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INORGANIC CtfEMJSTRY. Inorganic Chemistry. ii. 151 Derivatives of Hydrogen Peroxide. JOE D’ANs and W. FRIEDERICH (Zeitsch. ccnorg. Chem. 191 2 73 325-359).-The hydrogen atoms of hydrogen peroxide may be replaced by metals or acid radicles yielding derivatives which resemble the corresponding compounds of water in constitution and properties. Pure hydrogen peroxide is prepared by Ahrle’s method (hbstr. 1909 ii 395). It reacts in ethereal solution with sodium forming a white product sodium hydrogen peroxide 2NaH02,H202. This compound is shown to be identical with the compound obtained from sodium ethoxide and hydrogen peroxide by Wolffenstein and Peltner (hbstr. 1908 ii lSO) whilst the sodyl hydroxide obtained by Tafel (Abstr. 1894 ii 448) from sodium peroxide and absolute alcohol below 0’ has the composition NsH02 and yields the former compound with hydrogen peroxide or on further treatment with alcohol.The compound containing an additional molecule of hydrogen peroxide is the more stable. Potassium reacts more vigorously with ethereal hydrogen peroxide than sodium and there is much decomposition. The potassium hydrogen peroxide obtained has the composition 2KHO2,3H,O2. Another com- pound 2KH02,H202 identical with that prepared by Schone (Annalen 18’78 193 276,289) crystallises on mixing absolute alcoholic solutions of potassium hydroxide and hydrogen peroxide. Calcium does not react with dry ethereal hydrogen peroxide but in presence of a little water the action is vigorous and a mixture of compounds including calcium peroxide and calcium hydroxide is obtained.The compound formed by the action of alcoholic acetic acid on sodium peroxide or sodium hydrogen peroxide and regarded by Tafel as derived from a peracetic acid is shown t o have the composition 2 CH,* C02Na H202. Nitrogen pentoxide reacts with cooled hydrogen peroxide and the product oxidises aniline to nitrosobenzene and shows other reactions of a per-acid but pernitric acid has not been isolated. The prepara- tion of Caro’s acid and persulphuric acid has been described (Abstr. 1910 ii 706). Attempts have been made to prepare salts of Caro’s acid but the products are impure although the aniline salt C,H,*NH,!H,SO is precipitated from ethereal solution as a white salt containing 88.7% of the persulphate. Fluorosulphonic acid and hydrogen peroxide yield only a mixed product.Caro’s acid in aqueous solution has a molecular weight corresponding with H2S0 and it mayii. 152 ABSTRACTS OF CHEMICAJ PAPERS. be obtained quantitatively from persulphuric acid by the reaction H,S,O + H,O = 2H2S05. Acetyl chloride reacts with pure hydrogen peroxide yielding per- acetic acid CH,*CO,H a volatile highly explosive liquid or with a larger quantity of acetyl chloride diacetyl peroxide Ac,O is formed. C. H. D. The Weight of a Normal Litre of Hydrogen Chloride and the Atomic Weight of Chlorine. FRANK P. BURT and ROBERT WHYTLAW-GRAY (Trans. Rumday soc. 191 1 7 30-41).-The density of hydrogen chloride found by Scheuer (Abstr. 1909 ii 991) being higher than that obtained by the authors (Trans. 1909 05 1644) fresh determinations have been made and the sources of error have been examined.Some gas is dissolved by the grease used for the taps and is released when the vessel is exhausted. A pure paraffin lubricant gives better results than rubber grease. The adsorption by glass surfaces has been determined by displacing gas at constant pressure by means of mercury when the adsorbed film remains between the glass and mercury and can afterwards be collected by lowering the mercury and so producing a Torricellian vacuum. The adsorption with hydrogen is negligible whilst for hydrogen chloride the quantity condensed is very nearly directly proportional to the pressure. The correction however only amounts to 1 part in 10,300. A new apparatus has been used in which as the gas is absorbed by charcoal mercury is allowed to enter the bulb so as to keep the internal pressure constant and approximately atmospheric.Traces of mercury vapour are condensed by solid carbon dioxide or absorbed by gold wire. The gas is prepared from pure ammonium chloride and syrupy phosphoric acid and dried over re-dhtilled aluminium chloride. Pure hydrogen chloride does not react with meizury but the mercury is attacked in presence of traces of air. The final result obtained for the weight of a normal litre of hydrogen chloride is 1.63915 +_ 0.00004 grams identical with that previously obtained. This gives the value 35.460 for the atomic weight of chlorine identical with the International Committee's value. C. H. D. Formation and Decomposition of' Anhydroua Substances ; Case of Iodic Anhydride. MARCEL GUICHARD (C'ompt.rend. 19 1 1 153 1226-1229. Compare Abstr. 1909 ii 136).-The temperature at which iodic anhydride begins to decompose has been determined by heating the substance in a silica tube in a vacuum and measuring variations in pressure by the MacLeod guage. After forty-eight hours at 200' there is no appreciable decomposition the slight evolution of gas (0.08 C.C. from 10 grams) being partly from the walls of the apparatus and partly due to occlusion. After heating further a t 205' for two hundred and fifty-seven hours practically no more gas was evolved. A t 259' gas evolution was proportional to duration of heating. Baxter aud Tilley (Abstr. 1909 ii 225) heated the anhydride for four hours at 240° when it still retained a trace of water.Dehydration can be pushed further by heating for oneINORG A N 1C CHEMIYTK Y. ii. 153 hundred hours at 250° decomposition occurring to the extent of only 0.0002-0*0003 of the weight of material. w. 0. w. Chemically Active Modification of Nitrogen Produced by the Electric Discharge. 11. (Hon.) ROBERT J. STRUTT (Proc. Roy. SOC. 1911 A 86 56-63. Compare Abstr. 1911 ii 482 678). -The chemically active modification of nitrogen which is produced by the passage of the electric discharge through tubes containing pure nitrogen is not acted on by hydrogen. Oxygen destroys it but this change is not accompanied by the formation of any oxides of nitrogen. The same greenish-yellow flame with a continuous spectrum is obtained by the action of (1) ozone on nitsic oxide and nitrogen peroxide (2) active nitrogen on the two oxides of nitrogen and (3) when the two oxides of nitrogen are introduced into a Bunsen flame.Nitrogen peroxide is formed in the action of active nitrogen on nitric oxide. This reaction can be used to estimate the percentage of active nitrogen in the gas issuing from the discharge tube. The numbers obtained in this way show that about 2.5% of the active modification is present. The electrical conductivity of glowing nitrogen is very high a large deflexion being obtained with a single battery cell and an ordinary high resistance galvanometer. The ions are formed in the glow and the ionisation process does not appear to be much altered when metals or other substances are introduced between the electrodes so as to give rise to the corresponding spectra.The intensity of these spectra is not diminished when large potential differences are applied to effect the removal of the ions. When a current of nitrogen carrying phosphorus rapour is intro- duced into glowing nitrogen there is no immediate action but after the glow has disappeared a further glow effect is observed indicating that the nitrogen gets inho a state in which i t can react with phosphorus. Experiments with ozone show that this can in some cases give rise to metallic spectra when mixed with metallic vapours at comparatively low temperatures. H. M. D. Colloidal Arsenic Trisulphide. A. DUMANSKI (Zeitsch. Chem. I f i d . li'olloide 191 1 9 262-263).-The properties of colloidal arsenious sulphide are described.The particles which are negatively charged can be slowly segregated by rapid centrifuging. From measure- ments of the density and electrical conductivity of the colloidal solution and the dispersive medium it is found that the density of the colloidal sulphide is 2.938 and the specific conductivity 136 x The solution is coagulated by various electrolytes whilst others react with the sulphide. With an iodine solution reaction takes place according to As,S + 101 + 5H20 = As20 + 1OHI + 3s ; with a solution of potassium permanganate which has been decolorised by hydrogen peroxide the sulphide is also converted into arsenic acid and in this case also there is no coagulation. Solutions of alkali hydroxides and potassium cyanide have no coagulating action ; with silver nitrate and copper sulphate coagulation occurs but the precipitated substance containsii.154 ABS'TLLAC'I'S OF CHEMICAL PAPERS. considerable quantities of silver or copper. hand coagulates the colloid without formation of lead sulphide. Lead acetate on the other H. M. D. The Proportion of Carbon Dioxide in the Air of Antarctic Regions. ACHILLE MUNTZ and E. LAIN& (Compt. rend. 1911 153 11 16-1 1 19).-31n cold regions the dissociation pressure of hydrogen carbonates in the sea being lorn the proportion of carbon dioxide in the air should be below normal if Schloesing's theory of the distribu- tion of this gas is correct. Samples of air collected over the sea a t latitudes of 64-70' a t temperatures between 1 and - 2 O gave zt mean value of 2.0524 parts of carbon dioxide per 10,000 by volume a distinctly smaller proportion than is met with in warmer regions.w. 0. w. Action of Atmospheric Moisture on the Moisture Content and on thevelocity of Combustion of Black Powder. CARL KULLGI~EN (Arkiv. Kem. Min. Geol. 1911 4 No. 17 1-20).- Varying weights of black powder (H,O 1.10; KNO 74.0; C 15 ; S 9.8%) were placed in glass dishes in a desiccator through which was passed air of varying moisture content (38 aud 86% of the saturation content) the temperature being 16.5'. The glass dishes were weighed from time to time. According as the powder was dtied or not t h e equilibrium was approached from different sidea. It was found that with air containing 38% of moisture the percentage of moisture in the powder when equilibrium was attained was 0*91% whilst with air containing 86% of moisture the equilibrium percentage was 1.38%.The results are treated theoretically by the author and it is shown that the rate of absorption (or loss) of moisture by the powder is given by the expression dxldt = kfx. The velocity of combustion of the powder diminishes as the moisture content increases. T. S. P. The Solubility of Alkali Salts in the Corresponding Acids. WALTER HERZ (Zeitsch. anorg. Chem. 191 1 73 274-276).-The solubility of LiCl,H,O of NaCl and of KC1 in hydrochloric acid is less than that in water by an amount which is directly proportional to the concentration of the acid Hydrobromic acid depresses the solubility of potassium chloride less than hydrochloric acid.The solubility of sodium acetate is only very slightly lowered by acetic acid whilst sodium and potassium sulphates are more soluble in sulphuric acid solutions than in water. The Capacity of Potassium Halides for Forming Solid Solutions in Relation to Temperature. 11. MARIO AMADORI and G. PAMPANINI (Atti R. Accud Lincei 1911 [v] 20 ii 572-577. Compare this vol. ii 48).-1n the present paper the authors record the results obtained by the application of the method of thermal analysis to fused mixtures of these salts and compare the results thus obtained a t high temperatures with those previously arrived at for mixtures in the solid state. Potassium chloride and potassium bromide are miscible in all proportions both at low and at high C. K. D.INORGANIC CHEMISTRY.ii. 155 temperatures. I n the case of potassium bromide and potassium iodide the miscibility is complete a t a high temperature but limited at a low temperature. Potassium chloride and potassium iodide are miscible at a low temperature only to a- very limited degree but at a high temperature the miscibility is much greater although not complete (0-49 mol.% KCl in KI 0-9 mol.% KI in KC1). It is pointed out that this is in accord with the differences between the halogens In other respects. R. V. S. Symmetry of Crystals of Potassium Dichromate. A . SCHCBNIKOPF (Zeitsch. Kmyst. Min. 19 11 50 19-23).-Crystals were grown from a slightly supersaturated solution (containing 1.4-3 grams per 100 C.C. in excess of the amount given by the solubility) and the vessel containing the solution was immersed in a thermostat with a large volume of water a t 20.8".Small crystals of the salt were in- troduced to form nuclei for the growth. The crystals are tabular in habit parallel to (OOl) and when they have grown on the floor of the vessel there is an appreciable difference in-their form according to whether the face (001) or parallel face (001) was uppermost. The differences are such that they cannot be due to the influence of gravity and the consequent convection currents in the liquid. These effects are however eliminated by growing the crystals suspended in a vessel rotating on a horizontal axis. A crystal groyn under these conditions has the face (001) bright and smooth and (001) dull and rough; and in the case of other forms the parallel faces are not of the same size or one may be absent.Crystals of potassium dichromate therefore belong to the asymmetric class of the triclinic system. Mercury-Sodium Alloys. ERNEST VANSTONE (Truns. Phraclay SOC. 1911 7 42-63. Compare Schuller Abstr. 1904 ii 657).