. p. 198-199' (decomp.) and is converted by hydriodic acid and red phosphorus into 3-phenyl-8-methyt- isocoumarin C,H3Me<cH:bPh long colourless needles m. p. 131'. The latter compound is converted by alcoholic ammonia into 3-phenyZ- co.0 co-0 "-TH which crystallises in small CH:CPh' 8-n~et?~y~isocc6?~bost?/ri~ C,H3Me< groups of needles m. p. 331' and is converted by boiling phosphoryl chloride into 1 -cl~loro-3-pheny?- 8-methyl isoquino line C C 1 3 C 6 H 3 " e < ~ ~ 6 ph' crystallising i n needles m.p. 64 -65'. 3-Pl~enyl-8-metAyZisoquinoline C16HlJS obtained by reducing the last-named compound with hydriodic acid and red phosphorus has m. p. 51'; the hydriodide pale yellow needles m. p. 2 16-218' (decomp.) ; Iydrochloride long slender needles m. p. 236-240' ; chromate granular crystals m. p. 164' ; platinichloride pale yellow needles m. p. 221' (decomp.) ; picrate granular crystals m. p. 232O and aurichloride Cl6H:,,N,HAuC1 H,O microscupic needles m. p. 2 1 1' (decomp.) were prepared. 11. Nitration of m-Tohic Acid.-wh-Toluic acid when nitrated is conveKted into 2-nitro-m-toluic acid 4-nitro-m-toluic acid and 6-nitro- m-toluic acid. It was shown that the compound ILI. p. 215-216O is 6-nitro-m-toluic acid by reducing i t to the amino-compound and distil- ling the latter with lime whereupon o-toluidine was obtained.5-Amino-m-toluic acid C,H,02N crystallises i n groups of small needles with a pink tint m. p. 183' and yields nz-toluidine when distilled with lime. Methyl 6-nitro-m-toluute has m. p. 8 1-83° ; methyl 5-nitro-m-toluate crgstallises in plates m. p. 84-85' ; methyl 4-nitro-rn-toluate forms needles m. p. 7r3-79°. W. H. G. Claisen's Acid Cyanide Synthesis. FERDINAND MAUTHNER (Bey. 1909 42 188-195).-1t has been shown previously (Abstr. 1908 i 348) that 3 4 5-trimethoxybenzoyl cyanide may be prepared from 3 4 5-trimethoxybenzoyl chloride by Claisen's synthesis. I n the present communication it is shown that the chlorides OF anisic ctcid veratric acid dimethylgentisic acid 2 3 4-trimethoxybenzoic acid and 3 4 5-trimethoxybenzoic acid may be converted by this method into the corresponding cyanides which when hydrolysed are first converted into amides and finally into a-ketocarboxylic acids.This method of preparation of the a-keto-acids of phenol ethers is better than t h a t devised by Bouveault (Abstr. 1897 i 530 ; 1898 i 585 ; 1899 i 286) because in this case the positions of the radicles in tho molecule are known. By employing Bouveault's method of converting an a-ketocarboxylic acid into the corresponding aldehydeORGANIC CHEMISTRY. 161 (Abstr. 1896 i 649) it is possible t o pass from phenol ether carboxylic acids to the corresponding aldehydes thus R*CO~Cl-+R*CO*CN-+R*CO*C02H-+R~C~N*R'-+R*CH0. p-Nethoxybenxoyl cyanide C,H,O,N prepared by the action of hydrogen cyanide on anisyl chloride in the presence of pyridine crystallises in colourless needles m. p.63-64'. It is converted by cold concentrated hydrochloric acid into p-methoxyphenylglyoxylamide C,H,O,N colourless needles m. p. 15 I -152O and p-methoxyphenyl- glyoxyhc acid. The following compounds are prepared by methods similar to those just described m-Methoxybenzopl cyanide C,H,O,N forms colourless crystals m. p. 111-112' ; it is not readily attacked by cold concentrated hydrochloric acid. 3 4-Dimethoxpbenzoyl cyanide C,,~,O,N crystal- lises in colourless needles m. p. 11 6-1 17'. 2 ; 5-DzmethoxybenxoyZ cht?oride C,H,O,Cl prepared by the action of phosphorus pentachloride on 2 5-dimethoxybenzoic acid is a colourless oil b. p. 163-164'/ 15 mm 2 5-Dimethoxybenzoyl cyanide C,,H,O,N forms pale yellow needles m.p. 97-98'. 2 5 -DimethoxyphenylgZyoxyZamide C,H,lO,N crystallises in needleq ID. p. 128 - 129'. The corresponding acid first obtained by Bonveaiilt as an oil crystallise8 in needles m. p. 75-76". 2 3 4-Trimethoxybenzoyl chloride C,,H,,O,CI has b. p. 175-176'11 1 mm. m. p. 42'. The corresponding cyanide C,!HllO,N crystallises in colourless needles m. p. 89-90'. 2 ; 3 4-Trzmethozy- poAenylgZyoxy?ic acid C,,H,,O crystallises in colourless needles m. p. 139-140' ; the amide CllH1305N forms needles m. p. 106-107'. 3 4 5-Trimethoxybenzoyl cyanide has b. p. 17S-179'/14 mm. W. H. G. Methyl-carbonato-derivatives of Phenolcarboxylic Acids and their Use for Synthetical Operations. 11. EMCL FISCHER (Bey.1909 42 2 15-228).-The method of preparntion of the chlorides of phenolcarboxylic acids described recently (Abstr. 1903 i 892) cannot be employed with advantage when the hydroxgl group occupies a position ortho to the carboxyl group. o-Ethyl carbonate- benzoic acid has been prepared however by Hofmarm (Arne?*. Patent 1639 174 of Dec. 12 1899) by the action of ethyl chlorocarbonate on n mixtnre of salicylic acid and dimethylaniline in benzene. This method has now been employed to convert the two hydroxyl groups in 2 5-dihydroxybenzoic acid and 2 4-dihydroxybenzoic acid into methyl- carbonato-groups and fram the compounds formed the Corresponding chlorides have been obtained. o-Coumaric acid unlike salicylic acid adds on the methyl-carbonato-group in an aqueous alkaline solution and yields finally the chloride CO,Me*O*C,H,*CH:CH*COCI. p- M ethy Z-carbontctobenxo yloxy benxoic acid CO2Me*O*C6H,*CO*O*C6H,*CO,H obtained by the action of p-methyl carbonatobenznyl chloride on p-hydroxy Genzoic acid crystallises in very small slender needles m.p. 216-217O (corr. decomp.) ; it is converted by dilute aqueous ammonia into p-hydroxybenzoyloxybenzoic acid m. p. about 270' (decomp.) Klepl gives m. p. 261' (Abstr. 1884 446).162 ABSTRACTS OF CHEMICAL PAPERS. o-Methyl-carbonatobenzoic acid C0,Me*O*C6.H4;C0,H forms long glistening plates m. p. 135' (corr. decomp.) ; it is converted by phos- phorus pentachloride into o-methyl-carbonatobenzoyl chloride C,H704Cl a colourless liquid b. p. 107-110'/0*1 mm. ; the latter compound reacts with glycine or glycine ester forming methyl-carbo~tosalicylzlric a d d a viscid oil which is hydrolysed by aqueous sodium hydroxide yielding salicyluric acid (compare Bondi Abstr.1907 i 766). A substance Cl,H70,N is obtained as an intermediate product in the condensation of the chloride with glycine; it crystallises in very thin glistening microscopic plates m. p. 228' (corr.). 5-Methyl-carbonato-2-hydroxybanxoic acid C0,Me-O*C,H,( OH) CO,H obtained by the action of methyl chlorocarbonate on gentisic acid dissolved in N-sodium hydroxide solution crystallises in long colour- less needles m. p. 171' (corr.); it is converted by methyl chloro- carbonate and dimethylaniline in benzene into 2 5-dimetiiyl-carbonato- benzoic acid (CO2Me*O),C,H3*CO2H crystallising in thin plates m.p. 144-145' (corr. decomp.) ; the chloride CllH,07C1 forms microscopic needles m. p. 119' (corr.). 4-Methyl-carlonato-2-hydroxybenzo~c acid CgR,06 crystallises in long needles m. p. 143' (corr.). 2 4-Din~thyl-carbonatobsnzoic acid CllH,,O forms long needles m. p. 159' (corr. decomp.) ; the corre- sponding chloride CllHg07CI crystallises in slender needles or thin leaflets m. p. 86-87' (corr.). o-Xethyl-carbonatocinnarnic acid CO,Me*O*C,H;CH:CH*CO2H crystallises in slender needles m. p. 185' (corr.) ; the cldoride CllH,04C1 forms slender pliable needles. Condensation of Aldehydes with Phenolcarboxylic Acids. 11. E. HOST MADSEN (Arch. Pharni. 1909 247 65-77).-An extension of the reaction described previously (Abstr. 1907 i 423) to other aromatic aldehydes and acids.4 4'- Dihydroxy 5 ; 5'-dintethp?t~iphenylmethane-3 3'-clicarboxylic mid m. p. 248' (approx. decornp.) obtained from benzaldehyde and o-cresotic acid by the general process (loc. cit.) crystallises with 1H,O from ether on addition of light petroleum in tufts of colourless needles and gives in alcoholic solution on addition of ferric chloride a bluiah-violet coloration. The diacetyl derivative m. p. 140-1 45" separates from dilute alcohol in colourless crystale with lI-f,O and gives no colour immediately with ferric chloride but yields a bluish- violet colour with this reagent after boiling with water for some minutes. 4 ; 4'-Dihydroxy-6 6'-dintetl~yltri~l~en?/Z~net~~une-3 3'-dicarboxylic acid m. p. 271' (approx. decomp.) obtained by condensing benzaldehyde with m-cresotic acid crystallises from dilute alcohol in colourless felted needles and is similar in solubility to the first isomeride described but gives a redder coloration with ferric chloride.The diacetyl derivative m. p. 240-245' (decornp.) crystallises in colourless needles or rhomboidal plates and gives a violet coloration with ferric chloride after boiling with water. 2 2'-Dihydroxy-5 5'-dimetl~yltri~l~en?/l,meth~clr,e-3 3'-Jicarboxylic acid m. p. 240' (approx decomp.) obtained from benzsldehyde and W. H. G.ORGANIC CHEMISTRY. 163 p-cresotic acid forms a colourless crystalline powder and generally resembles the two isomerides described above but is somewhat hygroscopic. The diacetyl derivative in. p. I 35-140° crystallises in thin plates and unlike the two isomerides described above is soluble in chloroform ether or hot water.When vanillin is heated with salicylic acid in presence of hydro- chloric acid by the general process no condensation to a triphenyl- methane derivative occurs but decomposition ensues and phenols are formed. Vanillin salicylate m. p. 1 1 0’ (approx.) is obtained when phosphoric oxide is added to salicylic acid and vanillin dissolved in ether and the mixture heated under a reflux apparatus during twenty-four hours. It is coloured green by ammonia gives a violet coloration with Millon’s reagent and yields the characteristic colour reaction of salicylic acid with ferric chloride after boiling in water during a few minutes. The oxime m. p. 164*5’ of the ester forms long colourless needles. No condensation products could be obtained by the general process with (1) paraldehyde and o-cresotic acid (2) acetone and o-cresotic acid or (3) benzaldehyde and o-resorcylic acid.Derivatives of Phenenyltribenzoic [ 1 3 5-Triphenyl- benzene-2’ 2’ 2’”-tricarboxylic] Acid. GIORGIO ERRERA and A. VACCARINO (Gnzxetta 1909 39 i 1-1 l).-The authors have investi- gated further the two isomeric acids obtained by the action of concentrated sulphuric acid on phenenyltri benzoic acid (compare Errera Abstr. 1908 i 185) which are found to have m. p. 362O (instead of 349-350’) and 335-336’ (instead of 32 1’) respectively. The quantities of the two acids obtained are always very nearly in the ratio 4 (m. p. 362’) 1 (m. p. 335-336’) no matter whether the phenenyltribenzoic acid is used in the crude form or after repeated crystallisation.Both are transformed slowly but completely into tribenzoylenebenzene under the prolonged action of concentrated sulphuric acid on the water-bath. Both acids are also esterified moderately readily by Fischer’s method the one with the lower m. p. ratber more slowly than the other probably owing to its less solubility. The observation that tribenzoylenebenzene is formed the more readily from the acid m. p. 335-336’ leads the authors to interchange the two structural formulae previously given (loc. cit.). ~O-~*C(C,H;CO2H):~*~O C,H,*C*CH C* C,H,’ has therefore m. p. 362’. ethyl ester (m. p. 260° instead of 253’) and methyl ester C,6H,302’C02Me m. p. 336-337O were prepared.is deposited from nitrobenzene in yellow needles or large brick-red crystals m. p. about 429’. T. A. H. 2 3 5 6-Dibenzoylene- l-phenylbenzene-3’-carboxylic acid I t s sodium salt C,7H,,0,Na,H,0 and its Its nitro-derivative C,,H,,O,!NO,) 3 CO2 H 3 4 5 6-Dibenzoylene-1-phenylbenzene-2-carboxylic acid 70 -:=C(C,H,* CO,H):CH-)T;’* y,K C,H,*C c*co164 ABSTRACTS OF CHEMICAL PAPERS. crystallises from alcohol in pale yellow silky needles m. p. 335-336O. Its ethyl eRter C,,H,,O,*CO,Et crystallises from light petroleum in elongated yellow lamin% m. Q. 226O and its methyl ester C,,H,,O,*CO,Me cryetallises from light petroleum in minute yellow laminae m. p. 248-249’ ; the sodium salt C27H,,0,Na,5H,0 was prepared. Triethyl phenenyltribenzoate (compare Abstr. 1908 i 185) separates from light petroleum in faintly yellow prismatic crystals m.p. 71° belonging to the monoclinic system [FRANCESCO RANFALDI ~1 b c = 0.48681 1 0.958’73 ; /3= 88’31’24”J. Trimethyl phenenyltribenzoate C,H,(C,H,*CO,~~e) separates from methyl alcohol as a mass of colourless crystals m. p. 94-95’. The great differences between these esters of phenenyltribenzoic acid and the corresponding ones of phenylnaphthalenedicarboxy lic acid (Lamer’s ‘L diphenyltetrenedicarboxylic acid ”) (compare Michael Abstr. 1906 i 518; Lanser Abstr. 1899 i 916) afford a further confirmation of Michael’s views that these two acids are distinct. T. H. P. Inosic Acid. PH(EBUS A. LEVENE and WALTER A. JACOBS (Ber. 1909 42 335-338).-The authors furnish additional evidence of the constitution previously suggested for inosic acid (Abstr.1908 i 93 1). By heating a 28% aqueous solution of the barium salt for six hours at 126-130’ in a sealed tube barium phosphate is eliminated and from the solution which does not contain a pentose or hypoxanthine Haiser and Wenzel’s inosine (Abstr. 