-The alloys are prepared by melting sodium in carbon dioxide and allowing it to flow into a weighed tube when t8he shell of oxide remains in the first tube. The sodium may also be cleaned by dipping in ether containing alcohol and melted under paraffin. The thermal analysis shows the existence of the com- pounds Na,Hg Na3Hg NaHg Na7Hg NaHg and NaHg the formula Na,Hg being more probable than Na12Hg, given .by Schuller which is not consistent with the range of the transformation temperature.The specific volumes of alloys liquid below 237' have been determined by drawing up the alloys into graduated pipettes in carbon dioxide by means of a hand pump. The specific volumes determined at 110' lie on a smooth curve and almost smooth curves are also obtained at 184' and 237". The alloys near to NaHg (m. p. 353') have not been investigated but this compound probably exists in the liquid in an un- dissociated condition (Bornemann and Aliiller Abstr. 1910 ii 924). The specific volumes of the solid alloys have also been determined. The maximum contraction occurs at 48 atomic % Na. A relation cannot be traced between the specific volumes and the sum of the valencies in the compounds present. Microscopical examination shows that the compounds Na,Hg Na,Hg2 NaHg Na7Hg NaHg and NaHg occur in distinct crystals. L.J. S. Mercury is then added from a burette. C. H. D.ii. 156 ABSTRACTS OP CHEMICAL PAPERY. The Hydrates of Sodium Carbonate. RUDOLF WEGSCHEIDER (Zeitsch. anorg. Chew. 19 1 1 '73 256-258).-The hydrate considered to have the composition Na2C0,,2*5H,0 is probably the monohydrate. The apparent difference in crystalline form (Morel Bull. SOC. franc. min. 1889 12 546) is due to an error in the angles recorded and the range of stability is quite consistent with the compound observed by Morel being the monohjdrate. C. H. D. Reciprocal Solubility of Sodium Carbonate and Sodium DESIR~ DE PAEPE (Bull. SOC. Compare Abstr. 1911 ii 489).- Hydrogen Carbonate in Water. chim. Belg. 1911 25 413-419. Polemical. A reply to Herzen (Abstr.1911 ii 721). W. G. The Differentiation of True Peroxy-salts froni Salts with Hydrogen Peroxide of Crystallisation. ERNST H. KIESENFELD and W. MAU (Ber. 1911 44 3589-3595).-The authors maintain the thesis that the true percarbonates can be distinguished from carbonates containing hydrogen peroxide of crystallisation by the fact that the former give a quantitative liberation of iodine from a neutral solution of potassium iodide whereas the latter liberate practically no iodine (compare Abstr. 1910 i3 33 203 290 774 952). Even when hydrogen peroxide is added to a solution of potassium percarbonate in the proportion of 2 mols. H,O, 1 mol. K2C206 the liberation of iodine is very little affected. At 15' a solution of potassium percarbonate after keeping for a n hour still liberates iodine in quantity from a solution of potassium iodide whereas the so-called sodium percarbonate does not liberate iodine from such a solution either at room temperature or at Oo even when added as the solid.Tanatar has supposed (Abstr. 1910 ii 774) that part of the oxygen in the compounds prepared by the action of hydrogen peroxide on the alkali carbonates is at all events firmly combined. The salt Na2C0,,1 4H20 described by Tanatar must however be either wholly a percarbonate or else wholly a hydrogen peroxide additive product Na2C03,H,0q,frH,0 since it contains only one active oxygen atom per molecule. The authors find that it gives no appreciable liberation of iodine from potassium iodide so that Tanatar's supposition is incorrect.The so-called rubidium percarbonate prepared by Peltner (Abstr. 1909 ii 574) must be considered to have the formula Rb,CO3,3H2O2. Persulphates and sulphates wit'h hydrogen peroxide of crystallisa- tion (Willstatter Abstr. 1903 ii 537) react towards potassium iodide in a similar way to the compounds just mentioned so that the reaction may be considered a general one for differentiating between true peroxy-salts and hydrogen peroxide additive products. T. S. P. Isomeric Percarbonates. ERNST H. RIESENFELD and W. MAU (Ber. 1911 44 3595-3605).-ln the light OF the experience gained in the differentiation of true percarbonates from carbonates containing hydrogen peroxide of crystallisation (compare previous abstract) the authors have investigated the compounds prepared by the action of carbon dioxide on sodium peroxide (Wolffenstein and Peltner Abstr.,INORGANIC CHEMIS'I'RY.ii. 157 1908 ii 180). They find that the four supposedly different salts propared by Wolffenstein and Peltner are really salts of two different acids only namely monoperoxycarbonic acid H,CO and monoperoxy- dicaibonic acid H,C,O,. The salts to which was given the formulae Na,C05,H,0 and NaHCO are to be considered as Na,CO,,H,O and Na,C20,,H,0 respectively. This was proved by comparison of the reactions of Na,C04 and Na,C0,,H20 and Na,C,O and 2NaHC0 respectively with potassium iodide ; in all cases the iodine liberated which is due to percarbonate oxygen and not to hydrogen peroxide of crystallisation corresponded with the formulae Na,C04 Na9CO4,H2O2 and Na,C,O Na,C,O,,H,O,.It was also found that each of the last- mentioned pair of compounds could be transformed into the other by addition or withdrawal of hydrogen peroxide. The substance having the composition Na2C0 was shown to be a true compound and not a mixture of Na,O + Na,C206( = 2Na,CO,) by comparing its action on potassium iodide with {,hat of the mixtiire mentioned ; Na,CO liberated iodide whereas the mixture did not. i t follows that the carbonates containing peroxidic oxygen can be classified as follows (1) Carbonates containing hydrogen peroxide of crystallisation for example Na,C'c) l&H,O ; (2) monoperoxy- carbonates for example Na2C0 ; (3) percarbonates (monoperoxy- dicarbonates) for example Na,C,O,. The compound Na,C20 behaves towards potassium iodide solution differently from the potassium percarbonate (K,C,O,) prepared by electrolysis in that only about 50% of its active oxygen liberates iodine whereas the potassium salt gives a quantitative liberation.This may be due to a difference in constitution and in order to settle the question the authors hare prepared a compound K2C206 from potassium peroxide and carbon dioxide by a method similar to that used for making the sodium compouud (Wolffenstein and Peltner Zoc. cit.). This compound behaves towards potassium iodide solution whether added as the solid or as a solution differently from ordinary potassium percarbonate and similarly to the compound Na,C,O,. It is therefore isomeric with ordinary potassium percarbonate and its constitution may perhaps be represented as KO.O-CO*O-CO*OK as distinct from KO*CO*O*O*CO-OK.The constitution of the compound Na,CO would then be NaO*O*CO*ONa so that the percarbonates show similar relations to the persulphates (permono- and per- disulphates). The authors point out that there is no trustworthy evidence for the assumption that the sodium hydrogen peroxide (Na0,H) prepared by the action of sodium peroxide on ethyl alcohol is different in constitution from that obtained by the action of hydrogen peroxide on sodium ethoxide (compare Wolffenstein and Peltner Zoc. cit.). T. s. P. Colloidal Silver. NICOLA PAPPADA (Zeitsch. Chem. Ind. Kolloide 1911 9 265-270).-The mechanism of coagulation of colloids by electrolytes is discussed and experiments are described which show the relative coagulating powers of different electrolytes for colloidal silver.The silver particles are negatively charged and coagulation is VOL. CII. ii. 11ii. 158 ABSTRACTS OF CHEMICAL PAPERS. effected by the cations. I n the series of the alkali metal ions the coagulating power increases with increasing atomic weight. The hydrogen ion is still more active and it appears that the coagulating capacity is determined by the velocity of diffusion of the active ions. Non-electrolytes are without action but for multivalent ions the effectiveness increases with the valency. Colloidal silver is chemically active towards a number of substances. It reduces mercuric chloride ferric chloride and an acid solution of potassium permanganate. With a solution of iodine in 0.W-potassium iodide a slow reaction takes place silver iodide being precipitated and the solution becomes alkaline. With a solution of potassium nitrate reduction to the nitrite occurs to a small extent.It reacts with hydrogen cyanide and alkali metal cyanides and with the halogens to form the corresponding silver salts. H. M. I). Constitution of the Photo-halides 11. ADRIAAN P. H. Compare Abstr. 1911 A reply to Reinders’a criticism (Abstr. 191 1 TRIVELLI (Chern. Weekblccd 1912 9 2-11 ii 281).-Polemical. ii 490). A. J . W. Formation of Complex Compounds of Salts of Silver and Mercury. BICE FINZI (Gaxxetta 191 1 41 ii 538-543).-Freshly precipitated silver chloride is soluble in an aqueous solution of mercuric sulphate. The solubility increases (but not in proportion) with the amount of mercuric salt present but it is increased more by dilution so that the greatest amount of silver chloride is dissolved by a large excess of mercuric salt at considerable dilution.When to such a solution hydrochloric acid is added in quantity equivalent to the silver present the metal is not all precipitated. Similar results are obtained when hydrochloric acid is added to a solution of silver sulphate and mercuric sulphate. The amount of silver chloride remaining dis- solved increases with the amount of mercury present but not proportionately. When the precipitated silver chloride has been filtered the filtrate gives a further precipitate with hydrochloric acid or chlorides and with silver nitrate whilst sulphates nitrates and alkali acetates cause no precipitation.Similar phenomena are observed when other mercuric salts such as the nitrate or acetate are employed. R. V. S. Some New Basic Silver-Mercury Compounds. BICE FINZI (Gaxxetta 1911 41 ii 543-549).-Yellow mercuric oxide is soluble in solutions of silver nitrate silver sulphate and silver acetate especially in the warm The solubility increases with the dilution of of the silver solution. When a boiling solution of silver sulphate (saturated in the cold) is treated with yellow mercuric oxide until no more dissolves and filtered in a few days a pale yellow mbstance Ag,SO,,HgO is deposited ; it crystallises in aggregates of very small rhombic tablets. When a twice normal solution of silver nitrate is similarly treated a reddish-yellow substame AgN03,2Hg0 is obtained ; it forms tufts of acicular crystals.R. V. S.INORGANIC CHEMISTRY. ii. 159 The Freezing-point Diagram of the Binary System Silver Sulphide-Iron Sulphide. P. SCHOEN (MelaZZu?yie 19 1 1 8 737-738). -Ferrous sulphide prepared by heating crystalline pyrites mixes with silver sulphide in all proportions in the molten state The freezing-point curve of the system is a simple one with a n eutectic point at 615' and 11% FeS. The transformation of silver sulphide at 175' occurs at constant temperature throughout the series. The two sulphides do not combine with one another. C. H. D. Molecular Weight of Calcium Oxide. Atomic W e i g h t of Calcium. WILLIAM OECHSNER DE CONINCK (Compt. !rend. 1912 154 1479-1480).-1n four experiments pure calcium forrnate was ignited and the oxide weighed.I n another calcium oxdate was converted into the oxide by ignition. The mean of the five deterniinations gives 56.06 as the molecular weight of calcium oxide or 40.02 for the atomic weight of calcium. w. 0. w. The Reduction of Calcium Sulphate by Carbon Monoxide and by Carbon and the Oxidation of Calcium Sulphide. Ii. 0. HOFMANN and W. MOSTOWISCH (BUZZ. Amer. Imt. Mininy G'ny. 1910 917-939).-Cslcium and barium sulphates can be conveniently and quantitatively reduced by a stream of dry carbon monoxide at a temperature of 900-950' ; the sulphate is first rendered anhydrous by heating until the weight is constant ; the reduction commences at 680-700° becomes vigorous a t 750-850' and is practically finished a t 900'; the heating is continued until there is no further loss of weight.The reduction with carbon in an atmosphere of nitrogen begins a t 700' is vigorous a t 800-900" and completed at 1000"; at lorn temperatures the carbon is converted into carbon dioxide a t higher into carbon monoxide. The oxidation of calcium sulphide is carried oat by heating in a stream of pure dry a i r ; the action starts at SOO' and .yields 7376 calcium sulphate and 37% calcium oxide. F. M. G. M. T h e Constitution of Portland Cement Clinker. ERNST JANECKE (Zeitsch. nnoyg. Chem. 191 1 73 200-222. Compare Shepherd and Rankin Abstr. 1911 ii 725).-A part of the quaternary system CaO-SiO2-8l20,-Pe,0 has been studied by means of thermal analysis. The ferric oxide appears to occur only in combination with lime and solid solutions are not formed.The mixtures are heated by means of an oxygen blowpipe in an iridium crucible which can be unwrapped t o remove the mass after solidification. After powdering the mixture is re-melted and a cooling curve taken. A single definite ternary compound is found 8Ca0,2Si02,A1,0 with a melting point of 1382'. which is lowered by the addition of its components. This compound which was not observed by Shepherd and Rankin is regarded as being identical with alite the principal crystalline constituent of Portland cement clinker. The existence of such a ternary compound explains why the presence of alumina is necessary in cements its properties being different from those of the 11-2ii. 160 ABSTRACTS OF CHEMICAL PAPERS. binary calcium silicates.BIicroscopical examination confirms its homogeneity. Belite celite and felite are probably the compounds 2Ca0,Si02 3CaO,Fe,O and CaO respectively the latter being often absent. C. H. D. Fusion Experiments with Metasilicatea and Titanates. S. SMOLENSKY (Zeitsch. anorg. Chem. 1912 73 393-303).-Mixtures of silicate3 and titanates have been examined by thermal analysis in graphite crucibles in an electric furnace. Calcium silicate and calcium titanate form solid solutions and the freezing-point curve has a minimum at 1420" and 33.4 mol. % CaTiO,. At a lower temperature the solid solution is resolved into its com- ponents the transformation curve rising to a maximum a t 1350" and again falling The transformation is confirmed microscopically. Mixtures of manganese silicate and titanate form a eutectiferous series with the eutectic point a t 28.3 mol.% MnTiO and 1120'. Solid solutions are formed from 38.3 to 100 mol. % MnTiO but not at the other end of the series. A decomposition of this solid solution takes place at about 1050". Barium silicate and titanate form a com- plicated system of which the curve OF initial freezing points only has been determined. Synthetic titanite CaSiTiO forms blue crystals m. p. 1221" this colour being shown by all synthetic titanates. The crystals enclose small crystals of perowskite CaTiO,. C. H. D. Thermal Analysis of Binary Mixtures of the Chlorides of Bivalent Elements. CARLO SANDONNINI ( A t t i R. Accccd. Lincei 1911 [v] 20 ii 646-653. Compare Ruff and Plato Abstr. 1903 ii 588 ; Menge Abstr. 1911 ii 982 ; Sandonnini and Scarpa Abstr.1911 ii 984; and this vol. ii 162)-In the present paper the results are given of the thermal analysis of the bivalent systems formed by strontium chloride with the chlorides of barium cadmium lead and magnesium and by barium chloride with the chlorides of cadmium and lead. Strontium chloride and barium chloride form mixed crystals in all proportions; there is a minimum at 854" corre- sponding with about 35 mol. % of barium chloride. Strontium chloride and cadmium ehloride are miscible only in the liquid state; the eutectic lies at 502O corresponding with 58 mol. % of cadmium chloride. Strontium chloride and lead chloride give mixed crystals in all proportions. Strontium chloride and rnanganous chloride are miscible only in the liquid state; there is an eutectic a t 499' (45 mol.% of manganous chloride). The system BaC1,-CdCl is similar to the preceding; the eutectic lies at 450" (57 mol. % of CdCI,). Barium chloride and lead chloride give mixed crystals in all proportions. The author dissents from Menge's conclusions in regard t o the system CaC1,-CdCl,. His results give a simple curve of mixed crystals with a minimum. R. V. S.INORGANIC CHEMISTRY. ii. 161 The Reaction between Concentrated Solutions of Barium Acetate and Aluminium Sulphate. JULIUS F. SACHER (Chem. Zeit. 191 1 35 1447).-Concentrated solutions of barium acetate and aluminium sulphate react together very slowly and barium sulphate is not at first precipitated. Vigorous stirring or shaking heating or dilution with water brings about precipitation.Barium acetate and magnesium sulphate l)ehave similarly but precipitation is much more rapid in accordarice with the greater dissociation of magnesium sulphate. Saturated solutions of lead acetate and aluminium sulpbate give a precipitate immediately. I. Isolation of a Compound of Magnesium and Zinc. ARTHUE J. BERRY (Proc. Rog. Soc. 1911 A 86 67-71).-Mixtures of magnesium and zinc containing the latter in excess of the ratio 1Mg :2Zn have been distilled in highly exhausted glass tubes at temperatures somewhat lower than the temperature a t which the glass began to soften Analysis of the residual alloy gives numbers which correspond closely with the formula MgZn,. Since the existence of a definite compound of this composition is indicated by the freezing- point diagram it appears that this compound can be isolated by distilling off the excess of the more volatile component from a mixture of the two metals.Further experiments are described which C. H. D. Distillation of Binary M i x t u r e s of Metale i n a Vacuum. show that this compound can be distillid without change. H. M. D. Solubility of Magnesium Ammonium Sulphate. ATHERTON SEIDELL (Phamz. J. 191 1 [iv] 33 846).-Lothian (Abstr. 1910 ii 504) gave determinations of the solubility of crystallised magnesium ammonium sulphate much higher bhan those on record. The author calls attention t o a mistake in Lothian's calculations and shows that when this is corrected there is really a good agreement a t the higher temperatures ( 1 5- 27.22').At the lower temperatures (1 *11-1 oo) Lothian's results are Drobablv incorrect since his solubility curve for these temperatures is-very iriegular and abnormal in its cobrss. T. s. P. Action of Distilled Water and of Distilled Water Contain- ing Electrolytes on ~ e t a ~ i c Lead. MAHGHERITA THAUBE- MENGARINI and ALBERTO SCALA (Men?. R. Accad. Lirtcei 1911 [v] 8 576-598).-1n contact with distilled water quite free from oxygen metallic lead passes rapidly into colloidal solution at room temperature. I n contact with oxygen from the air the colloidally dissolved metal is rapidly transformed into the colloidal hydrated oxide the particles of which slowly aggregate to form crystals of various forms. Electro- lytes above a concentration characteristic for each prevent the corrosion of lead ; below this concentration corrosion continues but the colloid is coagulated and deposited on the surface of the metal.It is considered that the colloidal state is an ionised combination of a colloid with water and it is shown that this theory affords a satisfactory explanation of the behaviour of colloids.ii. 162 ABSTRACTS OF CHEMICAL PAPERS. All metals dissolve more or less easily in water in the colloidal state. Lead dissolves most readily zinc and iron also dissolve colloidally in water in the absence of oxygen and the results with these metals will be described in a later communication. Platinum comes at the other extremity dissolving only with very great difficulty. G . S. The Formation of Lead Carbonate from Metallic Lead in Presence of Metallic Aluminium. C.REICHAI~D (Pharm. Zeictr.-lb. 191 1 52 1395-1396).-Aluminium number plates on the wooden vessels of a hrowery were fixed on a backing of lead held in an iron- frame. After a time the plates became covered with a laminated deposit consisting of lead acetate and lead carbonate in which thin laminae of lead and aluminium were also t o be distinguished. C. H. D. Thermal Analysis of Binary Mixtures of the Chlorides of Univalent Elements. CABLO SANDONNINI and P. C. AUREGGI ( A t t i A?. Accad. Lincei 1911 [v] 20 ii 588-596. Compare Sandonnini Abstr. 1911 ii 800).-The paper deals with the thermal analysis of six more binary mixtures of the chlorides of these elements. Lithium chloride and thallous chloride aro completely miscible in the liquid state.There is an eutectic at 342" corresponding with about 62 mol. % of thallous chloride and the two substances do not give mixed crystals in any proportion. The eutectic point of the system NaCl-TIC1 lies at 412' (about 85 mol. % of thallous chloride) and probably the two suhstaoces are not miscible in the solid state Potassium chloride and thallous chloride are miscible in all proportions both in the solid and in the liquid state. The system RbCI-AgC1 shows an eutectic point at 253" (60 mol. % of silver chloride); this is analogons t o the system KC1-AgCl (compare Scherntschuschny Abstr. 1907 ii 259) and here also thermal analysis does not reveal the compounds which are known to exist. Rubidium chloride and tliallous chloride are completely mi~ciblc within wide limits.Thallous chloride gives with silver chloride a compound 2AgC1,3TlCl which decomposes on melting and is revealed by a pause at 252". There is an eutectic at 210' (41 mol. % of thallous chloride). R. V. S. Europous Chloride. GEORGES URBAIN and FRANCOIS BOURION (Compt. rend. 191 1 153 1155-1 158).-The action of chlorine and sulphur chloride vapour on europium oxide leads t o the formation of a black mass containing less chlorine than europic chloride. To obtain the latter in the anhydrous state it is necessary to employ the hydrated chloride dried at 100'. Europous chloride EuCl is best prepared by reducing the higher chloride in a current of hydrogen at 400-450". It is a colourless amorphous substance forming a neutral solution in water.When the latter is concentrated at loo" oxidation occurs in accordance with the equation 12EuC12 + 30 = 8EuC1 + 2Eu,O,. Europous chloride is more stable than the corresponding chloride of samarium the only other metal of the group known t o form a lower chloride. w. 0. w.INORCIANIC CHEMISTRY. ii. 163 Atomic Weight of Holmium. OTTO HOLMBERG (Adiv. Kern. Min. Geol. 19 1 1 4 No. 10 1-4).-The holmium material previously obtained by the author (Abstr. 1911 ii 286) has been further purified by a long series of fractional crystallisations. After 250 fractionations of the nitrate 10 chief fractions were obtained which contained only traces of erbium ; these were further fractionated by repeated partial precipitation with ammonia until finally an oxide was obtained which gave a value for the atomic weight of holmium which was not altered by further fractionation.As a mean of six determinations the atomic weight is found to be 163.5. Spectral examination of 2N- and 09N- solutions of the nitrate prepared from this oxide showed that only the merest traces of erbium and dysprosium were present. Examination of the atomic weights of the rare-earth metals shows that they may be divided up into pairs for example lanthanum and cerium praseodymium and neodymium etc. in which the atomic weights are very close together ; dysprosium (= 162.5) and holmium (= 163.5) form such a pair. Holmium oxide is pale yellow in colour ; the salts are yellow with a slight tinge of orange. Solubility of Aluminium Hydroxide in Sodium Hydroxide. ROLAND EDGAR SLADE (Zeitsch.EZektrochem. 191 2 18 1-2. Compare ibid. 1911 17 261 ; Herz Abstr. 1911 ii 728).-In a recent paper (Zoc. cit.) Herz who had previously from solubility measurements found the ratio Na A1 as 3 1 for solutions of aluminium hydroxide in sodium hydroxide criticised the author’s statement based mainly on freezing-point determinations that the solutions in question contain only NaA10,. The author has now carried out further solubility measure- ments and finds that the ratio Na:Al varies from 2 1 to 10 1 according to the conditions of precipitation and the mode and duration of drying of the hydroxide. The observation of Herz that the ratio Na A1 is always 3 1 is erroneous and there is no evidence that the solutions in any circumstances contain A10,”’ ions.The gelatinous aluminium hydroxide is always an unstable phase under these conditions. G. S. Solubility of Aluminium Hydroxide in Ammonium Sulphate Solution Artificial Production of Alumian. ROBERT KRE- MANN and K. HUTTINGER (Zeitsch. Krgst. Min. 1911 50 85 ; from Jahrb. k.k. geol. Reichs. 1908 58 637-658).-Starting with a con- centrated solution of aluminium sulphate the solubility of aluminium hydroxide increases with decreasing concentration reaching a maximum for 38% A12(S04) at 60° 32% at 20° and 28% at 40’; the solid in contact with the solution has now the composition A12(S04),,1 6H20. The solubility of the hydroxide then decreases slowly with decreasing concentration to 7.5% A12(S04) a t 60’ and 40° when the precipitate has the composition of alumian A1,O3,2S0,,1 2H,O.Corresponding basic sulphates with 10H20 and 11H,O were also obtained. T. 5. P. L. J. S. Some Artifloial Aluminosilicates of the Type R0,AI,0,,2Si02. A. S. GINSBERU (ZeitscA. anorg. Chem. 1912 73 277-292).-Theii. '1 64 ABSTRACTS OF CHEMICAL PAPERS method of thermal analysis has been applied to mixtures prepared by heating alumina and silica with the carbonates of other metals in graphite crucibles in a kryptol furnace. Synthetic anorthite CaA12Si,08 solidifies at 1440" when slowly cooled the readings being sharp. The value 1532O obtained by Day and Allen (Abstr. 1906 ii 177) for the melting point is probably high owing to superheating. The synthetic product is optically identical with the natural mineral. Synthetic nepheline Na,AI,Si,O tends t o form a glass unless the fused mass is heated to 1500-1600° before cooling when crystallisation occurs readily the freezing point being at 12.23'.The glass is slowly devitrified forming nepheline crystals at 900°. Anorthite and nepheline are isomorphous the freezing-point curve of their mixtures being continuous with a minimum a t 1130O and 70% nepheline. Mixtures near to the anorthite end of the series have a tendency to form glasses. The polymorphic transformation of anorthite a t 1150' can be detected in the mixtures. Kaliophilite K2Al,Si208 (potassium nepheline) crystallises with difficulty and the freezing point has not been determined. Eucryptite Li2A1,Si,0 crystallises readily forming twinned crystals. The freezing point is 1307".C. H. D. The Freezing-point Diagram of the Binary System Manganese-Arsenic. P. SCHOEN (Metallurgie 1911 8 739-741). -Alloys of manganese and arsenic prepared by adding the compound MnAs to manganese give a freezing-point curve which has a maximum at 1029' and 59.5% Mn corresponding with the compound Mn,As and another a t 955' corresponding with MnAs. Eutectic points occur at 932' and 78% Mn and at 880" and 50% Mn respectively. A reaction in the solid state accompanied by tho development of heat reaches a maximum at 752' and 52.5% &In and probably indicates the formation of a third compound Mn,As,. Alloys in the neighbourhood of this composition become magnetic on quenching from S50° whilst those containing from 45 to 4'7.2% Mn are even magnetic when slowly cooled.MnAs and Mn,As are not magnetic (compare Wedekind and Veit Abstr. 