1908 i 561) has been isolated ; by more prolonged heating of the barium salt carnine itself is formed. Haiser and Wenzel regard inosic acid and carnine as being derived from the same parent substance. The authors believe that carnine is c. 5. AUGUSTE B~HAL (Compt. rend. 1909 148 179-182. Compare this vol. i 145). -Benzaldehyde can be prepared by boiling for thirty-two hours a mixture of benzylidene chloride (1 rnol.) and acetic acid (2 mols.). Catalysts such as cobalt chloride facilitate the reaction which is probably expressed by the equation CHPhCI + 2HOAc = Ph*CHO + Ac,O + 2HC1.The formation of acetyl chloride which occurs when only 1 mol. of acetic acid is employed is probably due to the action of hydrogen chloride on the acetic anhydride. Curves are given showing the rate of evolution of hydrogen chloride when varying amounts of acetic acid are employed. This reaction is Asymmetric Synthesis PAUL FREUNDLER (Bey.. 1909 42 233-234. Compare Henle and Haakh this vol. i 6).-It was desired to carry out a reaction which requires the influence of light with a racemic compound in circularly polarised light. To this end the conversion of r-o-nitrobenzaldehydediamylacetal (b. p. 186-1 8 7 O / 11 mm.) dissolved in v-amyl alcohol into amyl o-nitrosobenzoate was studied.The Heraeus quartz mercury lamp was used as the source of light and screened so that the light was mainly X=398. Action a degradation product of inosic acid. Preparation of Aldehydes and Acid Anhydrides. stated to be general. w. 0. w.ORGANIC CHEMISTRY. 165 was continued for 400 hours but in a single experiment no evidence of optical activity could be detected. E. F. A. Constitution of Dichloropiperonal." HERMANN PAULY (Ber. 1909 42 417-422. Compare Abstr. 1907 i 709).-Dichloro- piperonal formed by the action of sulphur chloride or sulphur dichloride on piperonaldehyde could not be isolated in a pure state hitherto owing to the presence of colloidal sulphur (compare Schimmel & Co. Abstr. 1906 i 513). It is now found that the sulphur can be removed by passing a current of chlorine into the mixture and distilling off the sulphur dichloride under reduced pressure ; pure dichloropiperonal is obtained by crystallising the residue from chloroform.Since it is so readily prepared by this method i t seemed highly probable that dichloropiperonal had the formula originally given to it by Fittig and Remsen namely COH*C,H,<>CCI,; nevertheless it has been found that when this substance is reduced with zinc dust it does not regenerate piperonaldehyde but yields methylcatechol carbonate ; thus proving the correctness of Delange's view that dichloropiperonal is really dichloromethylcatechol carbonate (Abstr. 1907 i 700). Methylcatecho2 cadonate C8H603 has m. p. 34-35O b.p. 133-135*5O/26 mm. 238-241"/760 mm. It is converted by 50% aqueous pyridine into homocatechol (3 4-dihydroxytoluene) which has m. p. 65" (corr.) and b. p. 251' (corr.). Bdhal and Desvignes give m. p. 51' (Abstr. 1892 1312). W. H. G. Gryetalline Form of 3 4'-Dimethylbenzophenone. PAUL P. SCHORIGIN (BUZZ. Acad. Sci. Xt. Petersburg 1909 79-80. Compare Ber. 1903 36 2027).-This ketone crystallises readily from alcohol in the form of long monoclinic needles La b c = 1.0409 1 0.4154 p = 91°45'] m. p. 82' b. p. 328-330°/760mru. DY 1.134. Z . K. Completely Methylated Flavone Derivatives. JOSEF HERZIG and BR. HOFMANN (Ber. 1909,42 155-159. Compare Abstr. 1891 1386; 1893 i 413).-Morin reacts with methyl sulphate in the presence of a large excess of sodium hyclroxide solution yielding the pentamethyl ether C,,H502(OMe) which crystallises from alcohol in colourless needles m.p. 154-157'. Its alcoholic solution is colourless but turns yellow on the addition of potassium hydroxide solution. When boiled with alcoholic potash it yields 2 4-dimethoxybenzoic acid and the trimethyl ether of o-hydroxyfisetol @H*C,H,(@Me),*CO*CH,*OMe (6-hydroxp2 ; 4-dimethoxyphenyl rrhethoxymethyl ketone) which separates from alcohol in compact colourless crystals m. p. 102-104°. The oxime C,H,O,N(OMe) crystallises from dilute methyl alcohol in colourless needles m. p. 147-149' and the methyl ether has m. p. 49-52". A 25% yield of quercetin pentamethyl ether (Waliaschko Abstr. 1904 i 760) can be obtained by treating quercetin with methyl C6H2(0Me),*CO*CH,*OMe,166 ABSTRACTS OF CHEMICAL PAPERS sulphate and sodium hydroxide and keeping for several days.When warmed with alcoholic potash the ether yields 3 4-dimethoxy benzoic acid and the trimethyl ether of o-hydroxyfieetol. J. J. S. Bisdiketohydrindene. HUGO VOSWINCKEL (Ber. 1909 42 465-470).-Considernble amounts of Nathanson's bisdiketohydrindene (diphthalylethane) ( A bstr. 1894 i 38) are obtained in the prepara- tion of dihydrox naphthaceneqninone (Gab1 iel and Leupold Abstr. 1898 i 482). &hen treated with a mixture of glacial acetic and nitric acid (1.48) at O' the hydrindene derivative yields a mixture of two oxidation products. The one dissolves readily in cold benzene whereas the other is very sparingly soluble. This second conzpound C18H1208 crystallises from hot chloroform in short six-sided prisms m.p. 61l0 and the structural formula r - C,H4<co.o>CH*CH( co- OH)* CO*C6H4*CH0 is suggested. It yields an acetyl derivative C120H1407 m. p. 3 1 5 O a benzoyl derivative C25H,607 m. p. 268' and a methyl ether Cl9HI4O6 which turns brown at 240' and decompohes a t higher temperatures. With phenylhydrazine the oxidation product yields a complex con- densation product (Cl,H120 + 5C,H8N2- 5H,O) which crystallises from glacial acetic acid in red needles with a high metallic lustre and m. p. 209'. The oxidation product dissolves in cold normal sodium hydroxide solution and the immediate addition of hydrochloric acid yields an acid C,,H1,0,,2H,O which crystalliaes f com glacial acetic acid in clear prisms m.p. 240'. Its solutions in ammonia or alkali carbonates have a reddish-brown colour and those in alkali hydroxides a reddish- brown colour which changes rapidly t o blue. Hot sodium hydroxide transforms the oxidation product in to phthalonaldehydic acid CO H*C,H,*CO* CO,H which cry stallises f roni water in small prisms and plates m. p. 144'. Itsphenylhydrazone has m. p. 229'. J. J. S. The Naphthacene Series. 11. HUGO VOSWINCKEL (Ber. 1909 42 458-465. Compare Abstr. 1906 i 99).-Phenol and acetic acid react with naphthacenediquinone in the presence of sulphuric acid yielding a product C18H80,,C:,H60,C,H40 which crystallises from nitrobenzene in pale yellow prisms m. p. 283'. The formula C (OH) (C,H,*OH)$ CO C,J%<C (0 H 1 (O*c),-C C*>C,H49 dihY droxYacetoxY-hYdroxY - phe,~?/ldihydronaphthacenequinone is suggested.The phenolic group is firmly attached and cannot be removed by reduction or hydrolysis whereas the acetyl group is readily eliminated. Acetic anhydride and zinc chloride transform the condensation Droduct into the tetra-acetvl c(oA~)(c,H,=oA~).c.~o derivative C,H,<c(oAc) ,-j cO>C,H which forms pale yellow crystals m. 6. 28KORGANIC CHEMISTRY. 167 The condensation product dissolves in dilute alkalis yielding brownish-violet-coloured solutions and the addition of mineral acids yields the three products 1. ~riiLyd~ox?/-?LydroxypA~n yZdiA ydronaph thacenepuinone C( OH) ( CGH4-OH) * CO C"H,<C(OH),--C. C0>cGH4' -It is insoluble i u benzene but crystallises from dilute alcohol in yellow prisms m.p. 1 go" dissolves in alkalis giving characteristic colorations and dyes silk an orange colour. Its solution in concen- trated sulphuric acid has a reddish-violet colour which turns to a steel-blue .when warmed ; with acetic anhydride and zinc chloride i t yields a monoacetyl derivative C,,H,,O7 which Feparates from glacial acetic acid as a colourless cryhtalline powder m. 1'. 285'. . . - isolated as the calcium salt. The acid separates as a flocculent mass containing water of crystallisittion; wrieri heated a t 80" it loses 0*5H,O assumes a crystalline texture and then melts at 130". Treat- ment with acetic anhydride and zinc chloride leads to the elimination of water and the formation (jf an ucetyl derivative OAc*C,H,*~I'h-~H* CO which crystallises from glacial acetic acid in golden-yellow plates m.p. 2664 Treatment with inetbyl sulphate transforms the acid into a tetrametiLy1 derivative which forms colourless plates m. p. 124'. 0-c )*CH*CO ' >C,& OMe* CGH,*CPh( OMe)*C( C0,M.e) C( CO,Me)*COPh C( C,H,'OH)(OH)*~H* $!( OH) 3. A compound C,H,<CO C! H C(0H) >'GH4 (*) which crystallises from dilute alcohol in orange-coloured needles m. p. 174'. It dissolves in alkali hydroxides to a violet solntion and in sulphuric acid to a pure blue solution. Itl yields a monoacetyl deriv- ative C,,$,,O m. p. 1 7 2 O . Resorcinol orcinol and phloroglucinol condense with naphthacene- diquinone and glacial acetic acid in the absence of sulphuric acid. The product obtained from resorcinol has the composition C,,H,,O and forms a reddish-brown crystalline powder m.p. 234". Nupkdiacenepuinhydrone C18Hs04,C18HZ004 is obbained by the union of naphthacenediquinone with dihydroxynaphthacenequinone in nitrobenzene solution and is identical with the compound previously described as a desmot ropic modification of naphthacenediquinone. J. J. S. Reactions of 9 10-Dihydroanthracene and of Anthranol. ROBERT PADOVA (Compt. rend. 1909 148 290-292).-When 9 10- dihydroanthracene is heated at 250' for two and a-half hours with diphenyldichloromethane tetrccphen?/la~~t~LraxyliZene CP h 2 C<' '4>C CPh C6H4 is obtained. This has m. p. 305" and is identical with the substance168 ABSTRACTS OF CHEMICAL PAPERS. I I obtained by Staudinger (Abstr. 1908 i 410) by the action of anthraquinone on diphenylketenquinoline.On reduc- tion with sodium and benzyl alcohol it yields the /\/\/\ compound I (below) which has m. p. above 360" and I ' I I shows an intense violet fluoreFcence. formed by the action of amyl nitrite on a solution of A/\/\ dianthrone in pyridine. The action of chloroform I I I 1 and alcoholic potassium hydroxide onanthranol leads \/\/\/ to the formation of a substance crystallising in deep This is 10-oxanthryl-9- anthraquinonementhane (formula 11) The acetyl derivative has m. p. 201-202O. The bermoyl derivative forms canary-yellow prisms m. p. 2 1 6-2 1 8". 0 \/ Dianthraquinone (annexed formula) is said to be red prisms m p. above 310'. 0 230° but is not sharp. The name dianthranol is /\/\/\ assigned to this compound that previously described as I dianthrauol or dianthrone (Zoc.cit.) being regarded as IORGANIC CHEMISTRY. 169 the action of magnesium on a mixture of allyl bromide and a ketonic compound under the conditions previously laid down (Abstr. 1908 i 3-AZZyZmenthan-3-oZ C13H2*0 b. p. 1 30°/22 mm. prepared from 2-Allylborneol b. p. 130'/20 mm. from camphor and allyl bromide. A4-AZZyZ-3-p-rnenthen-3-oZ C13H,,0 b. p. 135'/27 mm. from pulegone and allyl bromide. These three alcohols which were obtained in about 90% yields are colourless mobile liquids. Treated under the above conditions with allyl bromide piperonal yields a thick yellow liquid b. p 169-1'70"/27 mm. ; furfur- aldehyde a thick yellow liquid b. p. 266-272'; menthyl oxide a colourless mobile liquid b. p. 168-170O (slight decomp.) with a smell like that of camphor ; benzylideneacetone an almost colourless liquid b.p. 165O a t which temperature water is given off ; benzil a thick brown liquid which decomposes when distilled under 22 mm. pressure. The reaction between allyl bromide and a ketonic compound in presence of magnesium sometimes fails without apparent reason. One condition necessary for success is a slow gentle action any strong heating always lowering the yield of alcohol. The Grignard Synthesis. Action of Magnesium Phenyl Bromide on Camphor. H. JERMAIN M. CREIGHTON (Trans. Nova Xcotha Inst. Sci. 1908 11 (4) 593-59i).-The interaction of ethereal magnesium phenyl bromide and camphor in equal molecular quantities at 60" leads to the formation of phenylborneol C,,H!,Ph*OH b. p. 258-260' or 143-145'/14 mm.D 0.977 [a]D 7'55 in alcoholic Attempts to Resolve Racemic Camphoric Acid and iso- Borneo1 into Active Components. ERNST BECKMANN (Ber. 1909 42 485-491. Compare Pickard and Littlebury Trans. 1907 91 1973).-The isoborneol obtained from camphene by Bertram and Walbaum's method (Abstr. 1894 i 204) has m. p. 212' and is slightly dextrorotatory in solution the value for [a]D varying from + 1.2' to + 3.9' according to the solvent used. When oxidised the isoborneol yields a camphor which is slightly Isevorotatory and on further oxidation a camphoric acid which is also slightly laevorotatory. No isocamphoric acid is formed as treatment with acetyl chloride completely transforms the acid into its anhydride. The acid obtained is mainly r-camphoric acid with a slight excess of the E-acid and can be resolved by repeatedly crystallising the acid cinchonidine salt from aqueous alcohol.The d-acid had m. p. 183' and [a]D + 44*4' and the Z-acid m. p. 186-187' and [a] - 50.7O. Attempts to resolve the isoborneol itself were made by conversion into the isobornyl hydrogen succinate and resolution of this by means of its cinchonidine salt. isoBornyl succinate C24H3804 has m. p. 37' and resembles camphor in appearance. isoBorny1 hydrogen succinate C,,H2204 is a clear oil with an acid taste and an odour of isoborneol. The cinchonidine salt 753). allyl bromide and rnenthone. These products are under investigation. T. H. P. solution (compare Zelinsky Abstr. 