1911 ii 985). C. H. D. Reduction of Neutral Potassium Permanganate Solu- tions in Presence of Normal Sulphates in Various Con- centrations. P. A. TSCHEISHWILI (J. IZuss. Phys. Chem. Xoc. 191 1 43 1402-1420 Compare Abstr. 1911 ii 43).-The author has examined the action of a number of normal sulphates on potassiuni permanganate in neutral solutions these being subsequently filtered through washed ignited asbestos and the permanganate estimated by titration. With all the sulphates employed except chrome alum a slow reducing action on the permanganate was observed and in some casee the percentage of the permanganate reduced was less after say eight months than after three months. Chrome alum exerted il far more rapid action as much as 80-90% of reduction occurring in twenty-four hours and 100% in a month; this result is probably due to the conversion of the chromic oxide into chromium trioxide,INORGANIC CHEMISTRY.ii. 165 Cr20 + 0 = 2Cr0,. A solution of permanganate in distilled water alone showed no reduction after eight. months. The general conclusion drawn from the results is that in many cases mineral salts play the part of positive or negative catalysts towards the reduction of permanganate in neutral solution. This action not only depends on the chemical nature of the constituent ions of the salts but varies widely with the physical conditions of the surrounding medium. Concentration of the salt also influences the intensity of the catalytic action which appears always t o increase with increase of the concentration.The System Iron-Carbon. ANDREAS SMITS (Proc. K'. Akccd. Wetenscl~ Amsterdccm 191 1 14 530-536 ; Zeitsch. Elektrochem. 1912 18 51-54).-Although cementite is metastable when found as a constituent of alloys of iron and carbon it may be formed by heating iron containing graphite a t or above 720' (Royston J. Iron and Steel Inst. 1897 1 166) and cooling rapidly. It may be supposed that the liquid phase and also the solid solution which separates from it contain carbon dissolved both as graphite and as carbide the equili- brium being 3Fe+C!,Pe,C. A n increase in the concentration of carbon shifts the equilibrium towards the right. When the solid solution is cooled rapidly from 1030° the greater concentration of carbon in the solid phase may shift the internal equilibrium so far to the right that the solid solution becomes supersaturated with respect to carbide which is therefore deposited.The Polyhedral S t r u c t u r e of Iron-Carbon Alloys. N. J. WARK (Metccllurgie 1911 8 731-736. Compare this vol. ii 52).- Xartensite in quenched steels often forms large polyhedra. Quenching experiments with carbon steels almost free from other elements show that this structure is probably that of the original austenite solid solution although it has not be found possible to obtain it in low- carbon steels entirely free from martensite owing to the difficulty of undercooling such alloys. Steel etched with hydrogen chloride at high temperatures within the austenite region shows a polyhedral structure whatever the proportion of carbon may be.Action of Heat on the Ochres. Allotropic Modifications. A. ROUCHONNET (Bull. Xoc. chirtz. 1912 [iv] 11 6-12. Compare Abstr. 1911 ii 495).-The author describes the properties of some modified ochres. The density increases from the natural yellow ochre upwards through the various modifications to the black obtained a t 1600O. The plasticity diminishes with rise in temperature and seems to have entirely disappeared a t 800-850". The yellow and red ochres are soluble in acids but the so-called '( a-variety,'' obtained a t 950° and the other modifications are insoluble in all acids except hydro- fluoric even on heating. The a-variety is highly magnetic. This property however disappears on prolonged heating only to reappear at 1600'.W. G. Comtitution of Ferric Sulphate. ALBERT RECOURA (Compt. rend. 1911; 153 1223-1226. Compare Abstr. 1909 ii 552 693).-The yellow T. H. P. C. H. D. C. H. D. A Compound of Ferric Sulphate a n d Alcohol.ii. 166 ABSTRACTS OF CHEMICAL PAPERS. compound Fe,0,,3S0,,3H20 obtained by dehydrating the hexahydrate at 108" forms an alcoholic solution in which barium chloride fails t o produce a precipitate of barium sulphate. The compound with alcohol Fe,03,3S0 2 H20,2C,H,0 previously described loses half its water at 105O without changing in appearance; the remainder is lost simul- taneously with the alcohol a t 1 1 5 O the material becoming temporarily black. The alcohol does not appear to be united t o sulphuric acid since it is removed by solution in water unlike the combined alcohol in ethyl ferrisulphate. These and other observations are explained by supposing that the trihydrate has the constitution Fe,(S0,),(OH)6 the salt in a manner resembling the green pentahydrate of chromic The Form of Certain Silicate Precipitates. RAPHAEL E.LIESEGANG (ZeitscA. Chem. I n d . Kolloide 19 11 9 298-300).-The various forms assumed by the colloidal precipitates of ferric silicate are described. These different forms arise when drops of concentrated solutions of ferric chloride are brought into contact with a solution of sodium silicate under varying conditions. Red and Blue Cobaltous Hydroxide. ARTHUR HANTZSCH (Zeitsch. anorg. Chem. 191 2,73,304-308).-Blue cobaltous hydroxide is generally regarded as a basic salt.It is found that when precipi- tated from a solution of the sulphate by an insufficient quantity of alkali and washed with cold water until no more sulphuric acid is removed the residue always contains much sulphate. Repeated boiling with water free from air however gradually removes most of the sulphate without altering the blue colour. The red hydroxide is obtained by precipitating with an excess of alkali washing with hot water in a n atmosphere of hydrogen and finally washing with alcohol and ether. It retains some water even after prolonged heating in nitrogen a t 300° whilst the blue hydroxide is completely dehydrated a t 170'; on the other hand acetyl and benzoyl chlorides react much more vigorously with the red than with tho blue compound.The case is regarded as one of '' chromo-isomerism," and the formulae Co(OH) and H,O*****CoO are suggested for the red and blue compounds respectively. C. H. D. Solubility of Uranous Oxide in Certain Acids. ALBERT RAYNAUD (Compt. rend. 1912 154 1480-1482).-The uranous oxide employed was obtained by the ignition of urnnyl oxalate. The oxide is readilysoluble in nitric acid with formation of uranyl nitrate; aqua regia also dissolves it readily. It is less soluble in the other common acids requiring 3100 grams of hydrochloric acid (D 1*17) 4650 grams of hydrobromic acid (n 1.52) 2200 grams of sulphuric acid (D 1-79) and over 12,000 grams of acetic acid to dissolve 1 gram of the oxide sulphate. w-. 0. w. 13. M. D. . at 17'. The solibility is slightly greater in the boaing acids. w.0. w. Pure Vanadium. OTTO RUFF and WALTER MARTIN (Zeitsch. angew. Chem. 1912 25 49-56).-Vanadium trioxide melting atINORGANIC CHEMISTRY. ii. 167 about ZOOO" gives better results in the preparation of pure vanadium than the pentoxide on account of the ready fusibility of the latter which causes it to pass into the slag. Vanadium trioxide prepared by reducing the pentoxide in hydrogen below 550" is mixed with aluminium and 2% of powdered carbon and pressed into a crucible lined with magnesia. The crucible is covered and heated to redness after adding a layer of ignition mixture. The product contains 95% of vanadium. Reduction with carbon in an arc gives a less pure product. Products containing 95 t o 97% of vanadium are obtained by moulding mixtures of the trioxide and carbon with starch into rods sintering in an electric furnace a t 1750" and finally fusing i n a n arc.The impurity consists of carbon or oxygen according to the proportions employed. Vanadium carbide VC prepared in the resistance furnace has m. p. 2750" DlS'7 5.405 and is silvery-white highly crystalline and extremely hard. When 6 grams of the powdered carbide are mixed with 4.76 grams of vanadium trioxide arid a little starch solution pressed into a zirconia crucible and heated a t 1950° the metal is fused and then contains V 98.11% and C 1.92%. . The melting points of different specimens of vanadium have been determined by heating in the electric vacuum furnace. Either oxygen or carbon raises the melting point of vanadium and by extrapolating the two curves obtained from mixtures containing varying quantities of carbon and of oxygen pure vanadium is found to melt a t 1715".The raising of the melting point is due to the formation of solid solu- tions with the oxide VO arid the carbide. The density is also found by extrapolation being lowered by impurities. The pure metal has D1s.7 5.688. The heat of combustion of 1 gram to the pentoxide is 2456 cal. C. H. I). Hetero-poly-acids containing Vanadic Acid. WILHELM PRANDTL [and MAURICE HUMBELIT] (zeitsch. anorg. Chem. 191 1 73 223-238. Compare Dullberg Abstr. 1903 ii 733; Prandtl and Lustig Abstr. 1907 ii 477).-The complex vanadiselenites may be regarded as derived from a hexavanadic acid and may then be formulated in accordance with Werner's theory.One molecule of a hexavanadate can combine with up to 12 mols. of selenious acid. The vanadiselenious acid 3V205,48e0,,4H20 which forms hydrates may be represented as 1 4-hexavanadiselenious acid H,V,017,4H,Se0 with 4H,O and 8H,O. The sodium potassium and :triimonium salts are obtained by adding a 20-25% solution of selenious acid in excess t o solutions of alkali vanadates. The following salts are described Na2H2V6Ol7,4H,SeO orange prisms ; Na,H,V60,7,4Se02,2H,0 dark red- prisms ; Na2H,V,Ol7,4H,SeO3 6H20 a bulky precipitate ; K3HV,OI7 4Se0 or K2Hz V,Ol7,4SeO2 a bulky orange precipitate ; K ,H,V,OI7 4H,SeO ; K,W2V6017 4SeO,,2 H ,O ; a yellow pulverulent precipitate ; (NH,)2H,V,017,4Se02 an orange I< 3HV6017 4Se02,2H,0 ; (N H4),HV~0,7,4se0,,H,0,ii.168 ABSTRACTS OF CHEMICAL PAPERS. precipitate. Higher proportions of SeO were found in some of the compounds prepared by Prandtl and Lustig (Zoc. cit.). Ammonium 1 12-hexavanadiselenite (XH4)3HV6017,1 2Se0 2 or 4H20 forms red transparent crystals with blue surface lustre and the potassium salt is quite similar. The 2 5-hexavanadiselenites have the formula 2M,V,0,7,5H,Se0,,xH,0 where M = NH I( Li Na. The yellow vanadiselenites have the formula M,O,V,O 2Se02,xH,0. The complex vanaditiiugstates and vanadimolybdates described in the literature are reviewed and formulated as derivatives of hexavunadic acid. C. H. D. Tantalum and Columbium Pentafluorides and the Preparation of Pure Tantalic and Columbic Acids. OTTO RUFF and EMIL SCHILLER (Zeitsch.anorg. Chem. 1911 72 329-357). -Tantalum pentachloride is best prepared from the oxide by heating in a quartz tube to redness i n a stream of chlorine and carbon tetra- chloride. The chloride reacts with anhydrous hydrogen fluoride in a freezing mixture in a platinum apparatus (Abstr. 1907 ii 268) and the resulting pentafluoride is purified by distillation under reduced pressure. Tantalum pentafluoride forms large colourless doobly refracting prisms D1"' 4.744 m. p. 96.S" (corr.) b. p. 229*2-289*5°/760 mm. (corr.). The vapour pressure has been determined in a modified apparatus of Smith and Menzies (Abstr. 1910 ii 1036) constructed of copper. The fluoride is inactive towards oxygen and most metals and non-metals up to its boiling point. It is rapidly decomposed by water acids and alkalis alcohol and ether.It forms potassium tantalum heptafluoride when fused with potassium fluoride. Columbium pentafluoride is prepared in a similar manner and forms colourless refractive prisms DIS 3.2932 m. p. 75.5" (corr.) and b. p. 217-220"/760 mm. (corr.). It is somewhat more reactive than the tantalum compound. I n order to improve the method of separation of tantalum and columbium by fractional crystallisation of their alkali double fluorides determinations of the solubility of these salts in presence of varying quantities of hydrofluoric acid and potassium fluoride have been made using pure ~ hydrofluoric acid prepzred by dissolving the anhydrous compound in water. The solubility of both fluorides diminishes rapidly with increasing concentration of potassium fluoride and decreasing concentration of hydrofluoric acid.The solubility increases rapidly with the temperature and is always greater for the columbium salt than for the tantalum salt. A method of fractionation is described based on these results and suitable for the treatment of large quantities of material. For the quantitative separation of tantalum and columbium 0-5-1 gram of the mixed oxides is dissolved in hydrofluoric acid the quantity of acid corresponding with an excess of 4,3%. Sufficient potassium fluoride is then added to combine with the columbium the solution is evaporated and the residue boiled with 0.75% hydrofluoric acid. After filtering the hot solution the residue is washed twice with 10 C.C. of hot water. The filtrate is then evaporated the residueINORGANIC CHEMISTRY.ii. 169 dried at 120’ and dissolved in hot water and N/lO-potassium hydr- oxide is then added until the precipitate formed just dissolves. The solution is evaporated the residue dissolved in 10 C.C. of hot water and again evaporated. This is twice repeated until the tantalum double salt remains. The united tantalum fluorides are then converted into oxides and the columbium is estimated in the filtrate. Tantalum is not carried off as vapour by hydrogen fluoride or ammonium fluoride and the supposed acid fluorides of tantalum and columbium do not exist. The separation of titanium from the two other earths is best carried out by heating in a stream of chlorine and carbon tetrachloride when titanium tetrachloride is first volatilised.C. 13. D. Interpretation of the ‘( Protective Action ” of Gelatin on Colloidal Gold. GEORGE R. MINES (Proc. physiol. Xoc. 1911 xxii -xxiv ; J. PLysioZ. 