1901 i 660). c. s.170 ABS'CRACTS OF OHEMICAL PAPERS. C,,H,,0,N2 crystallises from dilute alcohol in slender needles m.p. 107". By crystallising from its 40% alcoholic solution nine fractions with [aID varying from + 11.3" to - 2.5" were obtained. The genetic relationship of the camphors and borneols is repre- Fented by the following scheme ,I-isoborneol >-+ I-camphor. / d-isoborneol +\ I-borneol d-camphor ' d-borneol J. J. S. Components of Ethereal Oils. Constitution of Camphene. Its Oxidation with Ozone. FRIEDRICII W. SEMMLER (Bey. 1909 42 246-252).-When ozonised camphene forms only one ozonide which is decomposed in two ways on the one hand (to the extent of about 30%) into camphenilone C,H,,O and this t o a hydroxy-acid 6-hydroxycamphenilonic acid which forms a beautifully crystalline &lactone CgHI,02 whilst on the other hancl acids C,H1402 are formed.Ccmphene oxonide annexed formula prepared / I \ CH CH (~<cH by leading a stream of ozone through camphene I AH dissolved in chloroform is a viscid oil which C'H C<yH2 decomposes when distilled in a V ~ C L I U I ~ . Cum- /CH,*CH phenilone CH-CH2*CH has m. p. \CMe2*CO/ CH 40° D3* 0-9705. The semicarbazone CgH14:N *NH*CO*NH has m. p. 223' ; the oxime has m. p. log" b. p. 128-129'/14 nim. The nitride C,H,,N prepared by boiling the oxirne with dilute sulphuric acid has b. p. 85-90°/12 mm. D20 0.9449 n 1.47348. Camphoceenic acid obtained by the action of alcoholic potassium hydroxide ou the citrile has b. p. 145-146"/11 mm. D20 1.020 n 1.4862. P I \ \ I / 0 3 \ I / H,*CH( CMe,-OH) )CH forms a CH; CH( C0,H) 8-Hyd~oxycamphenilonic acid thin syrup b.p. 125-175O/lO mm. ihich 'decomposes forming a solid distillate of thelactone. This has m. p. 95-96' b. p. 1 26-128"/10 mm. and forms large plates ; it dissolves slowlyin a slight excess of potassium hydroxide and this solution yields a colourless silver salt. The silver ,salt interacts with methyl iodide forming methyl 6-hydroxycampheni- Zonate b. p. 126-127"/10 mm. D20 1.0423 n 1.46797. Both the acid and lactone behave as saturated compouuds to permangnnate. The acid CgH1402 obtained also by the decomposition of camphene ozonide in a vacuum is regarded as a mixture of an unsaturated monocyclic and a saturated dicyclic acid. It has b. p. 136-140°/10 mm. D*O 1-028 m 1.475 ; the methyl ester has b. p. 94-96'/10 mm. D20 0,988 n 1.46261.In view of these results crude camphane consists t o the greater /CH,-CH \CMe2-C(-CH,)/ part of semi-cyclic-camphene CH- C H9- ,'CH. E. F. A.ORGANIC CHEMISTRY. 171 Constituents of Ethereal Oils. Inversion of Carvenene CloH (Terpinene ?) into isoGarvenene CIoH (isoTerpinene 3). FRIEDRICH W. SEMMLER (Ber. 1909 42 522-52'7. Compare this vol. i 1 lo).-Carvenene has the following constants D202 0.8443 ng'2 1.49065 which result confirms the conclusion previously arrived at that cyclic conjugated double linkings cause an exaltation in the molecular refraction (cal. 45.240 found 46.6 19). When carvenene is heated with alcoholic sulphuric acid for two hours isocarvenene CloH16 b. p. 59-62'/10 mm. D20 0.845 nD 1.480 (the exalta- tion in t h i s case is only 0*4) and a dicarvenene C20H32 b .. p. 170-173'/10 mm. D20 0*92S n D 1.5175 are obtained. The physical constants for isocarvenene are identical with those of terpinene obtained from sabinene mono- or di-hydrochloride and i t has been found that all terpinenes are converted into a terpene by alcoholic sulphuric acid the physical data of which agree with those of isocarvenene. This compound yields terpinene nitrosite identical with that obtained from carvenene. I n order to investigate further the conversion of carvenene into the iso-compound the action of bromine on '' terpinene " from sabinene dihydrochloride in amyl alcohol-ether sdution was studied ; crystals of terpinol tetrabromide were deposited thus proving that terpinol is present in the "terpinene," which has hitherto been regarded as pure when prepared from the dih y drochloride.Carvenene on repeated reduction with sodium and amyl alcohol gives dihydrocccrvenene ( A2-tetrahydrocymene) CloHls an oil b. p. 55-56'/12 mm. D20 0.824 nD 1,461. Oxidation of carvenene with ozone yields dimethylacetonylacetone (b. p. S2-86°/10 mm.). Carvenene is regarded as A' '3-dihydrocymene and isocarvenene A' ; '-dihydrocymene. W. R. Sesquiterpenes. ERNST DEUSSEN (Ber. 1909,42,376-383 ; 680). -The author is unable to say from which of the two and possibly three isomeric hydrocarbons present in caryophyllene (Abstr. 1908 i 353) the following substances are derived. The oxidation of caryophyllene (a - 14') by dilute aqueous potassium permanganate at 0' yields a glycol Cl>H2,0 m. p. 120.5" (Zoc.cit.); from the oily potassium salts remaining after the removal of the glycol two acids have been obtained. One is a liquid monobasic acid Cl0H1,O3 which forms a crystalline semi- carbuzone C,,H,,O,N m. . p. 186' (slight yellow coloration) and the other is a crystalline monobasic acid CsH804 m. p. 179*5-1S0.5' which sublimes without decomposition does not form a semicarbazone and is not identical with Baeyer's A2 4-dihydro- phthalic acid. When a solution of caryophyllene in acetone containing a little water is cooled in a freezing mixture and oxidised by the gradual addition OF powdered potassium permanganate (two atomic proportions of oxygen) a substance ClOHlsO,,. m. p. 145-146' is obtained which separates from hot benzene in white needles is unchanged by dilute sodium hydroxide at loo' has a bitter-sweet taste and172 ABSTRACTS OF CHEMICAL PAPERS.appears to be a glycol since it is changed by dilute sulphuric acid to an amorphous white substance C1,H1,O2. [With A. LOESCHE.]-T~~ residue remaining after the distillation in a vacuum of oil of clove stalks freed from eugenol yields by treatment with alcohol a voluminous white substance (C21H300) m. p. 146O which can be purified by repeated precipitation of its chloroform solution by alcohol. c. s. Ethereal Oil of the Root Bark of Cinnamomum zeylani- cum. A. A. L. P I L a R m (Plharm. Weekblad 1909 46 50-54).-The chief constituent of the oil of the root bark of Cinnamomum xeykanicurn is camphor. The other constituents are pinene cineol dipentene phellandrene eugenol safrole probably carophyllene and borneol and possibly cinnamaldehyde. The oil from the leaves contains 76% of eugenol along with pinene and cinnamaldehyde. The oil from an old sample of the stem bark contained 50% of cinnamaldehyde and that from a specimen of young bark 70-75%.In both pinene benz- aldehyde and eugenol were also present. A. J. W. Extracts containing Glucosides. LEOPOLD ROSENTRALER and R. MEYER (Arch. Pharm. 1909 247 28-49).-The object of this research was to determine whether in the preparation of extracts of drugs containing glucosides by exhaustion with water as recommended by various Pharmacopeias decomposition of the glucosides ensued and if so whather this could be prevented by (1) neutralising the natural acids of the drug by adding calcium carbonate and (2) by rendering the enzymes inactive by immersing the drug in boiling 95% alcohol.Experiments with gentian centaury alder bark cascara sagrada bark and rhubarb showed that the first question must be answered in the affirmative that although in none of these cases did the calcium carbonate exert any deleterious action its protective action with respect to the glucosides was slight and that extraction with hot alcohol is harmful in the case of centaury is of no advantage in the case of alder bark but is to be recommended in the cases of gentian cascara sagrada bark and rhubarb. The methods adopted in esti- mating the glucosides etc. in these various extracts are described in detail in the original. T. A. H. Cholesterol as an Antidote to the Saponine. ADOLF WINDAUS (Ber.1909 42 238-246).-The action of cholesterol as an antidote to the power of saponins to dissolve blood-corpuscles discovered by Ransom has been ascribed to a chemical reaction and to a physical change such as absorption. The poisons of bees snakes and bacterial poisons are similarly counteracted by cholesterol. Digitonin and cholesterol when mixed in alcoholic solution immedi- ately give rise to a colourless crystalline precipitate in fine needles of digitonin- cholesteride C,,H,,O + C,7H,,0 formed as a simple molecular compound of the two components without any elimination of water. The compound decomposes above 2 4 0 O ; it is quite impossible to obtain cholesterol from it by prolonged extraction with ether,ORGANIC CHEMISTRY.173 It slowly dissociates when boiled in methyl-alcoholic solution for some hours. It is entirely without any solvent action on the blood-corpuscles. Other alcohols behave similarly to cholesterol towards digitonin. Phytosterol forms a molecular compound crystallising in thin needles ; the compound with stigmasterol is even less soluble. Digitonin-P- cholestanol is more soluble than the cholesteride and crystallises in stellar aggregates of needles. a-Cholestanol (cyclocholesterol) forms no such molecular compound. Digitonin-amyl alcohol (C,,H,,O + C,H,,O + 6H20) (compare Houdas Abstr. 1892 222) is more soluble than the cholesterol derivative. The air-dried product loses amyl alcohol when boiled with water. Digitonin-octyl alcohol behaves similarly. 0 t her alcohols linalool geraniol and sabinol also combine with digitonin.Cholesterol esters do not unite with digitonin nor do these esters counteract the poisonous action of saponins. When digitonin- cholesteride is acetylated it is easy to remove the cholesterol acetate. The reaction can be used to detect small quantities of cholesterol and to separate it from mixtures particularly in cases when cholesterol esters are also present. It is also applicable to the purification of digitonin. Solanin-cholestwide is very sparingly soluble in alcohol but crystal- lises with difficulty. Cyclamia cholesteride crystallises in minute needles but the cholesterol can be extracted from this with ether. Cyclamin also gives an insoluble crystalline additive product with octyl alcohol.From the analysis of this cholesteride the formula C36H56018 for cyclamin is obtained E. F. A. Scopoline. ERNST SCHMIDT (Arch. Phacrn. 1909 247 79-80).- It mas shown previously (Abstr. 1906 i 104) that scopoline is reduced without difficulty to hydroscopoline which contains two -OH groups. Further on oxidation with chromic acid scopoline yields pyridine- methochloride and from these observations the deductions are drawn that the -OH group of scopoline does not lie in the pyridine nucleus and that the same applies to the second oxygen atom which must be present in an ether or morpholine group. In confirmation of this view it is now shown that hydroscopoline when carefully oxidised with chromic acid yields a n z e t h y l ~ p e r i d i n e d i ~ ~ ~ o x y z ~ acid m.p. 214-21 6' (decornp.) which crystallises in transparent tablets and yields a crystalline azure-blue copper salt. The hydrochloride m. p. 224-225' (decornp.) is crystalline and the aurichlorids forms large yellow leaflets. act'-Dimethylpyridine on oxidation with permanganate furnishes methylpyridinecarboxylic acid (m. p. 129') and Ladenburg's act'- pyridinedicarboxylic acid. The latter on electrolytic reduction furnishes two isomeric hydrogenised acids of which one m. p. 206-207O seadily passes into the other m. p 158' and it is hoped by methylating these acids to synthesise the acid obtained by oxidising hyd roscopoline. T. A. H. C8HI,o,N 9 H2° VOL. xcvx. i. I)IL174 ABSTRACTS OF CHEMICAL PAPERS. The Chlorophyll Group. 111. New Method of Decom- position in the Chemistry of Chlorophyll.LEON MARCRLEWSKI (Biochem. Zeitsch. 1909 16 3-8. Compare Abstr. 2908 i 439).- The zinc compound obtained by the action of zinc hydroxide aud carbon dioxide on an alcoholic solution of chlorophyllan is termed “ zinc chlorophyll.” It is a complex metallic derivative of chlorophyll which it closely resembles in properties. Treatment with acids con- verts the zinc compound into chlorophyllan whereas alkalis (alcoholic potassium hydroxide) transform it into a substance analogous to alkachlorophyll the chief difference being that the new compound contains zinc whereas nlkachlorophyll contains magnesium. The name ‘‘ zinc-prophyllotaonin ” is suggested. The compound dissolves in ether yielding a brilliant greenish-blue solution with a red fluorescence.The solution gives five characteristic absorption bands between h 677 and h 492. Treatment of the new compound with concentrated hydrochloric acid yields phyllotaonin or allophyllotaonin. J. J. 5. Rotation of Tannin MAXIMILIAN NIERENSTEIN (Chem. Zeit. 1909 33 126).