43).-The experiments recorded confirm the view that the explanation of the ’‘ protective action ” of gelatin is due to the formation of a thin coating of gelatin over the gold particles ; this protects them from the action of electrolytes. Colloidal Gold and Platinum. NICOLA PAPPADA (Zeitsch. Chem. Ind. Kolloide 1911 9 270-275. Compare this vol. ii 157). -As a general rule the influence of electrolytes on the coagulation of gold and platinum hydrosols is exactly the same as on the coagula- tion of colloidal silver I n regard t o chemical activity however silver is much more active than either gold or platinurn. Colloidal gold is not coagulated by mercuric chloride in the cold neither is there any chemical action.When the solution is heated coagulation takes place but the mercuric salt is not reduced. When aqueous solutions of hydrocyanic acid or potassium cyanide are added to the gold hydrosol its colour changes from dark violet to yellow. The yellow solution is not coagulated when active multivalent metal ions are added. When acted on by the halogens colloidal gold is con- verted into the corresDondine auric salts. Towards these chemical W. D. H. L v reagents the behaviour of platinum hydrosol is similar to that of gold. H. M. D. Absorption of Hydrogen by Palladium at Small Pressures and Low Temperatures. S. VALENTINER (Ber. Deut. physikd. Ges. 19i 1 13 1003-1022).-The absorption of hydrogen by spongy palladium has been examined a t - 190° - 7 8 O and the ordinary temperature for small values of the gas pressure. A glass tube of about 100 C.C. capacity was filled with purified hydrogen and after its pressure had been determined by means of a McLeod gauge the gas brought into contact with a known weight of palladium con- tained in a capillary tube. After equilibrium had been reached the pressure in the apparatus mas again determined by means of the gauge and from the dimensions of tbe various parts of the apparatus the amount of hydrogen absorbed by one gram of palladium could be calculated. By admitting successive quantities of hydrogen into the apparatus it was possible to obtain the quantities of hydrogen absorbed for a series of pressures.ii. 170 ABSTRACTS OF CHEMICAL PAPERS. The data obtained in this way show that the absorption capacity of palladium for hydrogen increases very rapidly with falling temperature. The equilibrium pressure for palladium sponge which contains 0.1% of hydrogen amounts t o 0.025 mm. at - 78' and 0.001 mm. a t -190'. The absorption coefficient also increases con- siderably with diminution of pressure and this is especially marked a t the temperature of liquid air. The determination of the true value of the equilibrium is however complicated by the fact that the absorptive capacity of the palladium is found to depend on its previous history. On account of the extremely large absorptive capacity for hydrogen at - 190° and low pressures palladium can be very conveniently employed for the removal of the last traces of hydrogen from other gases and experiments are recorded which show that this can be done e ff el t i vel y. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9120205151

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 170 ABSTRACTS OF CHEMICAL PAPERS. Miner a l o g i c a1 C h e mi 8 t rg. Determination of the Crystallisation Power of Minerals. V. SCHUMOFF-DELEANO and EMIL DITTLER (Centr. Min. 2911 753-757).-A small amount (about 0.5 mg.) of the powdered mineral was fused in a small silica dish on the heating stage of the microscope and the temperature quickly reduced to a definite point below the melting point. After the temperature had remained constant for some time the number of centres of crystallisation seen in the field of view were counted. These numbers are plotted against the tempera- tures and different types of curves are so obtained. Spinel gehlenite and melilite exhibit a greater power of crystallisation than diopside hedenbergite and Egirite. L. J. S. Native Iron from Russian Island Vladivostok.A. A. INOSTZ- ANZEFF (Zeitsclk Kryst. Min. 1911 50 61-62 ; from Trav. SOC. Nat. St Pbtersbourg 1907 35 Sect. Giol. Min. 21-57).-The specimen described was obtained in a bore-hole passing through quartz-porphyry and Triassic sandstone. It is brown and resembles limonite in appear- ance but it has a much higher sp. gr. (7.007) than this and i t is strongly magnetic. On a fresh fracture it shows a peculiar oolitic structure with black grains set in a silver-white metallic ground-mass. The structure of the metallic portion as seen under the microscope is not like that of other native irons but is very similar to that of artificial cast iron there being bands of ferrite granular cementite and a ground-mass of pearlite whilst graphite is also present. Analysis by S.A. Jakowleff gave Fe. Comb. C. FreeC. Al. Mn. Si. S. Total. 93.87 0-33 2.87 0-16 0-66 1-55 0'04 99-48 In composition also the material is thus identical with artificial cast,MINERALOGICAL CHEMISTRY. ii. 171 iron. native cast iron ” was formed by the action of the intruded igneous rock on coal and iron ore in the sedimentary rocks. L. J. S. JULIUS YON ~ Z ~ D E C Z K Y (Petvoleurn 1911 6 773).-A natural gas exists in the neighbourhood of KissBrmBs which contains 99.25% methane 0.75% nitrogen and no trace of carbon monoxide and is ejected in daily yield of over 91 21 24 cubic metres and with a noise discernible at a distance of 10 kilometres. The geological aspect of the district is also described. It is suggested that this Earth-gas in Transylvania in the Tertiary Basin.F. M. G. M. A Hydrocarbon from the Diamond-washings of Bahia Brazil. JOHN CASPER BRANNER (Amer J. Xci. 1912 [iv] 33 25-26}. -The material is found as rounded masses beneath the diamond- bearing gravels a t Chique-Chique in the State of Bahia. It is jet-black and opaque ; and very friable breaking with a conchoidal fracture ; D 1.51 H 23. Analysis by L. R. Lenox gave water 19.43 ; volatile combustible matter 35.47 ; fixed carbon 40.06 ; ash (mainly Al,?,) 5-07 = 100.03. The material is soluble in sulphuric acid nitric acid and potassium hydroxide but insoluble in alcohol ether benzene etc. L. J. S. WLADIMIR N. IPATIEFF (J. Russ. Phys. Chem. Xoc. 1911 43 1437-1445 *).-The author discusses the theories of the mineral and organic origin of naphtha and the reason for the displacement of the former by the latter during recent years.All the available geological data testify that original deposits of naphtha occur only where there has been life and that emanation of naphtha has taken place only when it originated in presence of strata permeable to naphtha secondary deposits being thus jobtained. Support to the theory of organic origin is also given by the investigations of geologists and biologists on the destruction of life on the shores of seas and oceans such as is occurring at the present time in the Black Sea and by Andrasoff’s observations on the formation of hydrogen sulphide in the Black Sea owing t o this loss of life. A further hypothesis of the formation of naphtha might be based on the various simple syntheses of representatives of the different classes of hydrocarbons.Reference is made to Sabatier’s results which explain the formation of naphtha from acetylene; to the formation of methane and ethylene by the action of water vapour on carbon in presence of lime (compare Vignon Abstr. 1911 ii 391) and to the author’s own experiments which show that under the influence of heat and pressure ethylene condenses to higher hydrocarbons. Origin of Naphtha. T. H. P. Application of Colloid Chemistry to Mineralogy and Geology. Bauxite a Natural Alumina Hydrogel. EVIL DITTLER and CORNELIO DOELTER (Zeitsch. Chem. Ind. Kolloide 1911 9 282-290).-The behaviour of the chief constituents of bauxites t o wards certain colouring matters has been examined and the informa- * and J.pr. L‘hem. 1911 [ii] 84 800-808.ii. 172 ABSTRACTS OF CHEMIC.4L PAPERS. tion thus obtained has been applied in combination with microscopic observations to the examination and classification of bauxites from different sources. True bauxite is regarded as a hydrogel of alumina which has a large capacity for taking up other substauces such as silica water carbon dioxide sulphur dioxide phosphoric oxide and titanium dioxide. H. M. D. Baddeleyite [Native Zirconia] from Montana. AUSTIN F. ROGERS (Amer. J. Sci. 1912 [iv] 33 54-56).-This mineral pre- viously known only from Ceylon Brazil and the Island of Alno (Sweden) has been found in a gneissoid corundum-syenite from near Bozeman Montana. The minute crystals and grains are black with a sub-metallic lustre and they occur embedded in the felspar and in the corundum or more frequently on the surface of the latter.The mineral is infusible before the blowpipe (but fusible in the oxygen-gas blowpipe) and is decomposed by strong sulphuric acid. The corundum- syenite consists of felspar (microcline-microperthite) biotite and corundum with subordinate amounts of muscovite sillimanite and zircon. The low percentage (about 44) of silica in this rock no doubt caused the zirconia to crystallise as baddeleyite rather than as zircon. L. J. S. Analysis of Thorianite from Ceylon. W. J A K ~ B and STANISLAW TOLLOCZKO (BUZZ. Acad. Xci. Crucow 191 1 A 558-563).-A specimen of Ceylon thorianite gave on analysis Si02. PbO. Bi,O,. CuO. Ce,O,. (La,Di),OB. P,O,.A1,03. Pe,O,. TiO,. 0-250 2.867 0.003 0.008 0.107 0.178 0.030 0.260 0.348 1.295 ZrO,. CaO. Rh. Tho,. U,O,. H,O. C'O,. He. Insol. Total. 0.920 0-17 0 008 65.370 23'470 0.605 0-275 0.225 0.150 99.67 Also As,03 (T) SnO (?) Sb,O HgO tracts. This result when compared with those of other observers (which are tabulated) shows in most cases a much larger amount of uranium oxide and a consequent decrease in thorium oxide. This may be explained by the fact that the mineral is really an isornorphous mixture of uranium and thorium oxides. L. DE K. Minerals Accompanying the Ferriferous Deposit of t h e Buca della Vena near Stazzema Apuan Alps. Uao PAXICHI ( A t t i R. Accad. Lincei 1911 [v] 20 ii 568-571).-Interposed between the calcareous rock and the iron ore a t t h i s place is a reddish-brown mineral of which the main portion is a reddish-brown crystalline substance D 2.88 having the following composition CaO.FeO. MnO. CO,. H,O Total. 52.5a 1 *21 0.98 43.10 2-46 100.33 The mineral is therefore a calcite containing iron and manganese. It bears crystals of pure calcite and is traversed by veins of rnanganite with which a quantity of wad is associated. In the manganite crycltals of magnet,ite and of manganiferous siderite occur whilst in theMINERALOGICAL CHEMISTILT. ii. 173 powdery wad occasional crystals of hornblende are to be found. On the incrustations of wad a crystalline calciferous rbodocrosite is deposited in places. R. V. S. Mineralogical Nature of Russian Phosphorites. WLADIMIR TSCHIRWIKSKY (Jahrb. Min. 19 11 ii 5 1-74).-The material of the Russian phosphorites [that is phosphatic nodules] is in most cases crystalline ; it is not amorphous nor does i t always consist of massive apatite as has often been supposed.It forms the cementing material between grains of quartz felspar glauconite iron oxide etc. in the sandy phasphates which may contain 13-15% P20 and it also forms the base of the calcareous phosphates. Accordlug t o differences in optical character t w o main types are to be distinguished one with a higher birefringence of about 0.008 and the other with a lower birefringence of about 0.004 (as for apatite) or sometimes with little or no action on polarised light. These two types also differ chemically the latter corresponds with fluor-apatite and the former contains little or no fluorine but contains carbonate in combination with the phosphate.The following five chemical groups are distinguished (1) the fluor-apatite group in which the feebly birefringent cementing material has the composition of fluor-apatite 3Crs3(P0,),,CaF2 con- taining 6.97-7*74% CaF,. (2) The podolite group 3Ca,(€'O4)2,CatCO3 (Abstr. 1907 ii 481) ; these are well crystallised occurring either as single crystals or as large spherulites with hirefringenee 0 0075-0*008. (3) Those with the composition 2Cit,(pi),),,C~Co,,CaF~. The mean of three analyses of material of this type from the Kursk district Central Russia is Cit,(PO,) 76.96 C L ~ C O ~ 12.95 CsP2 1Ofl9%. Here the cementing material is radially fibrous with birefringence 0.00s ; the spherulitev are optically negative.(4) Those with the composition 3Ca3(P0,),,2CaC03 as given by the following analysis by A. lnodmmtzeff of a sandy phosphorite from Popova i n the Kursk district. Here the composition Oa,( PO,) 82.97 C'aUO 17*04% approximates to that of dahllite and of stafielite. P205. (20,. F. CaO. SO,. MgO. Al,O,. Fe,O,. matter. H,O. Sand. Total. 16.48 3-25 trace 23.80 0.33 trace 1-71 0'69 1.19 0.56 51'53 99.54 (5) Phosphorites in which the cementing material consists largely The several minerals which may enter into the composition of these Organic of aluminium and iron phosphates. phosphorites (compare W. T. Schnller Abstr. 191 1 ii? 1102) are Apatite ........................... 3Ca3( PO,),,CaF Podolite ........................ 3Ca,(I'O,) CaCO Uahllite ........................2Ca,( PO,) UaCO Francolite ........................ 5Ca3' k'O4) CaCO 20aF Staffelite ........................ 3Ca3( P0,),,CaCO~3,CaF2 * ........................ 3Ca3( PO,),,2CaCO3 * ........................ 2Ca3(P04),,CaC0 CaF L. J. 5. Crystallised Turquoise from Virginia. WALDEMAR T. SCHALLER (Amer. J. Xci. 1912 [iv] 33 35-40).-Bright blue turquoise from VOL. CII. ii. 12ii. 174 ABSTRACTS OF CHEMICAL PAPERS. near Lynch Station Campbell Co. Virginia shows thin layers of crystals cementing together irregular fragments of glassy quartz and in part a drusy botryoidal surface. The minute crystals not exceeding 4 mm. across are triclinic with very nearly the same habit and angles as crystals of chslcosiderite (CuO,3Pe,O,,2P,0,,8H,O or more probably 9H,O) with which turquoise is regarded as isomorphous.The mineral is insoluble in hydrochloric acid but soluble after ignition. No water is lost below 200°; most is expelled below 4-OOo and all below 650° the material being then green in colour. It is infusible before the blowpipe but becomes brown Analysis I after deducting insoluble quartz gives the figures under 11 corresponding with the formula Cu0,3A1,0,,2P20,,9H20. Written in the form of Penfield’s turquoise formula (Abstr. 1901 ii 27) this becomes 6 AI(OH) Cu(OH) H5,(P04)4‘ P,O,. A1,0,. Fe,O,. CuO. H,O. Insol. Total. Sp. gr. I. 29-84 31’91 0-18 7-87 17-59 12-57 99.96 2.816 L. J. S. II. 34.13 36.50 0’21 9.00 20’12 - 99.96 2.84 Pickeringite ( = Picroallumogene) froni the Island of Elba. GIOVANNI D’ACRIARDI (Jalwb.Min. 1911 ii Ref. 188 ; from Proc. wed. SOC. Toscana A%. flat. 1910 19 23-25).-Analysis I is of a mineral labelled as ‘‘ picroallumogene ” recently collected from an iron mine in Elbs and I1 of an original specimen of the “picro- allumogene” of G. Roster (1876). They prove the identity of the mineral with pickeringite and there must be an error in the old analysis of Roster. The mineral is soluble in water. It forms fibrous crusts with a silky lustre and white colour or when containing impurities of a yellow rose-red or brown colour. The fibres give bright polarisation-colours and an extinction-angle of 30” ; the optical sign is positive so,. Al,O,. MgO. H,O. Insol. Total. I. 37-11 10.21 5-25 [47*!21] 0.32 100’00 11. 3630 10.42 5’21 [46+89] 0.78 100’00 L.J. S. Composition of the Platiniferous Dunite of the Urals. S. P J ~ A DE RUBIES (Anal. Fis. Quim. 1911 9 87 294-308).- Numerous analyses of dunite disclose the composition as follows SiO,. Al,O,. Cr,O,. FcO. MgO. TiO,. Total. 40-13 0.45 0’49 8-45 50.45 0.03 100 00 The composition corresponcls with that of an olivine I?e2Si0 1 1 Mg,WiO,. The rock is of remarkably uniform cornposition and free from calcium. G. D. L. Bertrandite from Iveland in Southern Norway. THOROLF VOGT (Zeitsch. Kryst. Afin. 191 1 50 6-1 3).-Pseudomorphs after large hexagonal prisms of beryl from the felspar quarries in the pegmatite-veins at Iveland in SEtarsdalen consist of a compact mixtureMINERALOGICAL CHEMISTRY. ii. 175 of muscovite bertrandite and quartz together with some phenacite secondary beryl chlorite and orthoclase.The bertrandite a mineral not before recorded from Norway forms minute scales to plates 2 cm. across In cavities minute crystals are rarely developed; these are orthorhombic and hemimotphic ; they show a new crystal-form k(023) arid are often twinned on e(011). There are cleavages parallel to cc(ZOO) b(010) and m(110) the two former showing n pearly lustre. D2O 2.597 ; H 64. Refractive indices (Na) a= 1.5914 /3= 1.6053 y = 1,6145 ; 2V = 74'32'. SiO,. G10. CaO. H,O . Total. 51 -03 41.45 0.25 7 -18 99.91 Analysis of fre-h clear material gave agreeing closely with the formula H2Gl,Si,09 or 2G1,SiOq,H,0. The water is expelled only a t a red-heat. The suggestion of Vrba that bertrandite may be isomorphous with hemimorphite arid with the formula G1,Si0,,I120 is thus not confirmed.Nephrite Occurrences in the Alps and in the Franken- wald. OTTO A. WELTER (Jcch~b. Min. 1911 ii 86-106).-Masses of nephrite have been discovered in association with serpentine and gabbro rocks a t the following localities. Salux in Oberhalbstein Grisons (anal. I by F. Mathei 11 by H. Ludwig); here only as a loose blcck. A large mass in situ between serpentine and spilite a t Muhlen in the Val da Faller Oberhalbstein (anal. 111 by W. Mnu IV by L. Hezner); the somewhat weathered material consists of a felted mass of nctinolite fibres with chlorite pale green garnet :picotite and apatite and it presents the same characters as the nephrite imple- ments of the ancient lake-dwellings in Switzerland.I n serpentine and diabase at Schwarzenbach on the Saale in Frankenwalcl (anal. V by Stoepel); and in pbbro-serpentine rocks ,in the Harz (J. Uhlig Abstr. 191 1 ii 46). L. J. S. H,O 1r20 SiO,. A1,0,. Pe,O,. FeO. MgO. CaO. (comb.) (hygrosc.) Total. Sp. gr. z } 3'025 - I. 57.1 2'3 4'0 - 21.2 13'4 1 *9 11. 57.1 1.1 5.0 - 23.0 12.4 - III. 56.1 6.4 2'1 - 20'2 13.7 2.4 - 3.02-2*98 IT." 47'85 4'65 1'25 2-02 26-98 9.95 5'82 0.17 99.85 2.88 * Also P,06 0.39 ; MnO 0.15 ; NiO 0.47 ; Na,O trace ; K20 0.12 ; TiO Crz03 nil. The nephrite of these occurrences has probably been formed by the " cedem-metamorphism " (G. Steinmnnn 190s) of dyke rocks from the gabbro mass intrusive into the serpentine. P. P. P m P m r c o (Zeitscli. Kryst. Min. 1911 50 71-73; from Amzuaire G h l .Min. Russie 1908 10 189-21 1).-&4 detailed description is given of npophyllite crystals found lining geodes in melaphyre on the Lower Tersya a tributary of the Tom. Tho crystals show zonal structures optical anomalies etched figures contraction figures and glide-planes. Analysis gave SiO,. Fe,O,. CaO. K,O. F. N. H,O. Total. 52-12 0'26 2456 5.23 1.73 0.02 16-63 100.55 V. 55-41 2.79 - 3.32 22'41 11.75 3 80 0'11 99.59 3*01-3*02 L. J. S. Apophyllite from Tomsk Siberia. 12-2ii. 176 ABSTRACTS OF CHEMICAL PAPERS. The mineral loses water quickly at 250-260O with the production of "dissociation figures," etc. and it can be completely dehydrated at as low a temperature as 180-190' if ,the heating is prolonged and the material finely divided. L. J. S. An Apophyllite - Analcite Bomb from Monte Somma Vesuvius.STANISLAUS J. TRUGUTT (Centr. Min. 1911 '761-765). -Zeolites are of rare occurrence a t Vesuvias and only phillipsite scolecite thomsonite and analcite have hitherto been recorded from this locality. Analcite forms the main portion of the bomb now described occurring as small trapezohedra which show a milky cloudi- ness and usually a rose-red colour (due t o enclosed hzematite). Analysis I shows a slight excess of silica over that (54.63%) required by the analcite formula (NaA1Si20,,H20) and i t is suggested that this is present as opal giving riso to the milkiness of the crystals. The analcite is pseudomorphous after\ leucite (KA1Si20,) which contains rather more silica than analcite and the difference appears to have separated as opal when the leucite was cmverted into analcite. The presence of opal in cloudy crystals of analcite can be demonstrated by staining with methylene-blue.Total (less SiO,. AI,O CaO. MgO. K20. Na,O. F. II,O. OforF). Sp. gr. I. 56.27 22.24 - - 0.04 13-39 - 8'45 100'39 2'25-2'255 11. 52.76 - 23'69 0.05 6'14 0.65 1.35 16 85 99'62 2.37 The atpophyllite is present as clear asparagus-green cr j s t'als (anal. 11). I t has been derived together with some calcite from wollitsto~iite. -This apophyllite-analcite bomb thus represents an altered form of the wollustonite-leucite bombs which have been found as rarities at Monte Somma. L. J. S. Russian Zeolites Leonhardtte and Laumontite from the Crime&. ALEX. FERSMANN (Zeilsch. Kr?jst. Min. 191 1 50 75-76 ; from Z'rav.Jlus. G601. Pierre Ze Grand Acucl. Sci. St. Pitersbourg 1908 2 103-150).-Laumontite (Ca,A1,Si80,,,8H20) and leonhardite are regarded as distinct species. Of the latter two kinds are distin- guished namely secondary leonhardite Ca2A1,Si802,,'7H20 which results when laumontite loses part of its water on exposure to the air ; and primary leonhardite (Ca,K2,Na2)2A1,Si809,,7H20 which results by the weathering of diorite rocks in the Crirnea and is of importance in the formation of soils. Analyses of primary leonhardite from two localities near Simferopol gave SiO,. Al,O,. Fe,O,. CaO. MgO. K20. Na,O. 110". > l l O o . Total. Sp. gr. 50'94 22.30 0.12 7-65 - 4.01 2'06 2.03 11-39 100.50 2'9992-2'3094 H,O H,O 51.30 21.01 0.55 7-58 0.19 4.02 2 90 1.96 11-14 100.65 2'3134-2'3214 L.J. s. Composition of Nephelite. N. L. BOWEN (Arner. J. Xci. 1912 [iv] 33 49-54).-The excess of silica over that required by the orthosilicate formula (Nrt,K)AlSiO which is invariably shown by analyses of nephelite can be imitated in the artificial soda-MINERALOGICAL CHEMISTRY. ii. 177 nephelite NaAlSiO (hexagonal W = 1.537 E = 1.533 D 2-61 9). By fusing together sodium carbonate alumina and silica in the pro- portions required for this formula there is always a partial volatilieation of the soda and the product contains some corundum in addition to the soda-nephelite. The corresponding excess of silica cannot however be detected under the microscope and it must therefore be held in solid solution in the sotla-nephelite. Mixtures containing a n excess of silica up to that given by Nn,0,A120,,2*2Si0 are completely crystalline and r erfectly homogeneous.This lies iri the diagram (mentioned below) on the line between sotla-nephelite and albite (NaAlSi,O,); and i t Peems prohable that with a still greater excess of silica albite should separczt e. When the results of nephelite analyses are plotted on a triangular diagram with SiO K,O,A1,0 and Na,O,Al,O at; the three corners it is seen that the composition of the mineral cannot bs expressed by the mixing of any two components. With three com- ponents a number of alternntlves are poksible. From the experimental data noted above the three most likely components are tbose recently suggested by Schaller (Abstr. 1911 ii 992) namely the molecules NahlSiO (soda-nephelite) KAlSiO (kaliophilite) and NaAISi,Os (albite).(Compare also Foote and Bradley hbstr. 191 1 ii 122.) L. J. 8. Some Rock-forming Minerals from Hungary. B m A MAURITZ (Jahrb. Min. 1 9 11 ii Ref. 19 1 - 194 ; from Roldtani Ii*ozZijnp Budapest 1910 40 581-5YO).-'L'he following analyses are given I Microcline from the elzeolite-syenite of Ditr6 ; rrJoleciilnr per- centages Ab 31 Or 6 9 ; optical extinction on (001)= +17" on (010)= +6". IT Oligoclase [?] from the miascite variety of the same rock ; Ab,,O;,,An,. III Large felspara from pebbles of pegmatite in the Ditro stream ; Ab82.qAn12.00r5.1 ; extinction on (001) = + 2O on (010) = + 13". IV Elzeolite as crystals 4-5 cm. across from the elaeolite-syenite of Ditr6; the material is quite fresh but encloses a few small needles of aegirite.V Amphibole in crystals several cm. in size from a pegmatitic facies of the elzeolite-syenite of Ditrrj; c t = 1l0 optic axial angle very smdl. VI Albite crystals on ;t matrix of chalybite from Sajohaza Corn. G6mijr ; Ab99Ano.sOro.5 ; extinction on (001) = + 4'30' on (010) = + 19". VlI Garnet (almandine) from the andesite of the Garnet Hill at Szokolhyahuta Corn. Nograd. VIIT Olivine crystals several cm. across occurring as enclosures in the basalt of Medves near Sslgd-Tarjan ; molecular SiO,. I. 65.29 11. 60.28 111. 63.51 IV. 43.96 V. 37-69 VI. 68-95 VIII. 39-22 IX. 42-59 X. 61.27 vIr. 37-20 TiO,. AJ,O,. Fe,O,. FeO. MnO. - 19-06 trace - - - 22-40 - - - 22.14 - - - - 33.01 0.87 - - - 5-67 13-41 6.33 10.43 0'43 - 20.32 1.79 28.67 1-56 3-54 10.63 6'52 5-56 0'37 - 24'15 trace - - - 19.60 - - - - 16.57 - - - CaO.MgO. Na,O. K,O. H,O. Total. trace - 3.44 11'47 0'24 99.50 1.17 0.09 8'44 6-37 1'61 100-36 2-65 trace 10'13 1.00 0'62 100.05 - 15'84 5-39 0.67 99-71 10.97 8.61 3'66 2-33 - 99.5: 0.13 - 11.72 0.10 - 100.50 5.86 4'28 0.34 0.05 - 1 O O . O i - 44.01 - - - 99'80 21.47 7-86 1.67 - - 100.21 4'99 - 8.47 1-00 0-42 100*30 -ii. 178 ABSTRACTS OF CHEMICAL PAPERS. percentages Pe,SiO 17.5 Mg,SiO 82.5. IX Augite pitchy-black crystals several cm. across occurring as enclosures in the same rock ; t,he dispersion is very strong probably owing to the large amount of titanium present. X Oligoclase crystals 7-8 cm. across occurring as enclosures in the same rock ; Ab71.1An2,.20r,.; ; extinction on (001) = + lo on (010) = Oo. L. J. S. Glauconite from the Kurische Nehrung East Prussia. ARRIEN JOHNSEN (Zeitsch. Krpst. Mia. 1911 50 90 ; from Schr$ten php?.-okon. Ges. Konigsberg i. Pv. 1908 49 51-6O).-Analysis of a green mineral occurring in this spit of sand proves it t o be glauconite. The mineral has probably been derived from the Lower Oligocene beds of the neighbourhood. SiO,. AI,O,. Fe,O,. FeO. MgO. CaO. Na,O. K20. H20. Total. 49'67 9-29 19-88 1-28 4.03 1.95 3-00 3.68 7.88 100.66 L. J. S. Poechite an Iron Manganese Ore from Vare$ in Bosnia. FRIEDRICH KATZER (Oesterr. Zeitsch. Berg. Hultenw. 191 1 59 229-232).-A specimen of the mineral poechite obtained from Varei was amorphous with D 3.65-3-75 and hardness by Mohs scale of 3-5-4; i t s chemical composition was SiO,. A1,03. Fe,O,. MnO. CaO. 1160. BaSO,. P. S. H,O. 15.28 3'66 49.5 14-77 1'96 0'84 0.86 0'42 0-03 12.06 wi€h traces of Cu Pb Zn and CO,; and corresponding with the formula (MnO),Si03,2(FeO)2Si03,5H,0 + 2Fe20,,3Hz0. F. M. G . M.