-Feist’s view (7bid. 1308,32 918) that the rotatory power of tannin i s due to admixture of dextrose formed by the hydrolysis of a glycogallic acid is not accepted. Experiments show that specimens of tannin which are free from dextrose have a high rotatory power. J. J. S. Tannin MAXIMILIAN NIERENSTEIN (Ber. 1909 42 353-354. Compare Abstr. 190S i 40).-Since luteo-acid:(pentahydroxydiphenyl- methylolidecarboxylic acid) and ellagic acid are produced by the oxidation of tannin the author has suggested that the production of ellagic acid in plants may be due to oxidation (Abstr.1908 i 897). This suggestion is strengthened by the fact that the hot filtered pyridine extract of myrobalan after dilution with water boiling and keeping for thirty hours yields ellagic acid whilst the concentrated mother liquor deposits luteo-acid identical in all respects with that obtained synthetically from tannin. c. s. The So-called “Bloom” of Pyrogallol Tannins and Its Identity with Ellagic Acid. MAXIMILIAN NIERENSTEIN (Chem. Zeit 1909 33 87. Compare Abstr. 1905 i 365 805).-The “bloom ” of some samples of sole-leather and of various pyrogallol tannin materials has been examined and with but one exception was conclusively shown to be ellagic acid. The exception is ‘‘ white mangrove,” the bloom of which is laguncurin a yellow dye.W. H. G. Coumarandione the Analogue of Isatin in the Coumarone Series. RICHARD STOERMER (Ber. 1909 42 199-202. Compare Stoermer and Kahlert Abstr. 1902 i 457).-It has at last been found possible to prepare coumarandione the lactone of o-hydroxybenzoyl- formic acid which is the analogne of isatin in the coumarone series. 1-Nitro-2-diisobutylaminocoumarone when warmed with alcoholicORGANIC CHEMISTRY. 175 potassium hydroxide is decomposed with the formation of diisobntyl- amine and the potassium salt of aci-nitrocoumaranone obtained as lemon-yellow needles. acid it liberates nitric peroxide and yields " leuco-oxindigo," When this salt is treated with an obtained as a canary-yellow 'precipitate m.' p.276" (decomp.). The leueo-compound is oxidised by chromic acid in acetic acid into coumarandione C,H,O which crystallises with 1 H,O in small yellow needles m. p. 1 7 8 O (decomp.) and is converted by hot dilute hydro- chloric acid into o-hyclroxybenzoylformic acid Coumarandione when acted on by hydroxylamine yields diisonitrosocoumayone a colourless crystalline substance m.' p. 203-205'. o-Hydroxybenzoylformic Acids and Coumarandiones. KAXL FRIES (Be,.. 1909 42 234-236).-o-Hydroxybenzoylformic acid occurs in an anhydrous form and also as monohydrate. The hyd~ata of 2-hydroxy-4-methylbenzoylformic acid crystallises in plates m. ,p. 64'; it is faintly yellow and stable in the atmosphere. The anhydrous acid is more soluble in benzene than the hydrate; it crystallises in feather-like needles m.p. 1 0 2 O which are almost colourless except when viewed in mass. The hpdrate of 2-hydroxy-5- methylbenzoylformic acid forms yellow prisms m. p. 75'; the anhydrous acid crystallises in needles m. p. 107O. These acids lose carbon dioxide and water when heated forming methylcoumarandiones but the yield is small and the product di5cult to purify. They are conveniently prepared by heating the hydroxybeozoylformic acids in benzene or petroleum solution with an excess of phosphoric oxide for fifteen minutes. W. H. G. 5-MethyZcoz~marandione C6H,Ne<(o>C0 crystallises in well- formed yellow plates m. p. 112'. I n contact with water it is slowly converted into the hydroxy-acid and goes into solution. It dissolves in concentrated sulphuric acid with a yellowish-red coloration and on dilution the hydroxy-acid is formed. The ketone reacts immediately with o-phenylenediamine but 2-hydroxy-3-m-hydroxy-p- tolylquinoxaline and not methylcoumarophenazine is formed.4-Methylcoumarandione crystallises in long golden-yellow prisms m. p. 149'. These diketocoumarans and the hydroxy-acids give the indophenin reaction with benzene containing thiophen and concen- trated sulphuric acid. E. F. A. Method of Preparation of Ketothionaphthens. KARL AUWERS and F. ARNDT (Ber. 1909 42 537-545).-Starting with p-tolyl methyl thioether a method is described of obtaining thionaphthen derivatives by using chloroacetyl chloride. pToZyZ methyl thioethm C,H,,,S from the sodium salt and methyl n 2176 ABSTRACTS OF CHEMICAL PAPERS.sulphate is a colourlesa oil b. p. 209"/747 mm. 9 4 O / 3 1 mm. D1,6 1.0302 nz 1.57537 which when heated with chloroacetyl chloride and aluminium chloride in carbon disulphide solution for five hours and subsequently distilled with steam is converted into keto-4- rnethy2thionaphtAen C,H,Me<';>CH,. It crystallises from petroleum in colourless needles m. p. 103" which gradually change when moist to carmine-red. On oxidation with potassium ferri- cyanide in diln te alkali '' 4'-dimethylthioindiqotin," C,,H,,O,S is formed which crystallises from nitrobenzene in brownish-red needles m. p. over 300'. C,H,Me<yf> C CHPh is formed by the condensation of benznldehyde and ketomethylthio- naphthen in alcohol in the presence of hydrogen chloride and forms long yellow glistening needles m.p. 145 *5O. forms stout yellow prisms m. p. 116O and is re-converted into the parent substance by alkali or alcohol. hT'tobenxylidene-thionu~htkeiz C,,H,,OS crystallises from alcohol in yellow needles m. p. 131.5"; its dibronzide C1,HloOBr,S forms crystals m. p. 114-115°. 6-Met~~Zthiol-3-rnethyZa,ceto~~~~enone SMe*C,H,Me*COMe from tolyl methyl thioether acetyl chloride and aluminium chloride crystallises from light petroleum in white needles m. p. 51.5". It is not hydrolysed by known methods either being I ecovered unchanged or suffering decomposition. The 6-thiol-3-methylacetophenone could not be obtained from the thiocresol by a similar method to the methyl ether. p-Tolyl chlorothiotacetate C,K,Me*S*CO*CH,Cl from thiocresol and chloroacetyl chloride which forms snow-white crystals m.p. 38" could not be converted into the o-chloroacetyl isomeride (compare Fries and Pinck t h i s vol. i 42). The acet2l compouud of thiocresol J,H,,OS is an oil b. p. 121'/14 mm. Cinchonamine and Certain Other Rare Alkaloids. BERNARD F. HOWARD and 0. CHICK (J. Xoc. Chern. Ind. 1909 28 53)-The results of trials with cinchonamine hydrochloride as a test for nitric acid and for the estimation of nitrates by the formation of cinchon- amine nitrate which is nearly insoluble in water especially in presence of free acid (compare Absti.. 1905. i 102) are given. Certain data respecting cinchonamine quinicine cinchonicine cupreine and concus- conine are also recorded. Cinchonamine hydrochloride may be used for the estimation of nitrates in certain cases where other methods present difficulties and yield results but little inferior to those given by the nitrometer process but is unsuitable for use in presence of salts of bismuth or other metals which yield insoluble oxychlorides. In aqueous solution 1/100,000 OF nitric acid can be detected and in acetic acid 1/500.Cinchonamine C19H240N [aID + 120° in alcohol does not contain methoxyl. Quinicine U20H2402N8 [a] + 38'40' in chloroform yields a Keto benx y Zidene - rneth y 1 t?Lionapht?Len The dibromide c16H120Br2S9 W. R.ORGANIC CHEMISTRY. 177 crystalline tartrate B,H2C4H406 and oxalate 2B,H,C,0,,9H20 and contains one methoxyl group. Cinchonicine C1,H,,ON [a] + 47O13' like quinicine could not be obtained crystalline ; it does not contain methoxyl.are crystalline. Concusconine C,,H,,O,N [.ID + 19'34' was prepared from cinchonamine residues ; it contains two methoxyl groups. Cupreine U,,H,,O,N,,. [.ID - 163'45' in alcohol contains no methoxyl. The amorphous platzmchloride B,H,PtCI,,H,O was prepared but the salt B,,H,PtC1,,4H20 referred to by LBger could not be obtained. Cupreine sulphate B,,H,SO is stated to crystallise with 6H20 but this salt prepared under various conditions was found to be anhydroue. The acid sulphate B,H2S04,H,0 crystallises in short stout yellow prisms. The disulphate B,2H,S04,3H,0 forms short silky needles and is deliquescent. The hydrochloride B,HCl,H,O crystallises in small slightly brown needles and the dihydrochloride B,2HCl is also crystalline The formulae assigned to these' alkaloids were confirmed by determination of the platinum in the respective platinichlorides.T. A. H. The tartrate B,H,C4H,0,,H,0 and oxalate 2B,H2C204 7H20 Isomerism of Ephedrine and +-Ephedrine. HERMANN EHDE (Arch. Phwrm. 1909 247 54-55).-In a previous paper (hbstr. 1908 i 203) the author has shown that ephedrine is better represented by the formula NHMe-UHPh*CHMe*OH than by OH*CHPh*CHMe*NHMe and that +-ephedrine is an optical isomeride of ephedrine. Gadamer (this vol. i 49) accepted this but suggested that the conversion of the one isomeride into the other by the action of hydrochloric acid is probably due to racemisation in the asymmetric complex containing the hydroxyl group rather than in that con- taining the methylimino-grouping.The author now points out that this explanation is not excluded by his former paper and that he left this point as an open question. T. A. H. Crystallography of the Ephedrine Damascenine and Aconitine Groups. K. SCHWANTKE (Zeitsch. Kryst. Min. 1909 46 73-115).-$-Ephedrine rhombic [a b c = 0.84492 1 1.8598 . Ephedrine hydriodide rhombic [a b c=0*73703 1 0*28643]. +-Ephedrine hydriodide rhombic [a b c = 0 60282 1 1.37221. Methylephedribe methiodide rhombic [a b c = 0.97926 1 0.760881. Methyl-$-ephedrine methiodide rhoubic L0.64227 1 1 *2088]. Damascenine hydrochloride triclinic [a b c = 0-66527 1 0.453 18 ; a= 89'51'; /3= 103'30'; y=89'11']; hydrobromide monoclinic [ a b c = 2.7575 I 2.4825 ; fi = 100°6'] ; hydriodide monoclinic [a b c = Aconitine rhombic [a b c = 0.54492 1 0.389171 ; hydrobromide rhombic [a b c=O*86455 1 1.30951 ; hydrochloride rhombic [a b c= U.1174S8 1 1.30401.Piciaconitine could not be obtained crystalline. Methylpicraconitine rhombic [a b c = 0.995'72 1 :1*31416]. Ethylpicraconitine rhombic [a b c = 0.117952 1 1.2700]. Aconine hydrochloride monoclinic [a 6 c = 0.6346 1 1 1.0374 ; /3 = 90'1. 2.7519 1 2.43'72 ; p = 99'27'1. L. J. S."178 ABSTRACTS OF CHEMICAL PAPERS. Dicyclic Quaternary Bases. AUGUST ALBERT (Ber. 1909 42 545-556).-1t has been shown by Gabriel and Uolman (Abstr. 1906 i 881) that when evaporated with water y-chloropropyl- piperidine is transformed into the quaternary salt and that the reaction is a reversible one. This paper deals with the preparation of a dicyclic quaternary salt containing one more methylene group in one of the rings.1-&Phenoxybutylpiperidine OPh.[CH,],*C,NH1 obtained by heating 8-chlorophenoxybutane with piperidine for four hours at loo' distils at 316-320'. It is purified by means of the hydriodide CI,H,,ON,HI which forms white feathery needles m. p. 147'; the hydrochloride has m. p. 156O the hydrobromide m. p. 159O the picrate m. p. 120-121' the rnercurichloride m. p. 138O and the gold salt m. p. 121'. When the hydrochloride is heated with hydro- chloric acid in a sealed tube at 150' for five hours 1-6-chlorobutyl- piperidine hydrochloiGde CH2C1* [CH2],*C5NH,,,HCl is formed quanti- tatively; it crystallises in white plates from acetone m. p. 162'; the auricldoride CgHlgNC1,Au has m.p. 93' the picrccte m p. 132O. 6-Bronrobutylpiperid~~ hydrobromide C,H,,NBr prepared in a similar rdanner forms plates m. p. 162.5'. A cold ethereal solution of 8-chlorobutylpiperidine is quickly converted into tetramethylenepiperylium chiloride >CH2 FH,*CH CH,*CH CH2*CH >NC1<CH,*CZ32 which forms white hygroscopic leaflets ; the auriclbloride C H,,NCl,Au has m. p. 245' the picrate C15H2,07N4 m. p. 232' the mercuri- chloride CgH,NC1,6HgCl m. p. 2 2 9 O the platanic?doride m. p. 237". Alkali converts 8-bromobutylpiperidine hydrobromide at once into the quaternary salt. That it is not the diquaternary salt C ~ H ~ ~ C 1 < ~ ~ ~ 3 > N C l C ~ H ~ ~ is proved by its synthesis from e-chloropentylpyrrolidine whereas if diquaternary salts were obtained in such regctions the isomeric compound C,H,NCl<[C8215>NC1C,H would be the result.This was accomplished by heating echlorophcnoxypentane with pyrrolidine at 100' for four hours when r-phenoxypentylpyrrolidine which distils at 317-318'/760 turn. was obtained. OPh*[CE2]5*C4NHfi,HCI has m p. 139' the hydriodide m. p. log' the aurichloyide C1,H,,ON Cl,Au m. p. logo and the piwaate m. p. 99-100'. forms light yellow very hygroscopic crystals ; the picrate and pzbolonate have been prepared. The base undergoes in ethereal solution isomeric change into the tetramethylpiperylium chloride. This quaternary salt does not give 6-chlorobutylpiperidine on evapor- ation of its aqueous solution thus proving more stable than the trimethylene compound. W. R [CH215 The hydrochloride r-Chloropentylpyrrolidine c1py O,"p,ORGANIC CHEMISTRY.179 Synthesis of Inactive 6-Coniceine. KARL LOFFLER and HANS KAIN (Ber.. 1909. 42. 94-107L-The constitution suggested by Lellmann (kbstr. 1890 l i 2 8 ) for 8-coniceine has been confirmed by direct synthesis. Pyridylacrylic acid (Einhorn Abstr. 1892 77) when reduced by Ladenburg's method with sodium and alcohol yields piperidyl- propionic acid which was isola?ed in tho form of the hydrochloride of the ethyl ester. The free acid when distilled under reduced pressure yields the which on reduction yH,*CH,* $7 H*CH2 lact im 2 -piprolidone CH,*CH,-N-CO>CH2' with sodium and alcohol ;ieldi piperolidine 5!H2*CH2*$7 H*-CH c H,. CH2*N-CH2>CH2* This is identical with inactive 6-coniceine which was prepared from i-coniine by a process similar to that used by Lellmltnn in the preparation of active 8-coniceine.Ethyl pperidylpropionate hydrochloride C,H,,N*CH,-CH,*CO,Et HCl crystallises from acetone in glistening colourless needles m. p. 122O. The aurichloride CloH190,N,HAuC14 forms yellow needles m. p. 127-128'; the platinichloride has m. p. 127-130'. The free ester has b. p. 143-144'/21 mm. and Di6 1.0214 and is hydrolysed by hot hydrochloric acid to the hydrochloride of the acid C,H,,O,N,HCl which melts at 188'. The aurichloride C,H,,O,N,HAuCl has m. p. 151' and the platinichloride 197O. The acad crystnllises from water in large rectangular plates containing water of crystallisation. It begins to sinter at 70' and melts at 105' or when anhydrous at 2-Piperolidone has b.p. 126-127'/12 mm. or 263-264'/760 mm. and Di5 1.0715. The hydrochloride is hygrxcopic ; the platinichZoride (C,H1,0N),,H,PtC16,2H20 forms large hexagonal plates and has m. p. 138' ; the aurichloride is oily. Piperolidine has b. p. 161' and DY 0.904 and its aqueous solution is strongly alkaline. The picimte C,H,,N,C,H,O,~ has m. p. 226'; the hydrochloride is hygroscopic ; the aurachlorade crystallises in compact needles m. p. 192' after sintering at 189'; the platini- chloride melts and decomposes a t 213' ; the mercuric salt has m. p. 235-238'. The ethiodide is formed immediately on the addition of ethyl iodide to an ethereal solution of the base and the corresponding platinichloride (C,H1,NEt)2PtC16 begins to decompose at 21 8' and has m.p. 229-230'. 147-148'. C;H,*CH,*Q H*CH CH,*CH,*N-CO 3-Hydroxy-2-piperolidone 2>CH*OH is obtained when Einhorn's a-pyridyllactid acidi is reduced and the aqueous solution of the resulting acid evaporated. It separates from acetone in colourless crystals m. p. 129-130° b. p. 183-184'/18 mm. or180 ABSTRACTS OF CHEMICAL PAPERS. 304-305'/760 mm. The aurichloride C,H1,O,N,HAuC1 m. p. 89-90° and the pIatinichZoride (C,H1,0,N)2,H2PtC1 m. p. 92 -94" are both readily soluble in water. J. J. S . Synthesis of p-Coniceine (I-a- Allylpiperidine). KARL LOFFLER and GOTTHOLD FRIEDRICH (Ber. 1909 42 107-1 16).-2-/3-Hydroxy- propylpiperidine (Ladenburg Abqtr. 1890 68) wheu heated at 100' with phosphoric oxide yields a mixture of two isomeric secondary bases one of these i a solid m.p. 18'. This can be resolved into active components the I-form of which is identical with p-coniceine (Loffler Abstr. 1905 i 917) which is thus shown to be l-a-allyl- piperidine. The isomeric b<tse iso-a-allylpiperidine which can be isolated from the alcoholic mother liquors of the picrate of the solid base can also be resolved into active components by means of the hydrogen tartrates. 2-P-Hydroxypropylpiperidine forms a picrate m. p. 11 1 -1 12' a platinichloride m. p. 148-149' and an aurichloride m. p. a-Allylpiperidins forms a well-defined picrate C,Hl,N,C,H,O,N m. p. 113-1 14.5'. The hydrochloride C8H,,N,HC1 crystallises in glistening plates sparingly soluble in acetone m. p. 206-207'. The awrichloride has m. p 107-108' and the platinichloride m.p. 184'. The free base has m. p. 18' b. p. 168*5-17OC/753 mm. and Di5 0 8716. It readily reduces permanganate and yields a nitroso- amine with nitrous acid. It combines with hydrogen iodide and the additive compound when reduced yields a-propylpiperidine. The d-tartrate of the d-base is less soluble than t h a t of the I-base ; it has m. p. 39' and iso-a-AZAylpiperidine yields an oily picrate. The hydrochloride C,H,,N,HCl has m. p. 186-187' and is stable when exposed to the air ; the pkatinichloride has m. p. 138-139' and the base has b. p. 166*5-168*5' and DF 0.8695. has m. p. 70-71'. The base from the tartrate has [ a$ + 24.8'1' at 15O and the corresponding hydrochloride m. p. 189-190'. The liquid base obtained together with p-coniceine by the elimination of water from conhydrine has [a]= - 25.5' and its hydrochloride has m.p. 189-190'. This base can be partly transformed into p-coniceine by saturating with hydrogen chloride at - 16" heating in sealed tubes a t 100' for several hours and then eliminating hydrogen chloride. When reduced by Ladenburg's method solid p-coniceine yields I-coniine and this affords a simple method of passing from conhydrine to I-coniine. J. J. S. 136-137'. + 49.89. The d-hydrogen tartrate C,H'l,N C4H606 Constitution of J/-Conhydrine. KARL LOFFLER (Bep. 1909 42 116-124. Compare Ladenburg and Adam Abstr. 1891 1119).- +-Conhydrine and conhydrine are readily separated by means of their hydrochloiides ; the salt derived from conhydrine is extremely hygro- scopic whereas that from the $-base crystallises well from alcohol and has m.p. 212-213'. The +-base has m. p. 105-106' (not 100-lOZ") b. p. 236-236*5' and aD + 10.98' to + 11 *06'. It crystallises from anhy-ORGANIC CHEMISTRY. 181 drous ether in extremely slender needles but from-moist ether in hydrated plates m. p. about 80'. Engler and Bauer's statement (Abstr. 1894 i 471) that $-conhydrine can be transformed into coiihydrine by simply preparing the gold salt and decomposing this in the usual manner is not confirmed. $-Conhydrine aurichloride C8H170N,AuC1 has m. p. 133-1 34O and the platinichloride forms slender golden-yellow needles m. p. 185-1 86'. $-Conhydrine is an hydroxyconiine since when treated with hydriodic acid a $-iodoconiine is obtained which on reduction yields d-coniine whereas conhydrine under similar conditions yields l coniine.Con- hydrine and $-conhydrine are not stereoisomeric as the latter yields no trace of peonicehe or its oily isomerids (compare preceding abstract). Similarly when the $-base is transformed into the iodo-derivative and hydrogen iodide is eliminated from this no trace of the dicyclic 8-coniceine is formed. It is shown that the hydroxyl group of the $-base cannot be present in the side-chain and must thus be attached to a carbon atom of the nucleus probably in the y-position. The $-coniceine CSHl5N obtained by the action of phosphoric oxide on $-conhydrine at 100-120° has b. p. 171-172' Dt5 0.8776 and [aID + 122.6' at 15'. It does not dissolve readily in water decolorises permanganate and forms a nitrosoamine. Its hydrochloride crystal- lises from a mixture of alcohol and acetone. and has m.p. 205-206O. The platinichloride has m. p. 153-154' and the aurichloride is an oil. The iodoconhydrine obtained by the action of hydriodic acid on $-conhydrine yields a hydriodide C,HIGNI,HI m. p. 2 16-2 17" whereas the isomeric compound obtained by the addition of hydrogen iodide to $-coniceine has m. p. 182'. $-Conhydrine. CARL ENGLER (Ber. 1909,42,559. Compare Engler and Bauer Abstr. 1894 i 471.).-As Loffler (preceding abstract) has shown that Ladenburg and Adam's $-conhydrine (Abstr. 1891 i 11 19) is a solid solution of conhydrine and $-conhydrine there is no foundation for the supposed conversion of the pseudo-compound into conhydrine. J. 3. S. w. K. 4-Picolylalkine [ 4-p- Hydroxyethylpyridine] 4 - Pipecolyl - alkine [ 4-P-Hydroxyethylpiperidine and Quinuclidine.KARL LOFFLER and FRITZ STIETZEL (Ber. 1909 42 124-1 32l-4-Methyl- pyridine condenses readily with 40% formaldehyde solution yielding Eoenigs and Happe's trimethylol derivative (Abstr. 1903 1 S51) but with a 20% aldehyde solution at 135-140' it yields the mono- methylol derivative 4-/3-hydroxyethylpyridine C,NH,*CH2*CH,*OH as a colourless syrup Di5 1.1016 and b. p. 125-126'/15 mm. It is most readily purified by means of the picrate C1,Hl,O,N which forms compact dark yellow crystals m. p. 122-123'. The platinichloride forms crystalline plates m. p. 164' (decomp.) readily soluble in water. The aurichloride has m. p. 124-125'. When heated with hydriodic acid and red phosphorus 4-P-hydroxyethylpyridine yields the oily iodide C,NH,-CH,*CH,I.The corresponding picrate forms long refractive prisms m. p. 108-110' and the platinichloride forms pale yellow needles m. p. 147-1489 When warmed the iodide is readily182 ABSTRACTS OF CHEMICAL PAPERS. \\ HCH-CH \CH=CEi!/ transformed into the isomeric pyridoniuin iodide C-CH,*CH - NI (compare Abstr. 1905 i 265) which crystallises from dilute alcohol in minute colourless needles m. p. 216-218'. The corresponding chloride forms minute crystals and the plutinichloride ( C7H,hT),PtC16 an insoluble flesh-coloared precipitate decomposing at about 300". It has not been found possible to transform Happe's tri-iodohydrin from the trimethylol derivative into an isomeric pyridonium salt. _ _ 4-p-Hydrox yethylpiperidine NH<C CH2*CH2>CH*CH,-CH2*OH H,.CH ob- tained by reducing the corresponding iyridine derivative by Laden- burg's method has b. p. 120-125'/15 mm. or 227-228"/760 mm. and Di5 1.0059. The uurichloride C7HI,0N,HAuC14 forms large compact crystals m. p. 108-1 10" ; thepzcrate is oily. With hydriodic acid and phosphorus the base yields the hydriodide C7H14NI,HI which crystallises from hot water in needles m. p. 158-159". The iodo-base is readily transformed into the quinuclidine hydriodide CH-CH;CH -NHI when its etheieal solution is boiled. The hydriodide forms a colourless syrup retidily soliible in water. The picrate crystidlises in slender pale yellow needles. The base C7Hl8N has b. p. 140-141' and DT' 0.9139. It does riot decolorise permmganate and forms an ethiodicle which is hygroscopic.It. has an intense odour of semen. /CH**CH2\ \C H,. c H:/' The platinichloride (C9Hl,N)2PtC16 has m. p. 3 12'. J. J. S. Condensation of 2 6-Lutidine with Formaldehyde and Derivatives of %Methyl-6-methylolpyridine. KARL LOFFLER and FRITZ THIEL (Ber. 1909 42 132-140. Compare Koexiigs and Happe Abstr. 1903 i 850). 2-Methyl-6-d,hylolpyridine distils at 121-12Z0/15? mm. and has m. p. about 55". It does not decolorise permanganate and yields a picrate which crystallises in pale yellow needles m. p. 102-102s50. The platinichloride has m. p. 183-185' (decomp.). I n the preparation of the monohydroxy-derivative an appreciable amount of a dihydroxy-compound C,H,,O,N is formed. This crystal- lises from a mixture of chloroform and ether in colourless prisms m.p. 73-74-5' and b. p. 185.5-186°/15 mm. The picmte crystallises from alcohol in yellow needles m. p. 133.5-134.5'. The platini- cidoride (C,H,,~,N),,H2PtC1 has m. p. 1'71-1 73" (decomp.) and the ccu?*ic/doride m. p. 141-142'. When oxidised with nitric acid the base yields dipicolinic acid and hence is presumably 2 6-diethylol- yyridine. 2-Methyl-6-ethylolpyridine condenses with benzaldehyde at 125-130' yielding a brown oil the platinichloride of wbich de- composes at 200-806°. This condensation product is probably 6-phenylmbthylol-2-ethylolpyridine OH*CH,*CH,*C5NH,*CH,*CHPh*OH. When heated at 125-130" with hydrobromic acid which has been saturated at O' the methylethylol derivative yields 2-methyl-6-bromo-ORGANIC CHEMISTRY.183 ethylpyridine. The picrate CSHloNBr,C6H302N3 crystallises from benzene in slender prisms m. p. 111'; the plutinkhloride separates from water in compact pointed crystals m. p. 183-186" (decomp.) and the aurichloride forms reddish-yellow needles m. p. 159-162' (decomp.). The free base is slowly isomerised to the pyridonium - I - - CH:CH-E-yH ' CH:CMe-NBr-CH,' bromide I which crystallises from acetone in snow- white needles m. p. 155-156'. 2-Me thyl- 6-e thylpyridine is obtained when the met h yl-bromoe thy 1- pyridine is reduced with zinc dust and hydrochloric acid ; it is usually accompanied by a certain amount of methylvinylpyridine which can be removed by treatment with acidified N/100 permanganate. The pure metbylethyl derivative is a colourless liquid b.p. 160-161*5°/ 760 mm. and D15 0.9229. The picrate C,H,,N,C6H307N3 forms yellow plates m. p. 127-127.5O ; the platinicldoride small crystals m. p. 188-190' (decdmp.) and the aurichloride yellow needles m. p. 1 2 7.5-1 2 8.5'. When reduced by Ladenburg's method the base yields two stereo- isomeric 2-methyl-6-eth~Z~iperidines which can be separated by means of their hydrochlorides C,H,,N,HCl. Of these one is sparingly soluble in acetone and forms long snow-white needles m. p. 153-5-154O. The corresponding platinichloride ( C,H17N) H,PtCI forms well developed prisms m. p. 188-190° and is readily soluble in water. The aurichloride has m. p. 134O and the picrate forms long needles m.p. 135'. The free base has b. p. 151-151.5'/T55 mm. (corr.) and DI4O5 0.8306. The base can be resolved into its active components by crystallising the acid tartrates.The sparingly soluble tartrate m. p. 58-59' gives a base with 13-97'. The platinichloride of the active base decomposes at 204-206O ; the aurichloride has m. p. 133*5-134*5O and the hydrochloride m. p. 287-288'. The hydrochloride which is readily soluble in acetone forms needles m. p. 171*5-172.5°. The platinichloride has m. p. 196-197' and the bme iso-2-methyl-6-ethylpiperidine is a colourless liquid b. p. 157-15S0/760 mm. and D 0.845. The picrate has m. p. 101.5-102° and the aurichloride is an oil The base can be resolved by means of camphorsulphonic acid but the acid tartrates are syrups. J. J. S. N-Hydroxydioxindole Trioxindole. GUSTAV HELLER [ with JULIUS SOLLING] (Ber. 1909 42 470-479).