ISSN:0368-1769    

DOI:10.1039/CA9120205170

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 178 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Gaseous Metabolism of Animals with Plain and Striated Musculature. OTTO COHNHEIM (Zeitsch. physiol. Chem. 19 12 76 298-3 13).-Tbe investigation was undertaken with the view of ascertaining whether animals with smooth muscles differ i n their gaseous metabolism from those in which the muscles are striated The animals used were various crustacea molluscs and worms. No typical differences were discovered between animals in relation to their muscular structure. The numerous analyses made are given in tabular form. The gaseous metabolism in these invertebrates is always small although perhaps not much lower than in the smooth muscles of vertebrates. W. D. H. The Primary and Accessory Respiration. Fit. BATTELLI and (Mlle.) LINA STERN (Biochem.Zeitsch. 1912 38 163-165).-ThePHYSIOLOGICAL CHEMISTRY. ii. 179 authors reply to some criticisms of Harden and Maclean (Abstr. 1911 ii 905) who failed to obtain the same results as themselves in experi- ments on pnein. They maintain the correctness of their own experimental results. S. B. S. The Speciflc Action of Carbon Dioxide on the Respiratory Centre. ERNST LAQUEUR and FRITZ VERZ~R ( PJEiiger’s Amhiv 19 11 143 395-497).-The respiratory centre is excited by carbon dioxide and by other acids (hydrochloric acetic). The cause however is not increase in the concentration of hydrogen ions but to the amount of CO H,CO or HCO,’ liberated in the tissues by the acid. The stimulating effect of carbon dioxide on the respiratory centre is specific ; in acetic acid however the aceto-ions form the specific factor.W. D. H. The Influence of Adrenaline on Gaseous Metabolism. PAUL HBRI (Biochem. Zeitsch. 1912 38 23-45).-The experimental method employed for measuring the gaseous exchanges was Tangl’s modifica- tion of Zuntz-Geppert’s method. It was found that adrenaline in doses of 0.0005 to 0.001 gram per kilo. of body-weight when given intraperitoneally and of 0-0001 to 0.0002 gram when given intra- venously cause measurable changes in the gaseous metabolism of dogs. The changes consist in the case of curarised animals in a considerable diminution of the oxygen consumption and a slight diminution of the carbon dioxide production and consequently an increase in the respiratory quotient. This result indicates that the carbohydrates take a larger part in the general metabolism a fact which is in accord with the observed glyczemia after administration of adrenaline and t’ne so-called ‘( sugar-mobilisation ” ; in other words adrenaline causes increased combustion of the sugars.The rise of blood-pressure and the “ sugar mobilisation ” occur at the same time. s. B. s. The Influence of Acids on the Reduction of Arterial Blood. G. C. MATHISON (J. Physiol. 1911 43 347-363).-A simple method for bubbling gases through blood is described. I n the present experi- ments this method was used for observations on the rate of reduction of arterial blood by the passage of a current of nitrogen. The reduc- tion is accelerated by the presence of carbon dioxide and also by lactic acetic formic hydrochloric and sulphuric acids.This effect is mainly due to change in concentration of hydrogen ions but there are indications that this is not the sole factor. Since concentrations of carbon dioxide or lactic acid such as occur in the tissues during deficient oxygenation frequently double the rate a t which arterial blood gives up its oxygen at low oxygen tensions their presence must be an important factor in tissue respiration. W. D. H. The Relative Rates of Oxidation and Reduction of Blood. SOROKU OINUMA (J. Physiol. 1911 43 364-373).-The rate of reduction of blood is greatly increased and that of oxidation somewhat retarded by a rise of temperature. Carbon dioxide not only increases the rate of reduction but retards the rate of oxidation.A t theii. 180 ABSTRACTS OF CHEMICAL PAPERS. temperature and carbon dioxide tensions of the body the curves re- presenting the rate of reduction by a neutral gas (hydrogen) and of oxidation are symmetrical with those produced by a mixture equivalent t o alveolar air. I f the amount of oxygen in this mixture is halved the rate of oxidation is halved also. W. D. H. The E l e c t r o r n e t r i c Method for Measuring the Reaction of the Blood at Body Temperature. KARL ALBERT HASSELRALCII and CHR. LUNDSGAARD (Biochem. Zeitsch. 1912 38 77-91).-Tn the investiga- tions Hasselbalch’s apparatus (Abstr. 1911 ii 182) was employed. The hydrogen-ion concentration at 38.5 under a carbon dioxide tension of 40 mg. mercury was 0.44 x low7. The variations of the hydrogen-ion concentration due t o the respiratory changes of carbon dioxide tension are measurable quantitie$.The results indicate the presence of ‘‘ buffer” substances in the blood t o prevent large changes in the hydrogen-ion concentration a fact which was ascertained by measiiring the variations of this constant iinder different carbon dioxide tensions with different soIul;ions such as the Sorensen’s phosphate mixtures. The importance of the slightly alkaline reaction of the blood in regulating the variations of the hydrogen ion concentration WRS demonstrated by measuring changes when the blood was made slightly acid. The concentration of the whole blood is greater than t h a t of serum and less than that of the corpuscles under the same carbon dioxide tension. It is suggested that for clinical purposes the hydrogen-ion concentration of the blood should be memiired under the mean carbon dioxide tension of the alveolar air.s. B. s. The Nitrogen a n d S u l p h u r C o n t e n t of H u m a n Blood. KENJI KOJO (Zeitsch. phpsiol. Chem. 1912 78 170-172).-Two specimens of blood were obtained from women suffering from uterine operations. In both the percentage of nibrogen was 3.8; that of sulphur was 0.11) in one case and 0.21 in the second. W. D. H. Physiology of Blood Sugar. IV. The Carbohydrates of Red Corpuscles. E. FRANK and A. BRETSCHNEIDER (Zeitsch. physiol. Chem. 1912 76 226-233 Compare Abstr. 1911 ii 301 409).- Washed blood corpuscles yield no dextrose because the dextrose is removed by the process of washing. The fresh red corpuscles of man dog cat and xabbit all contain dextrose in considerable amount.There is also present in both plasma and corpuscles a complex carbo- hydrate of uncertain nature ; it is not fermentable with yeast but after boiling i t with dilute acid a fermentable sugar is obtained from it. W. D. H. The Distribution of Reducing Substances in Blood. IVAR BANG (Biochem. Zeitsch. 1912 38 166-16’7).-1n view of the recent controversies as t o the distribution of sugars in blood the author insists on the fact that the presence of dextrose or other sugars in the corpuscles has not yet been positively demonstrated. S. B. S.PHYSIOLOGICAL CHEMISTRY. ii. 181 Action of Salts on the Coagulation of the Blood. C. GESSARD (Conzpt. re?ad. 191 1 153 1241-1243).-Tho fact that blood from which calcium has been removed by the addition of an oxalate is no longer coagulable has been thought to be due to an inhibitory action of the excess of soluble oxalate.On the other hand i t has been supposed that calcium is essential to the coagulation of blood. I n the author's opinion the former view is the more correct. and experiments are described which support this contention. w. 0. w. The Individual Differences of the Blood Corpuscles. LUDWIG DIENES (Biochem. Zeitsch. 1912 38 159-160).-A reply t o a criticism of Rusznytik (Abstr. 191 1 ii 1108). Substances which Constrict and Dilate the Blood-vessels of the Frog. S. SAMELSON (Arch. exp. Path. Pharrn. 1911 66 347-35 I).-The met hod of Laewen and Trendelenburg was employed. Choline was found to act as a vaso-constrictor and it is thus considered not t o be an antagonist of adrenaline.Substances of t h e digitalin group act in the same way except strophanthin which causes vaso- dilatation. Bile acts as a vnso-dilator but a second dose causes constriction ; the second effect is attributed to some intermediate substance formed from the bile salts. S. B. S. W. D. H. The Influence of Diuretics of the Purine Series on the Permeability of the Blood-vessels. FELIX GAISB~CK (Arch. exp. Path. Phcwn?. 1911 66 387-397).-The same alteration in the water and sodium chloride concentration of the blood is produced by diuretics of the purine group as is produced hy simple bleeding. This holds for normal animals and for thoso from which the kidneys have been removed.It is independent of the previous state of chlorine nutrition. This gives no support to the view that purine derivatives increase the permeability of the blood-veEsels. W. I). H. Total Energy Exchanges of Intact Cold-blooded Animals at Rest. ARCHIBALD V. HILL (J. Physiol. 1911 43 379-394).-The rate of heat production for frogs snakes and newts measured in the author's micro-calorimeter is about 0.5 calorie per hour a t 20° either in oxygen or air. A rise of 10" in frog and snake increases this rate two or three times. If the rate is calculated for 37" i t would he much the same as in man and in other large warm-blooded animals but less than in small warm-blooded animals. I n the newt a rise of 10' only increases the rate 1.5 times ; this may be due to a rudimentary form of heat-regulation.Fasting produces a decline in the rate to a constant value. W. D. H. Enzyme of Saliva which Decomposes Di- and Tri-peptides. ARTHUR II. KOELKER (Zeitsch. physiol. Chem. 191 1 76 27-36).- Experiments on the hydrolysis of alanyl-glycine by saliva from nine different sources gave positive results in every case. The saliva was sometimes slightly acid or slightly alkaline and sometimes neutral. Further experiments with d-alanyl-d-glycine glycyl-l-tyrosine racemiCii. 182 ABSTRACTS OF CHEMICAL PAPERS. leucpl-glycine and racemic glycyl-alanine showed that all these substances except the last are hydrolysed. The tripeptide I-leucyl-gl ycyl-d-alanine yields I-leucine and glycyl- d-alanine. I n this case therefore the action of saliva is identical with that of the erepsin from dogs’ intestines.The Distribution of Enzymes in the Stomach and Intestines of Fish. Osw. POLIMANTI (Biochem. Zeitsch. 191 2 38 114-128),- The following fish were used as subjects of experiment Scylliunz catulus Scyllium cGcrt.icuZc6 Box saZpa Conger vulgaris. The enzymes were extracted from various parts of the mucosa by means of Hamburger’s agar-agar-gelatin cylinders. The pepsin pepsinogen m d chymosin idistribution in the stomach varied in the different varieties of fish but the largest quantities were always found in those parts of the stomach where the food remains longest. Arnylolytic ferments and invertase were never found in the stomachs. The lipase distribution varied in the different fish investigated. Erepsin increases in quantity in the passage from the duodenum towards the rectum.N. H. J. M. S. B. S. The Secretion of Gastric and Pancreatic Juice. SVANTE ARRHENIUS (Medd. K. Vetsnsk. Nobelinst. 2 No I 1-20).-The author discusses the results obtained by Khigine Lobasoff Lonnqvist and London on the influence of various foodstuffs on the rate of digestion and the rates of secretion of the juices and their com- positions in experiments on dogs most of which were carried out by the technique of Pawloff. The main conclusion drawn from the various results is that the mean amount of gastric secretion within a given time (which is less than that of the digestion time) is proportional t o the square-root of the amount of foodstuff. A similar law applies to the relationship between the amount of pancreatic juice secreted and the amount of acid causing the secretion.Phosphoric lactic and acetic acids in this case have a more powerful effect than hydrochloric acid. Similar conclusions can be drawn as to the laws governing the secretion of bile from the limited number of experiments on record. The Biological Importance and Metabolism of Proteina. V. The Metabolism of Young Dogs Fed on Meat and the Products of the Artificial Digestion of Meat. GIUSEPPE BUGLIA (Zeitsch. Biol. 191 1 57 365-396).-The experiments recorded confirm the previous work of others that the cleavage products obtained by digesting meat are of equal metabolic value to the meat itself. The former indeed are more readily absorbed; the urine under these conditions contains a relatively large amount of nitrogen in the form of ammonia and amino-acids.This militates against the view held by some observers that synthesis of protein from its cleavage products occurs in the wall of the intestine. S. B. S. W. D. H. Protein Absorption. 111. OTTO COHNHEIM (Zeitsch. physiol. Chern. 1912 76 293-297).-Experimentp on fishes are described inPHYSIOLOGICAL CHEMISTRY. ii. 183 which the absorption of tyrosine alanine sodium aspartate and glutamic acid was studied. It was found in all cases t h a t a partial splitting off of ammonia took place and it is considered probable that this also occurs in the absorption of customary diets. Experiments on higher animals are contemplated. W. D. H. The Ovarian Factor Concerned in the Recurrence of CEjtrus.F. H. A. MARSHALL (Proc. Physiol. Xoc. 1911 xxi-xxii ; J . Physiol. 43)-In the dog the interstitial cells in the ovary appear to be the source of the internal secretion formed during “heat,” and riot the corpora lutea. W. D. H. The Reduction Ferments. The Presence of a Go-ferment of Perhydridase in Animal Tissues. ALEXIS BACH (Biochem. Zeitsch. 1912 38 154-158).-Animal tissues contain a co-ferment capable of accelerating the reduction of nitrates by milk which is stable on heating is not precipitated by alcohol is easily dialysable and not destroyed when a stream of air is led through the solution. The liver is richest in the co-ferment and then follow the other organs in the following order kidneys spleen brain and lungs. It is suggested that the co-ferment may be an alloxan-like substance which when i t acts on amino-acids produces therefrom aldehydes with scission OF ammonia (Strecker’s reaction).S. B. S. The Chemistry of the Cell Granules. The Composition of the Eosinophile Granules of the Bone-Marrow of the Horse. EUGEN PETRY (\Biochem. Zeitsch. 19 12 38 92-1 12).-The granules from tho bone marrow were prepared by washing it several times with water containing ether and centrifugalising then treating the residue with trypsin as the granules resist digestion by this enzyme. The product thus obtained was examined chemically and found to contain sulphur but no phosphorus and t o behave ‘generally as a protein. I n i t s general properties it appears to behave like elastin and horn. The ash contains relatively large quantities of iron.The iron is not however bound in the form of haematin but appears to exist in a somewhat labile Porm and can be detected by somewhat prolonged action of ordinary reagents for iron and can also be separated from a state of organic combination by trypsin. A method is given by means of which iron-containing granules can be obtained from the blood. A description is given of the microscopic appearances of the granules and the conclusion is drawn that it is probable that these iranules-play an important part in the iron transpirt in the body. S. B. 8. The Duration of Contraction of Plain Muscle. OTTO COHNHEIM and J. VON UEXKULL (Zeitsch. yhpiol. Chem. 1912 76 314-321).-l’he prolonged contraction (tonus) OF plain muscle was studied in various invertebrate animals; i t is accompanied with an increase in oxygen consumption and this is roughly parallel to the amount of work done. Numerical details are given W.D. H.ii. 184 ARH‘I’RACTS OF CHEMICAL PAPERS. The Influence of Calcium on the Action of Muscular Excitation by their Constant Current. EDUARD KAHN (PJiiger’s Amhiv 1911 143. 428-452).-1f calcium is added in excess t o a physio1ogic:tl saline solution the irritability of muscle (frog’s uncurarised sartorius) to the constant current is increased. W. D. H. The Passage of Colostrum into Milk Especially in Relation to Nitrogenous Substances (Cow Sheep Mare). ST. ENGEL and A. DENNEMARK (Zeitsch. phgsiol. Chern. 1913 76 148-158).- The properties of colostrum and its passage into milk are ahont the same in cows which are prirniparn or multipnm.I n the disease of cows known as milk fever the milk may remain in the colostral state for a week. The colostrum of the sheep behaves like that of the cow but the colostral properties are not so marked. The colostrum of the mare is richer in camhogen than the milk. The acidity in all three animals’ colostrum is high. The change in acidity occurs simultaneously with the change in the protein. KENNETH MACKENZIE (Quart. J. exp. Physiol. 1911 4 306-330).