-Reissert has already prepared N-hydroxyindole (hbstr.1896 i 389 ; this vol. i 51). N-liydroxy- dioxindole (trioxiradole) C,H4<N(OH)>C0 is obtained when ammonium o-nitromandelate is reduced with zinc dust and water in the presence of ammonium chloride and then acidified with hydro- chloric acid. It crystallises from water in colourlesa prisms sinters at 167" and melts and decomposes at 172'. The aqueous solution has an acid reaction gives a blue coloration with ferric chloride and reduces Fehling's solution in the cold. Alkalis decompose the com- pound and in the presence of atmospheric oxygen anthroxanic acid is formed; if an excess of alkali is present isatin is also formed. CH(0N)184 ABSTRACTS OF CHEMICAL PAPERS. Trioxindole is converted into N-hydroxyisatin when its acetone solution is oxidised with a dilute acetic acid solution of permanganate ; acetoxy- dioxindole under similar conditions yields isatin.Oxidation with a hot alkaline solution of permanganata converts trioxindole into azoxy- benzoic acid and reduction with zinc dust and acetic acid yields isatyd (Heller Abstr. 1904 i 516). Acetoxydioxindole CloH,O,N crystallises from benzene in prisms which turn red a t 100' and then melt a t 125'. Its alkaline solutions deposit salts of isatoic acid when kept and its aqueous solution yields isatin when boiled. The N-benzoyl derivative C,H,O?N*COPh obtained by the action of benzoyl chloride in the presence ot aqueous sodium acetate solution has m. p. 126'. A different benzoyl deriv- ative is obtained by benzoylating in pyridine solution ; it bas m.p. 152O. With hydraziue sulphate and sodium acetate solution the trioxindole yields a compound C,H,O,N m. p. 243' which is insoluble iu alkaiis ; the mother liquors from the compound yield isatinhydrazone. With phenylhydrazine a cornpound C20H17N6 is obtained. It crystallises from alcohol in large pliable plates m. p. 226". Isatinosaxone which is isomerlc with this compound crystallises from a mixture of chloroform and light petroleum in slender reddish-brown needles rn. p. 183' (decomp.). J. J. S. Asymmetric Nitrogen. XXXV. One-sided Addition of a Tertiary Base to a Dihalogenide. EDGAR WEDEKIND (Ber. 1909 42 300-303).-The author attempted to synthesise an optically active compound containing two asymmeti ic nitrogen atoms.A completely analogous compound to tartaric acid is scarcely possible but it was hoped to prepare one in which the nitrogen atoms were separated by one or more methylene groups. It was found however that interaction of ethylene bromide with isokairoline (N-methyltetra- hydroisoquinoline) does not lead to the formation of ethylenebis-iso- kairolinium bromide but t o bromoethylisokairolinium bromide 'GH4<C €3,. N Me Br C H ,*CH,Br' which crystallises from a mixture of alcohol and ether decomp. 1 8 3 O . This compound has no further action on isokairoline and this inability to form a further additive compound is ascribed to steric hindrance. The iodide C,,H!7NBrI readily obtained from potassium iodide and a n aqueous solution of the bromide crystallises from ether and if the iodide or bromide is shaken with moist silver oxide neutralised with hydrogen chloride and plittinic chloride added the platinichEoride ( C,NHloMe CH,*CH,*OH),PtCYl is precipitated.N-Ethyitetrahydroisoquinoline has no action on ethylene bromide and ethylene iodide gives with isokairoline an abnormal salt. CH2- 7 H ~~h~lenebis-isokairoliniunl iodide CH,*YH CH,* C,H,' FH2-cH2>N MeEr* CH,*CH X MeBr< C,H,*CH easily obhained from ethylenebistetrahydroisoquinoline (1 mol.) andORGANIC CHEMISTRY. 185 methyl iodide (2 mols.) separates from alcohol as a crystalline powder decomp. 232O and the free base forms the pZcctinicldoride C,,H,oN,C1,Pt. The dicamphorsulphonate from the iodide and silver d-ca,mphorsul- phonate in moist acetone could not be resolved into fractions of differing rotatory power and the regenerated iodide is inactive.W. R. 5-Methylisooxazole. LUDWIG CLAISEN (Ber. 1909,42 59-6S).- The substance b. p. 103-105c/20 mm. obtained by Schmidt and Widmann (Abstr. 1908 i 456) and designated 5-methylisooxazole cannot be such. The author has already prepared 5-methylisooxazole b. p. 12d0 or 29-30'/20 mm. (Abstr. 1892 1072). I n the isooxazoles as in other homologous series the b. p. of the methyl derivative must lie between those of the parent substance and of the dimethyl deriv- ative. isoOxazole has b. p. 95.5" and dimethylisooxazole 141-142". A substance of b. p. 103-105°/20 mm. would have b. p. above 200" under atmospheric pressure and consequently cannot be a methyliso- oxnzole.Moreover Schmidt and Widmann's substance does not possess the unpleasant odour of pyridine which is so characteristic of the lower isooxazoles. The author contributes the following new properties in cormexion with the methylisooxazoles. The sesquioxime C8HI3OaN3 obtained previously (Abstr. 1 S9 I 41 6) is decomposed by warm N/%hydro- chloric acid yielding pure 5-methylisooxazole whilst with concentrated hydrochloric acid a mixture is obtained of 80% of 3-methylisooxazole and 20% of 5-methylisooxazole from which the latter is easily removed by treatment with sodium ethoxide (Abstr. 1904 i 14). 5-Jrlethylisooxazole in aqueous-alcoholic solution forms with platinic chloride a yellow crystalline compound (C,H,ON),PtCl m. p. 21 0-21 2' and a white crystalline merczcrichlorzde C,H,ON,BgCI and cadmicldoride C,H,ON,CdCI with aqueous mercuric and cadmium chlorides respectively. I n dilute aqueous potassium hydroxide 5-metbylisooxazole forms a clear solution of potassium cyanoacetone from which phenylhy drazine hydrochloride precipitates cyanoacetone- phenylhydrazone.Sodium cyanoacetone is obtained quantitatively as a white crystalline precipitate by adding alcoholic sodium ethoxide to a dilute ethereal solution of 5 -methylisooxazole and in aqueous-alcoholic solution yields with diazobenzene chloride a yellow crystalline phenyl- azocyanoacetone and with aniline hydrochloride cyanoacetoneanilide. 5-Methylisooxazole yields /3-iminobutyronitrile by heating a t 100" with alcoholic ammonia ; 5-stmino-l-phenyl-3-methylljyrazole by prolonged heating with phenylhydrazine and with methyl iodide at 100' a methiodide C,H,ONMeI m.p. 125-126" which in cold aqueous solution is converted by silver oxide into acetoacetmethylamide the iV-benzoyl derivative of which CH,*CO*CH2*CO*NMeBz m. p. 107O is obtained by slowly warming 5-methyl.isooxazola and methyl sulphate a t TO" pouring the product into water and adding a solution of potassium benzoate. The preceding reactions are quoted by the author as additional evicleuce for the correctness of the constitution of his 5-methyl- isooxazole. c. s.186 ABSTRACTS OF CHEMICAL PAPERS. Asymmetric Nitrogen. XXXVI. Quaternary Amino- ammonium Salts a New Type of Asymmetric Nitrogen. EDGAR WEDEKIND and WOLDEMAR MEYER (Bey. 1909 42 303-309). -The result of the experiments on isokairoline (this vol. i 184) lead t o the examination of other ditertiary bases with regard t o their additional activity towards alkyl haloids.The type employed was Ph>N=[CH2],*N<F a ; when x = 2 and a is Et benzyl bromide gives no additive compound ; when x = 3 and a is Me then benzyl bromide is quickly taken up by both tertiary nitrogen atoms ; if x = 2 and a is Me then only one molecule of benzyl bromide is absorbed to form a monoquaternary salt. An analogous amino-ammonium salt is formed from diphenyldimethylothylenediamine and methyl iodide ; the diquater- nary salt can be obtained indirectly however by the action of methyl sulphate and subsequent conversion of the methyl sulphate salt into di-iodide. The diquaternary or the amino-ammonium salt can be obtained from ally1 iodide and diphenyldimethylpropylenediamine according to the conditions.The conclusion is drawn that the inability t o form diquaternary salts in the case of dimethylme compounds is due to steric hindrance (Zoc. cit.) and that the lengthening of the chain t o three methylene groups enables the latent additive activity of the other nitrogen atom to become operative. The high molecular rotatory power of the amino-ammonium salts examined is in accord- ance with their high degree of asymmetry. Phen~ZbenxyZmethyZ-(methyZalzilinoethyZ)-an~monium bromide C,H 7*NMePhBr*CH2-CH2*NMePh from diphenyldimethylethylenediamine and benzyl bi omide is obtained in 59% yield and IS crystallised from acetone containing a little alcohol decomp.119-139O. Once with excess of bromide a dibromide C,,H,,N2Br2 was formed decomp. 124-1 25'. The amino-ammonium compound is very easily resolved into its optical antipodes as the solubility of the I-base-d-camphorsulphonate in methyl alcohol is very much less than the d-compound. The extreme [MI of the fractions for the ions were - 4 4 2 O and + 417'. The two camphorsulphonates form snow-white needles decomp. 125O. The d-base-d-bromocamphor- sulphonate is the less soluble salt when t h e bromo-compound is used. The I-amino ammonium iodide C,,H,7N2T forms rhombic plates decomp. 115O [MI -411.5' in alcohol and [MI -424.6' in chloro- form. The d-iodide has [MI +403-2' in alcohol and undergoes autoracemisation in solution ; the velocity constant in 50% alcohol- chloroform solution is K = 0 00024 and in 96% alcohol K = 0*000033. The rate is therefore much slower in alcohol than in chloroform but that it takes place in alcohol which has a high dielectric constant is surprising in the light of Wedekind and Paschke's work (Abstr.1908 i 722). As benzgl bromide can be detected in the inactive solution the conclusion drawn previously that racemisation is due to decomposition and not t o intramolecular change is supported. P~~nyImet~yZethyZ-(ethyZaniZinoethyZ)-c~mmonizcm iodide NEtPh* C2H,-NMeEtPhI obtained from diphenyldiethylethylenediamine and methyl iodide in a closed tube heated at 80' for six hours crystallises from ether decomp.ORGANIC CHEMISTRY. 187 18O*,and the symmetricalcompound C,H,(NPhMeEtT) from diphenyl- diethylethylenediamine and methyl sulphate at 120' and precipita- tion by potassium iodide is yellow decomp.119-120'. ~ ~ p ~ e n y Z d ~ b e n z y Z d i ~ e t ~ ~ Z t r ~ m e t ? ~ ~ t ~ ~ e d ~ a ~ ~ o n dibromide CH,(CH,*NPhMeBr*CH,Ph), forms coloiirless crystals decomp. 195-1 97". The dicamphor- sulphonate is well characterised. W. R. Migration and Reciprocal Displacement of Acid Groups in Acylated Dibromohydroxybenzylphenylhydr- wines. KARL AUWERS (Ber. 1909 42 267-277).-An extension of the inquiry (Abstr. 1908 i 458). It has been shown that treatment of the dibromo-a-N-acetyl-o-benzoxybenzylphenylhydrazine OBz*C,H2Br2*CH2*NAc*NHPh with alcoholic potash does not yield a 1 3 the gxpected a-N-acetate but the a-N-benzoate OH*CsH2Br2*CH,*NBz.NHPh whether the hydrolysis is carried out with excess of alkali or not or in the warm or in the cold. The 0-radicle is usually the first to be split off and this may then displace the acetyl group from its position or the rule is reversed in this case the N-acetyl being first hydrolysed with subsequent migration of the benzoyl group. It is however to be noted in this connexion that the N-acetates a and p are very stable towards alkalis (lo%) whereas the NN-diacetate and ONN-triacetate give the a-N-acetate with a 1% alcoholic solution of potassium hydroxide ; further one molecular equivalent of alkali with the triacetate does not give the NN-diacetyl compound-a portion of the compound is not attacked the remainder being hydrolysed to a- N-a ce t a t e.With other esters the behaviour is quite otherwise the O-propionyl- a-N-acetyl compound on partial hydrolysis with aniline gives a- N-acetate and propionanilide ; alcohol potassium hydroxide giving however a-N-propionate and acetanilide.The 0-acetyl-a-N-pro- pionyl derivative is hydrolysed to a-N-propionate in the normal manner. The question of whether i t is .the greater mass of the migratory group which displaces the other acyl radicle or whether it depends on the space occupied by the groups was also examined b u t the results so far obtained have been meagre. The reactivity of phenyl- hydrazine is largely decreased by the introduction of heavy acyl groups and 8-benzoyl or heptoylphenylhydrazide do not react with dibromo-o-hydroxybenzyl bromide or its esters under ordinary conditions. Indirect methods of preparing these a-N-derivatives from phenylhydrazine and the corresponding ester of the bromide whereby subsequent intramolecular change would be induced have led to mixtures which could not be separated.The crude product however obtained by benzoylation of the a-N-heptoate on hydrolysis gave the a-N-benzoate so that it would appear that the heptoyl radicle containing the same number of carbon atoms as the benzoyl group is nevertheless displaced by it. The formyl compounds are distinguished by the easy displacement188 ABSTRACTS OF CHEMICAL PAPERS. of the formyl group ; thus the actidn of s-formylphenylhydrazide and dibromobenzoxybenzyl bromide leads to the formation of the a-N-ben- zoate and an analogous result is obtained with the acetoxy-compound.[With HUGO DANNEHL and K. ISIULLER.] -8- Plwayldibromo-o- hydroxybenxyl-a-N-formylhydraxine C1,H12@,N2Br2 prepared by heating 2 mols. of s-formylphenylhydrazide with 1 mol. of dibromo- o-hydroxyben zyl bromide in benzene solution crystallises from alcohol in colourless crystals m. p. 164-165". The a-Nformyl- 0-P-N-diacetyl derivative Cl~H,,0,N2Br2 is a yellow amorphous powder which on hydrolysis yields the a-N-acetate. The 0-benaoyl- a-N-formyl derivative C21H1G0SN2Br2 crystallises from alcohol in very slender white needles ni. p. 154O (decomp.). The 0-acetyl- a-N-propionyl derivative Cl,H,803N2Br2 crystallises from alcohol i n glistening leaflets m. p. 173-1749 and is not dissolved by aqueous alkali showing that under these conditions migration of the acetyl group to the P-N does not occur.The a-N-propionyl-0-benzoate C22H?o03N2F2 forms colourless needles m. p. 176-177O and on hydolpis yields the a-N-benzoate. The heptoate of dibromo-o-hydroxybenzyl bromide Cl4HI7O2Br3 prepared by heating the bromide with heptoyl chloride for three hours at 160° crystallises from methyl alcohol in silken needles m. p. 41'. The a-N-heptoate forms slender needles m. p1 146-148" and is soluble in aqueous alkali. W. R. Transformation of Azines into Hydrazones. GUSTAV KNOPFER (Monatsh. 1909,30,29-38).-The results of the author's investigation of the behaviour of aldazines and ketazines towards phenylhydrazine show that all these azines are converted by this means into the corre- sponding hydrazones (compare Fulda Abstr. 1903 i 199 ; Ofner Abstr.1904 i 818; Ott Abstr. 1905 i 376; Fiirth Abstr. 1907 i 61). That the translormation which takes place according to the equation CHR:N*N:CHR + 2NHPh*NH = 2CHR:NoNHPh + N,H is not a consequence of the mass action of the reagent is shown by the fact that the reacting substances were taken in approximately theoretical proportions the conversion of the azine being practically complete. The azine suspended in alcohol (or acetic acid) was heated with phenylhydrazine in a reflux apparatus until complete solution occurred. The following azines .of aldehydes and ketones giving azines and hydrazbnes which are readily identified were employed. (1) Benzaldazine. (2) Salicylaldazine. (3) Anisaldazine. (4) Gin- namaldazine. (5) Cuminaldazine. (6) Furfuraldazine. (7) p-Hydroxy- benzaldazine.(8) Vanillddazine. (9) Piperonaldazine. (10) p- (1 1 ) 0- and (1 2) m-nitrobenzaldazines. (1 3) p-Dimethylaminobenzaldazine. (14) ProtocatechzLaldazinu Gl,H1204N2 decomp. about 245O which is readily soluble in alcohol. (1 5) Resorcylaldazine C14H1204N2 which does not melt at 310'. (16) Methylphenylketazine. (17) Methyl-m- nitrophenylhtaxine C1,H1,O,N4 m. p. 194-195'. (18) Methyl-p- aminophenylketaxine ClGH18N4 which forms heavy yellow crystals m. p. 16 6" and dissolves readily in alcohol. (1 9) BenxyZi~erLeacetaxine CIOH20N2 which forms yellow crystals m. p. 160" and with phenyl-~ ~ G A N I C CHEMISTRY'. 189 hydrazine yields benzylideneacetonephenylhydrazone m. p. 159' (Fischer Abstr. 1884 1150 found 157'). T. H. P. The Aeoxine Analogue of aposafranine.FRIEDRICH KEHRYANN and WERNER GRESLY (Ber. 1909 42 347-349).-The azoxine analogue of aposafranine and of apothionine has been prepared by eliminating an amino-group from diaminophenazoxonium chloride (Abstr. 1903 i 279) in the usual way and has been isolated as the dark red crystalline platinichloride (C,,H,ON,),PtCI,. The chloride and impure nitrate have been prepared. c. s. Experiments on the S y n t h e s i s of H i s t i d i n e . OTTO GERNGROSS (Ber. 1909 42 398-405).-The object of this investigation was the synthesis of histidine which it was proposed to eEect starting from 4-methyliminazole (4-methylglyoxaline) by the following series of changes THoCH>CMe + CCl,*CHO -+ CH=N SJH*OH CH=N -+ >C*CH,*CR(NH,)-CO,H. The condensation product of 4-methylglyoxaline with chloral when hydrolysed with an aqueous alcoholic solution of sodium hydroxide yields however a-methoxyglyoxaline-4-propionic acid which has not yet been converted into histidine. 2-Methylquinoline and chloral when mixed form an additive product C,,H1,0NC13,H,0 which crystallises in large glistening cubes and prisms sinters at 56' m.p. 63' and dissociates into its components when kept or when dissolved in water. 4-Methylglyoxaline and chloral form a similar additive product C,H,ON,CI which crystallises in rosettes of hexagonal plates sinters at 116' and has m. p. 123' (decomp. ). 4-yyy- Trichlor 0- p-h y droxyprop ylg l y omline C3H3N,*CH,*CH(OH)*CC13 is prepared by heating 4-methylglyoxaline with chloral for forty-two hours a t 78-80'; it crystallises in prisms m.p. 195' (decomp.9 ; the hydrochloride C,H,ON,C1 forms stellate groups of crystals and decom- poses between 230-2460' ; the nitrate forms large colourless glisten- ing prisms decomposing above 195'; the omlate forms rosettes of prisms. The base is converted by sodium hydroxide in aqueous methyl alcohol at 2 5 O into amthoxygZyoxaline-4-propionic acid which crystallises in rectangular plates turns yellow at 2 1 0' and decomposes at 221O ; the hydrochloride C7H,,0,N,,HCI forms small needles sinters at 170° and decomposes a t 172'. The methyl ester hydrochloride C,H,,O,N,,HCl prepared by the action of hydrogen chloride on a solution of the acid in methyl alcohol forms silky needles which become orange-yellow at 173' and have m.p. 185' (decomp.). a-Chloroglyoxaline-4-propionic acid prepared from histidine by the VOL. XCVI i. 0190 ABSTRACTS OF CHEMICAL PAPERS. method of Windaus and Vogt (Beitr. chern. Physiol. Path. 1907 9 406) has m. p. 191" and yields a methyl esder hydTochZoride crystallising in large thin glistening plates m. p. 140". W. H. G. ERNST MOHR (Verh. Ges. deut. Naturforsch. Aerxte. 1907 ii 96-97).-Isatoic anhydride dissolves in an excess of cold sodium or barium hydroxide ; the clear solution yields sodium or barium carbonate and anthranilate when boiled. Isatoic anhydride dissolves in water containing an C7qO,N,,HCl Isatoic Anhydride (Anthranilcarboxylic Acid). v equal molecular quantity of sodium hydroxide forming a solution which probably contains the sodium derivative C,H,<NNa.co or co-p C H precipitates a corresponding barium derivative on N=C*ONa the addition of barium chloride and regenerates isatoic anhydride when acidified After a short time the solution deposits isatoic anhydride and under certain conditions contains sodium anthranoyl- anthranilate due to the action of the anhydride or its sodium derivative on the sodium anthranilate produced. Similarly isatoic anhydride reacts with glycine to form o-aminohippuric acid. Action of Hydriodic Acid and of Iodine on Dimethylamino- antipyrine (Pyramidone). HENRI COUSIN (Bull. Xoc. chim. 1909 [vi] 5 121-124; J. Phccrm. Chim. 1909 [vi] 29 49-54).- Hydriodic acid acts on pyramidone forming the iodide C13HlfON3,HI colourless prisms m. p. indistinct above 200' (decomp.). When iodine is added to this salt or to the free base in alcoholic solution the periodide C13HlfON3,HI,12 is obtained as brown needles insoluble in water.G. B. 5Amino-1-phenyl-3-methylpyrazole. ERNST MOHR [and in part LUDWIG SCHMIDT] (J. p. Chem. 1909 [ii] 79 1-49),- A continuation of the researches of von Walthel (Abstr. 1897 i 297) Many of the compounds described in this paper have already been investigated (compare Michaelis Abstr. 1905 i 476 ; Michaelis and Klopstock Abstr. 1907 i 735). The cyanoacetonephenyl- hydrazone prepared by the interaction of p-aminocrotononitrile and phenylhydrazine in dilute acetic acid has m. p. 99-100" (compare Burns Abstr. 1893 i 314; von Walther loc. cit.). The product obtained when the two substances are heated together or in alcoholic solution has m.p. 88-94" and dissolves in cold concentrated sulphuric acid forming an intense blood-red solution ; the substance m. p. 99-100° does not give an intense coloration ; these differences cannot yet be explained. Both substances when warmed with dilute hydrochloric acid at about 55' yield 5-amino- 1-phenyl-3- methylpyrazole. The latter compound appears to react both and as an aminopyrazole as an iminopyrazolone C. S. CMwYH N e ~ ~ ~ o ~ ~ ~ 9 for when it is tqeated with sodium nitrite and N<N P h C N H,'ORUANIC CHEMISTRY. 191 dilute hydrochloric acid it yields 4-oximino-5-imino-l-phenyl-3- methylpyrazolone (compare von Walther loc. cit.) and 5-diazo-l- phenyl-3-methylpyrazole chloride ; the presence of the latter in the solution is shown by the formation of an azo-dye on the addition of an alkaline solution of &naphthol. 4-Oximino-5 -imino-1-phenyl-$-methylpyrazolone appears to behave as CMe*fi*NO NPh*C*NH a tautomeric substance represented by the formulse N< CMe*?:N*oH; thus it reacts both as an acid and as a base; and NqNl?h*C:NH the solid substance is bright red the molten substance is dark green; the dilute solutions in indifferent solvents are sky-blue the alcoholic solution is reddish-violet. 5 -Amino- 1 -phengZ-3-meth y lpyrazole hydrochloride when crystallised from hot dilute hydrochloric acid forms long white needles; it contains water and hydrogen chloride in a loose state of combination and does not give a sharp m.p. crystallises in slender reddish-yellow needles m. p. 169O which when kept in the mother liquor change into compact orange-red prisms m.p. 176-178" (decomp.). l-PhenyZ-3-methylpyraxole-5-axo-~-naphthol C,oH160N4 wystnllises in glistening bright red microscopic needles m. p. 209-2 loo. During the preparation of 4-oximino-5-imino-l-phenyl-3-methpl- pyrazolone a by-product was obtained which is possibly 5-imino-i- CMe*Co it crystallises in NPh*b:NH ' phenyl-3-methyl-4 5-pyraxoqzcinone N< aggregates of lemon-yellow needles m. p. 133-1 34O. 4 5-Diamino-1-phenyl-3-methylpyrazole condenses with benzil CMe*E=N:$JPh mhich yielding tr~phenylmethylpyraxopyrazine crystallises in very pale lemon-yellow needles m. p. 190°. 4-Oximino-5-imino-l-phenyl-3-methylpyrazolone is converted by an alkaline solution of potassium hypochlorite into 1-phenyl-3-methyl- >0 straw-yellow 4 5-pyraxopinonedioxime anhydride N< plates m.p. 94-95O and by potassium permanganate in dilute sulphuric acid into 4-nitro-5-amino-l-phenyl-3-methylpyra~ole NqN€'h*C*NH,' a yellowish-brown powder m. p. 167-168O. The platinichloride C,oH,,N3,H,PtCl,,H,O N%Ph*C*N:CPh' CMe*C]:N NPh*C:N CMe$*NO W. H. G. Pyrimidines XLI. Formation of Purine Derivatives from 4-Methylcytosine. CARL 0. JOHNS (Amev. Chem. J. 1909 41 58-65. Compare Abstr. 1908 i 917).-When 2-oxy-6-amino-4- methylpyrimidine (4-methylcytosine) is nitrated in presence of sulphuric acid an almost quantitative yield of 5-nitro-4-methylcyto8ine &O- NH>Cl\le is obtained; it crystallises from water in C (NH,) C( NO2)' 0 2192 ABSTRACTS OF CHEMICAL PAPERS.small yellow prisms decomp. 260-280'. The position of the nitro- group is shown by the formation of Behrend's 5-nitro-4-methyluracil when it is heated with 30% sulphuric acid in a sealed tube. When treated in a similar manner with 20% acid cytosine and nitrocytosine give respectively uracil and nitrouracil. Attempted reduction of 5-nitro-4-methylcytosine by means of ammonium sulphide regenerated 4-methylcytosine but aluminium amalgam reduces it to 5 6-dianzino- co NH 2-oxy-4 - methylpyimidine N<C(NH,) .C( NH2)>cMe crystallising from water in long prisms containing 1 mol. H,O which do not melt but decomp. at 280-285'; the HN/\\C/\CO picrate decomp. 240'. I I I 5 6-Diamino-2-oxy-4-methylpyrimidine con- oc\/c-NH denses with carbamide when the anhydrous sub- stances are heated together at 170-180° giving 2 8-dioxy-6-methyZpurine (annexed formula) forming small sparingly soluble crystals that do not melt below 345".This compound is the last of t'he three possible dioxypurines t o be prepared. In a similar manner by condensing with thiocarbamide 2-oxy-8-thio-6-methyZpurine is obtained ; it is an almost insoluble crystalline powder not melting below 345". 5 6-Diamino-2-oxy-4-methylpyrimidine when heated with formic acid yields the monoformyl ~ ~ / \ \ c / \ c H compoiind C,H70N,,CH0 which forms minute I I 1 1 crystals from hot water solutions not melting OC,//c-N below 345'. This substance gives a white crys- talline sodium salt which loses water vigorously at 200' leaving a porous mass 2-oxy-6-methyL purine (annexed formula) readily soluble in water crystallising therefrom in slender prisms not melting but decomp.at 300-345". J. V. E. CMe NH N CMe NH N Synthesis of 1-Methylxanthine. MAX ENGELMANN (Ber. 1909 42 177-182).-1-Methylxanthine was first isolated from human urine by Kriiger and Salomon (Abstr. 1898 i 699). Since it had not been synthesised hitherto the author has effected this starting from cyanamide and methyl alcohol. Methylisocarbamide (methyl imino- mrbimate) prepared from cyanamide and methyl alcohol (compare Stieglitz and McKee Abstr. 1900 i 340) condenses with ethyl cyanoacetate in the presence of sodium ethoxide forming 4-imino- 6-oxy-2-metl7Lox~/d~hydropy~~imidi~~e NH<co-cH,>C:NH C( OMe) N a crystal- line substance m. p. 214-216" which when treated with methyl sulphate and aqueous sodium hydroxide yields 4-imino-6 -oxy-2-methoxy- 1 - methyldihydropyrimidine C6H,0,N colourless crystals m.p. 206-208'. The latter substance is converted by sodium nitrite and acetic acid into 5-oximino-4-imino-6-oxy-2-metltoxy- 1 -mPthyldzhydro- pyrimidine small violet needles m. p. about 145" (decomp.) which when reduced with ammonium sulphide yields 4 5-diamino-6-oxy- 2-methoxy-l-methylpyrimidine cry stallising in needles m. p. 160". The latter substance is converted by hot concentrated hydrochloric acidORGANIC CHEMISTRY. 193 into 4 5-diamino-2 6-dioxy-1 -methylpyrimidine the hydrochloride of which when heated with sodium formate and formicBacid at looo yields 5-formylamino-4-amino-2 ; 6-dioxy-l-methylpyrimidine crystallisiag in needles which do not melt at 300O; the crystalline sodium salt when heated at 230-240° liberates 1H20 with the formation of 1-methyl- xanthine.W. H. G. Action of Unsymmetrical Benzoylphenylhydrazine on o-Benzoquinone. WILLIAM MCPHERSON and H. 5. LUCAS (J. Amer. Chm. Soc. 1909 31 281-284).-1t has been shown in earlier papers (Abstr. 1896 i 127 ; 1900 i 411 ; 1901 i 572) that unsymmetrical acylphenylhydrazines react with p-benzoquinone t o form hydrazones of the general formula 0:R N*NAcR. Willstatter and Veraguth (Abstr. 1907 i 453) have found that under certain conditions these hydrazones readily undergo a rearrangement into the isomeric hydr- oxyazo-compounds OAc*R*N:NR’ in which the acyl group is attached to the oxygen atom. By the action of U-benzoylphenylhydrazine on o-benzoquinone o-benzoxyazobenzene OBz*C6H4*N:NPh is produced.It is probable that in this reaction the hydrazone O:C6H,:N*NBzPh is formed first and instantly undergoes rearrangement. o-Benzoxyazobenzene m. p. 93O crystallises in orange needles or plates and on hydrolysis yields o-hydroxyazobenzene (Bamberger Abstr. 1900 i 531) which on benzoylation is re-converted in the original substance. a-Benzoylphenylhydrazine reacts with tetrachloro-o-quinone with formation of the compound C,C1302-NH*NBzPh. E. G. Mechanism of Coupling Reactions. HANS TH. BUCHERER (Ber. 1909 42 47-49. Compare Dimroth a d Hartmann this vol. i 66).-The author and Sonnenburg have found that 2-naphthol-1- sulphonic acid couples with diazotised p-nitroaniline in sodium acetate solution to form p-nitrobenzene-azo-P-naphthol whilst in sodium carbonate solution the product of coupling is an easily soluble substance which readily changes to the preceding compound and is regarded as an 0-azo-derivative SO,Na*C,,H6*O.N,*C,H;NO,.0-Azocompounds have also been obtained from a-naphthol-6 8- disulphonic acid or salicylic acid and diazotised naphthionic acid or diazotised aniline ; these compounds readily change to ordinary 0- or p-hydroxyazo-compounds. c. s. Decomposition of Diazo-solutions. CARL G. SCHWALBE (Ber. 1909 42 196-199. Compare Abstr. 1905 i 618 843).-Polemical. Mainly a reply to Cain (this vol. i 70). Emphasis is laid on the fact that the author studied the rates of decomposition of diazo-solutions as prepared technically.The quantity of nitrous acid present in such solutions is sufficient to produce an increase in the velocity of decomposition. W. H. G. Gain’s Theory of Diazonium and Ammonium Salts. ARTHUR Compare Abstr. 1908 i 1021). The chief HANTZSCH (Ber. 1909 42,394-398. -Polemical. A further reply to Cain (this vol. i 70).194 ABSTRACTS OF CHEMICAL PAPERS. points raised are as follows (1) Comparison of the instability of the C,-ring in benzoquinone towards halogens hydrogen chloride mild oxidising agents etc. with the stability of the benzene nucleus in diazonium salts towards these reagents shows that these two classes of compounds do not contain the same C,-ring as represented by Cain’s formula ; (2) contrary to Cain’s statement the double linking in the group -N:N- is readily resolved by mild reducing agents as in the conversion of azobenzene into hydrazo- H benzene A compound having the annexed for- \/=\ - N.X mula would yield OR reduction a diamine and not /\=/- I I phenylhydrazine since the nitrogen atom in the I N group z>C<g would not be separated from the carbon atom by mild reducing agents; (3) it does not necessarily follow from the non-existence of aliphatic diazonium salts that the presence of the benzene nucleus is essential for the formation of diazonium salts.The stability of the latter is greatly influenced by substitution in the benzene ring and it is not remarkable that the compound resulting Irom the total replacement of the benzene nucleus by an alkyl group decomposes spontaneously ; (4) the process of ionisa- tion of ammonium salts in the manner represented by Gain is very improbable since in the case of trimethylethylammonium hydroxide and the corresponding nitrate dissociated ethyl alcohol and ethyl nitrate would be formed intermediately ; ethyl nitrate does not how- ever form ions.Further if the addition of alkyl halides to amines takes place thus R,N+ClR -+ R,N:Cl*R then the compound formed from methylamine and hydrogen chloride namely should be isomeric with that derived from ammonia and methyl chloride namely NH,:Cl*Me. W. H. G. NH,Me:Cl*H Change of Colour in Additive Reactions. DANIEL VORLANDER (Verh. Ges. deut. Nnturforsch. Aevxte. 1907 ii 91).-The salts of aminoazo-compounds and acids may be regarded as additive com- pounds or as ammonium salts.I f the latter is correct azobenzene- trimethylammonium chloride should be red; this is not the case the azo-ammonium ion being orange-yellow like azobenzene and aminoazobenzene. Solutions of hydrogen chloride or bromide in benzene carbon tetra- chloride or chloroform immediately colour dimethylaminoazobenzene. Moreover dimethylaminoazobenzene and p-methoxydimethylaminoazo- benzene form dark red conducting solutions in dry liquid sulphur dioxide whereas the solution of aminoazobenzene is yellow and non- conducting. An additive compound with sulphur dioxide is probably formed in the former but not in the latter case. The author draws the conclusion that the colour of the compounds of aminoazobenzenes and acids is conditioned by an additive relation between the amine and the acid.The cause of the different colour of the acid derivatives and of the quaternary ammonium salts is attribnted to the fact that in the former the union of the constituents is loose and of the natureORGANIC CHEMISTRY. 195 of that of a double salt whilst in the case of the ammonium deriv- atives the constituents are more intimately united as in complex salts. c. s. Study of the Constitution of Proteins by the Hydrolytic Action of Hydrogen Fluoride. Preparation of Definite Natural Peptides. LOUIS HUGOUNENQ and ALBERT MOREL (Compt. rend. 1909 148 236-238. Compare Abstr. 1908 i 706).-The author has extended his experiments on the use of hydrogen fluoride in the hydrolysis of proteins. The 60% acid diluted with twice its volume of water effects the complete hydrolysis of gelatin with production of free amino-acids.More dilute acid however is incapable of bringing about such profound decomposition ; the products in this case consist of diamines and certain uncrystallisable polypeptides which have been isolated in the form of well-defined picrates and are analogous to some synthetic polypeptides described by Fischer (Abstr. 1906 i 73). They appear to exist in proteins in definite combination and not to have arisen through the synthetic action of the hydrogen fluoride. The following compounds have been isolated from the products of hydrolysis of pepsin extract. A~gimyl-arginine dipicrate - m. p. 207' (corr'). GZutamzn-Zysi.lze pacrate C,,H2,0,N2,C,H3N,01,H,0 prisms m. p. 2 16". Lysyt-Zysine dipicrate C12H,,03N4,(C6 E1307N,) small tablets m.D. 238-242". C18H3804N12)(C6H307N3)2*2H20~ From gelatin &ginyt-o.r.ginine picrate C,2H,,03N8,C,H,07N,,2H,0 has been prepared. It forms needles m. p. 313'. w. 0. w. Combining Power of Egg-white for Hydrochloric and Sulphuric Acids. HEBBERT E. ROAF (Proc. physiol. Xoc. 1908 iv ; J. Physiol. 38).-Diluted egg-white was placed in a series of dialysing tubes immersed in various strengths of acid. After some days the amount of acid in the outer vessel was estimated and it was found that with two acids (sulphuric and hydrochloric) and varying concen- trations equivalent amounts are taken up by the same quantity of protein. It was to be expected that proteins as complex amino- acids should show a definite combining power for acids and alkalis. W. D. H. Osmotic Pressure of Haemoglobin. HERBERT E. ROAF (PTOC. phpiot. SOC. 1908 i-ii ; J. Physiol. 38).-The experiments were made by laking red corpuscles of the cow freed from serum with water The haemoglobin was reckoned as 90% of the dry organic matter. Their object was t o determine the effect of altered conditions on the '' solution aggregate " of the haemoglobin. Three determina- tions of osmotic pressure were made (1) with distilled water (2) with 0.34% sodium hydrogen carbonate and (3) with 0.2% of sodium carbonate; the results for 1% of haemoglobin were 5.7 5.3 and 11.6 mm. of mercury respectively which correspond with '' aggregates " of 29787 32035 and 14636 respectively. The osmotic pressure of protein solutions is altered by electrolytes and non-196 ABSTRACTS OF CHEMICAL PAPERS. electrolytes. Substances which prevent laking lower the osmotic pressure of hsmoglobin ; hsmoglobin is more affected by electrolytes than are serum-proteins. It is possible that the osmotic changes which occur in muscular contraction may be due t o alterations in the aggregation of proteins and not to liberation of inorganic salts. W. D. H. Nucleo-protein of the Pig’s Liver VITTORIO SCAFFIDI (Zeitsch. physiol. Chem. 1909 58 272-281).-By boiling and precipitation with acetic or tartaric acid a nucleo-protein was obtained from pig’s liver which contains 3-48-3.73% of purine nitrogen 2.67% of phosphorus and a pentose. It also contains iron in quantities varying from 0.5 to 3.6%. Schmiedeberg’s ferratin which was prepared in much the same way contained 6% of iron. W. D. H. Action of Rennet at Various Temperatures. C. GERBER (Compt. rend. 1908 147 1320-1322).-There are many causes which produce deviations from the law that the times taken to curdle a given quantity of milk are inversely proportional to the amount of ferment added. The present paper is concerned with such deviations as are due to a too speedy curdling so that the product of time and quantity of ferment is lowered. These deviations increase with the temperature and at the same temperature they increase with the quantity of ferment added. For the same quantity of rennet they are largest with specimens of rennet containing a high proportion of saline constituents. Calcium chloride however (and t o some extent hydrochloric acid) has an accelerating effect which is greatest when the enzyme concentration is greatest so that the above- mentioned negative deviation due to the large quantity of ferment present is annulled; the process thus becomes regular and the law is followed. G. B. A New Artificial Peroxydase. E. DE STOEKLIN (Compt. rend. 1908 147 1489-1491. Compare Abstr. 1908 i 490 746; ii 573). -Iron tannate can act as a peroxydase and in conjunction with hydrogen peroxide oxidises a number of substances which are resistant t o all peroxydases hitherto known. I n particular it attacks substances containing a single phenolic hydroxyl for instance guaiacol. I t acts like a true enzyme oxidising many times it own weight of ethyl alcohol to acetaldehyde and it produces a black substance from tyrosine in the same way as tyrosinase. LEONOR MICHAELIS and PETER RONA (Biochem. Zeztsch. 1908 15 217-219).-1n refer- ence to Resenscheck‘s work (this vol. i 74) the authors state that they also find that the presence of negative adsorbents diminishes the fermentative capacity of yeast juice to a small extent. Positive adsorbents have a somewhat greater inhibitory influence. G. B. [Effect of Adsorbents on Yeast Juice.] S. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9099600125

出版商:RSC    

年代:1909

数据来源: RSC