-The secretion of inilk is not under the direct influence of the nervous system; neither section nor stimulation of the nerves supplying the mammary gland has any effect on the secretion. Pilocarpine which stimulates and atropine which inhibits secretory nerve-endings have no effect on tbe secretion of milk.The agents which cause activity of the gland or the reveree reach i t by the blood stream. The following organs produce hormones which stimulate the gland to activity pituitary body corpus luteiim pineal body involuting uterus and the lactating gland itself; of these the pituitary (posterior lobe) is the most powerful. Extracts of the bird’s pituitary also contain the galactogogue sub- stance. Hormones which inhibit the mammary secretion are produced by the fmtus and the placenta. The Iron Content of Cow’s Milk. F. EDELSTEIN and F. VON CSONKA (Biochem. Zeitsch. 1915,38 14-22).-The iron was estimated by various methods including the recently published colorimetric method of Lachs and Friedenthal (Abstr. 1911 ii 542). When the milk was collected directly into glass vessels the iron content was found to vary between 0.4 and 0.7 mg.of iron per litre (average 0.6 mg.). The fact that this result is smaller than that recorded by earlier observers is due to the method in which the milk was collected being kept entirely out of contact with metallic vessels. Nevertheless t h e quantity of iron in COW’S milk is only one-third to one-half of that in human milk. S. B. S. A. F. STANLEY KENT (Proc. Physiol. Soc. 19 1 1 ,a xxiv ; J. Physiot. 43)- Certain salts (not mentioned) increase the amount of curd obtainable from a given quantity of milk by the action of rennet. The Passage ofEDrugs i n t o the Sweat. HERMANN TACHAU (Arch. exp. Path. Pharm. 1911 66 334-346).-A great number of W. D. H. Mechanism of Milk Secretion.W. D. H. Influence of Salts on the Action of R e n n e t on Milk. W. D. 11.PHYSIOLOGICAL CHEMISTRY. ii. 185 medicaments (iodine br online boric acid phenol salicylic acid salol antipyrine methylene-blue) are excreted in the sweat. The amount is however extrerriely small ; they pass into other secretions milk bile etc. in larger quantity. The amount however may be sufficient to cause skin eruptions in certain cases. W. D. €3.. Physico-chemical Researches on Animal Liquids. VIII. Chemical Reaction of Urine. G. QUAQLIARIELLO ( A t h R. Accccd. Lincei 1511 [v] 20 ii 659-666).-The author has estimated the phosphoric acid by titration and measured the concentration of the hydrogen ions and the neutralising power in the case of a number of fresh samples of urine from healthy individuals.The concentration of hydrogen ions was determined by means of a hydrogen electrode 0-O1N-hydrochloric acid being the second solution and a solution of potassium chloride being used t o connect i t with the urine. The quantities of alkali and of acid which must be added to t h e urine t o make the concentrations of the hydrogen ions 1 x respectively are called the potential acidity and potential alkalinity of the urine and the sum of the two is the neutralising power The degree of acidity found varies from 82.6 x 10-7 to 2 x gram- equivalents of hydrogen ions per litre. The ratio of the potential acidity to the potential alkalinity bears a relation to the concentrntion of the hydrogen ions. The neutralising power gives an approximate idea of the concentration of tho phosphates arid if the amount of phosphates prebent be known the ratio between the neubralising power of the urine and that calculated for a solutiou of phosphoric acid of the same conceritrirtion as in the urine can be used to estimate the net concentration of the other acids and bases in the urine.The neutralising power of urine is about four times as great as that of a solution of phosphates of the same concentration as in the urine. I t is pointed out t h a t a simple titration of urine is absolutely worthless for the purpose of obtaining information as t o its degree of acidity. On the other hand if the urine is titrated as an acid against phenol- phthalein and as a base against methyl-orange results are obtained which may be taken as a n approximate measure of the ielative concentrations of hydrogen ions in different urines.and 2 x R. V. S. The Excretion of Ammonia in Human Urine by the Adminis- tration of Urea and Sodium Hydrogen Carbonate. N. JANNEY (Zeitsch. physiol. Chern. 1912 76 99-1 35).-The ammonia of human uriue has only one function namely to neutralise acid substances. If by the administration of sodium hydrogen carbonate this is super- fluous the urinary ammonia vanishes alniost completely. A conversion of urea iuto ammonia never occurs in the human body normally. Fifteen grams of sodium hydrogen carbonate in an adult on a mixed diet reduces urinary acidity to nil and lessens the ammonia to one- third. Urea given by the mouth causes increased protein catabolism or the washing out of nitrogen from the body.I n acute catarrhal j tundice true acidosis accompanied by an increase of acid substances in the urine occurs. w. 1). u.ii. 186 ABSTRACTS OF CHEMICAL PAPERS. The Excretion of Quinine by the Dog and a New Method for the Estimation of this Alkaloid. G. GIEMSA (Biochern. Zeitsch. 1912 38 161-163).-A claim for priority with regard to certain results arid methods detcribed by Katz (Abstr. 1911 ii 1013). S. B. S. Certain Concretions in a Cyst of the Mammary Gland in a Horse. ARTHUR SCFIEUNEILT and WALTIIER GRIMMER (Zeitsch. ph?~siol. Chew&. 1912 '76 3'22-329).-The concretious examined contained iu percentages water' 69 ; protein 4-5 ; fat 13.7 ; cholesterol 10 ; lecithin 0.7 and ash 1.7. Casein mas absent and the fat present is not identical with the milk fat or the body fat of the horse but somewhat resembles colostrnl fat in being intermediate between the two.W. D. H. The Chemical Nature of the Substance which Cures Polyneuritis in Birds Induced by a Diet of Polished Rice. CASINIR PUNK (J. Physiot. 19 11 43 395-400).-Polyneuritis in birds 011 a diet of polished rice is due to the lack of a substance which is present in the polishings in minute amount probably not more than 0.1 gram per kilo. of rice. The substance in question is an organic base which is completely precipitated by phosphotungstic acid silver nitrat,e and barium hydroxide. It is partly precipitated by mercuric chloride in alcoholic solution in the presence of choline and is not precipitated by platinum chloride in alcoholic solution.It yields a crystalline nitrate containing C 55.63 H 5-29 N 7.68%; but these figures must be regarded as provisional until a larger yield is obtained. The curative dose for pigeons is very small. W. D. H. The Influence of Intravenous Injections of Pancreatic Extract on Pancreatic Diabetes. ERNEST LYMAN SCOTT (Arne?*. J. Physiol. 1913 29 306-310).-Intravenous injection of pancreatic extract in depancreatised dogs diminishes the glycosuria temporarily. Whether t h i s is due to the internal secretion of the gland or t o a rise of body temperature which occurs is not yet definitely settled. Control experiments with extracts of other organs are in progress. W. L>. H. Metabolism in Experimental Salt Fever. HERMANN FREUND and E. GRAFE (Arch.ezp. Path. Pharrn. 1911,67 55-71).-After the injection of rabbits with isotonic solutions of sodium chloride sugar adrenaline and Ringer's solution fever sets in with rise of tempera- ture and increase of protein catabolism and in this and in other ways the fever produced resembles that due to infection. W. D. H. Infective Methemoglobinemia. ARTHUR E. BOYCOTT (J. Hygiene 1911 11 443-472).-1n rats infection with Gartner's bacillus causes methaemoglobinaemia and sometimes amrnia. The s ame strains do not cause this effect in rabbits mice or guinea pigs W. D. H.PHYSIOLOGICAL CH ERIlBTLtY. ii. 187 The Excretion of Creatine a n d Creatinine Under Pathological Conditions. ISERNHARD VAS (Bioclmn. Zeitscl’. 19 12 38 65-76). -In the two cases of leiicamia investigated no direct relationships between the excretion of creatinine and the purine bases could be ascertained ; there was however a certain pnrallelism between the excretion of creatinine and the total nitrogen. No rise in the creatinine value could be ascertained after treatment by light. I n a case of muscular atrophy (where a limb was kept i n plaster after operative treatment) creatine could be detected in the urine as a consequence of The Serum Reactions (Complement Fixation) of the Meningo- coccus and the Gonococcus. J.A. AHKWRIGHT (J. Hygiene 1911 11 515-530j.-Gonococcus serum and extracts are on the whole more potent than similar preparations from meningococci as regards complement-fixation but no satisfactory distinction betweon the two can be demonstrated.The Physiological Influence of Ozone. LEONARD E. HILL and MARTIN FLACK (Proc. Roy. SOC. 1911 R,84 404-415).-0zone although a deodoriser masks rather than destroys smells. A concen- tration of one part in tt million irritates the respiratory tract ; exposure for two hours to a concentration of 15 to 20 per million is not without risk to life. In concentration even less than one per million i t reduces respiratory metabolism and rapidly causes a fall of body temperature. Its beneficial effect as popularly believed i n is a myth. The irritation of the olfactory nerves may relieve the monotony of close air and in concentrations of more than 1 per million for brief periods may be of therapeutic value by acting in appropriate cases as a sort of “blister” to the respiratory tract.Persistent Radioactivity of the Organism under t h e Influence of Injections of Insoluble Radium Salts. Radium Serotherapy. H. DOBIINICI G. PETIT arid A. JABOIN (Compt. rend. 19 12 154 1509-1 5 1 l).-One mg. of radium sulphate was injected into the venous system of an old horse. For a short time after injection the elimination of radium from the organism was rapid but afterwards became very slow. After a year the blood was still radioactive. Increase in weight was produced after a second injection and the number of red blood-corpuscles was doubled. Preliminary experiments appear to show that the blood serum of animals treated in this way is effective in alternating or arresting pathogenic processes of infectious origin in man and animals and that it tends to raise the resistance to infection w.0. w. muscular atrophy. s. B. s. W. D. H. W. D. H. The Influence of Sulphur and Thiocarbamide on the Excretion of Phenol. KENJI KOJO (Zeitsch. physiol. Chena. 1912 ’76 159-169).-The administration of finely divided sulphur and thio- carbamide raises especially on the second day the total sulphur the ethereal sulpbates and the phenol of the urine. This is probablydue not to increased formation of phenol but because less is oxidised in the body as it combines with sulphuric acid and is excreted. W. D. H.ii. 188 ARSTRACTS OF CHEMICAL PAPERS. The Action of Intravenous Injections of Concentrated Solutions of Salt and Sugar. FRANK P. UNDERHILL (Arch. exp. Path. Phurrn. 19 11 66 407-408).-Polernical against Wilenko who has made certain mistakes in his references to the work of the mesent author in relation to the glycosuria produced by salt solution.w. D. H The Degree of Acidity of Monatomic Alcohols. HERMANN FUHNE~ (Zeitsch. L’ioE. 1912 57 465-494).-1n the homologous series of alcohols starting with methyl alcohol the capillary activity of the individual members stands according to Traube in the relation 1 3 32 . . . (Abstr. 1905 ii 13). As their pharmacological activity on plant-cells blood corpuscles and sea -urchin eggs increase in the same uiarmer it appears that in these cases the action is not dependent on the lipoids present in the cells. Their narcotic action how- ever tested on various aquatic animals is in the relation l 4 42 . . . This is parallel to the increased lipoid content in the central nervous system of such animals and these observations therefore support the Meyer-Overton theory of narcosis.w. D. I€. Influence of Trimethylamine Hydrochloride on Nutritive Exchanges. ALEXANDRE UESGREZ P. REGNIER and It. MOOG (Compi. r e 9 2 4 :1911 153 1238-1241. Compare Abstr. 1902 ii 574)- Injection of trimethylamine hydrochloride dirninish6s the excretion of nitrogen with men and guinea-pigs and lowers the respiratory quotient. I n the case of men suffering from obesity who were given doses of 0.05 gram of the hydrochloride t h e e times a day durktg one to four months loss of weight t o the extent of 1.5-6 kilograms was observed. The author considers t h a t trimethylamine increases the amouri t and activity of internal secretions and is the cause of the physiological action of choline.w. 0. w. Formation of Methyl Propyl Ketone from a-Ethylbutyric Acid in the Animal Organism. Lhox BLUM and MAX KOPPEL (Ber. 191 1 44 3576-3578).-The subcutaneous injection of aqueous sodium a-ethylbutyrate into dogs causes the appearance in the urine not of acetone substances (Blum and Baer Abstr. 1907 ii 285; Embden and Wirth Abstr. 1910 ii 789) but of methyl propyl ketone (identified as the p-nitrophenylhydrazone). Without doubt it is produced from the primarily-formed ethylacetoacetic acid the formation of which is regarded as a strong support of the theory of the oxidation in the animal organism of fatty acids a t the P-carbon atom c. s. The Fate of the Stereoisomerides of Lactic Acid in the Organism of the Normal Rabbit.JAKOB PARNAS (Biocihem. Zeitsch. 1912 38 53-64).-The optically active isomerides of lactic acid behave differently in the organism of the normal rabbit for whereas the dextrorotatory isomeride is non-toxic and is almost entirely burnt in the organism the laevo-isomeride is toxic and is for the most part secreted unchanged in the urine The racemic form is attackedPHYSIOLOGICSL CHEMISTRY. ii. 189 unsymmetrically and an excess of the Isvo-acid is excreted ; in this case however considerably more of the laevo-acid is burnt up in the organism than is the case if this acid be administered by itself. The author gives f u l l details as to the method of isolating the various acids in the lorm of their zinc salts. S. B. S. The Effect of Adrenaline on the Intestine. R.0. HOSKINS (Amer. J. P/~ysioZ. 19 12 29 363-366).-In high dilution adrenaline inhibits peristalsis in isolated segments of rabbit’s intest,ine. I n still higher dilutions these movements are increased. This difference nullifies attempts to estimate adrenaline by its effect on intestinal muscle. W. D. H. The Action of Pilocarpine on the Heart. FELIX GAisBijcK (Arch. exp. Path. PImrm. 19 11 66 398-406).-From expeiiments on frogs and cats tJho conclusion is drawn thab pilocarpine slows the heart by acting on a peripheral mechanism for slowing is produced after the preganglionic fibres of the vagus are completely thrown out of action by nicotine. With certain doses of the drug the result of va,gus stimulation (either of the nerve trunk or of the sinus) or of action of muscarine is lessened or abolished.W D. 13. Effects of Certain Pituitary Extracts. H. CLAUDE and A. EAUDOUIN (Gompt. rend. 1912 154 1513-1515).-The lipoid-free pituitary glands of oxen were extracted with water and the extract treated with alcohol. The precipitate suspended in physiological salt solution partly dissolved giving an active extract X. The alcoholic filtrate gave an extract 2‘. Injections were carried out on men itnd the results found to vary considerably according to the condition of the patient’s glandular system. In general extract S lowered the arterial pressure whilst extract T’ raised it; but in cases of glandular dystrophy the reverse took place. I n norma subjects slight glyco- suria was produced but this was more marked in Easidow’s disease ovarian insufficiency and in acromelagic pluriglandular inadequacy.Extract T’ produces diuresis. w. 0. w. The Influence of Benzene Toluene Xylene and Light and Heavy ‘‘ Benzines” on the Organism. KARL B. LEHNANN RUDOLF WEISSENBERG ADOLF VON w OJCIECHOWSKI LUIG and GUNDERMANN (Arch. Hygiene 1911 75 1-1 19)-A short account of the various products employed under different trade designatious is given together with the modes of preparation and chemical characteristics. Detailed accounts are given also of the cases of poisoning arisiug from the trade use on a large scale of the different products and the conditions under which cases of poisoning are likely to occur together with the results of personal inspection of factories. These investigations supplement a series of detailed laboratory investigations on the toxic effects of the vapours oE the various substances on cats dogs and human beings and the effects of both chronic and acute intoxication were investigated.Lehmmn gives in conclusion the precautions which should be taken to guard against VOL. C ~ I . ii. 13ii. 190 ABSTRACTS OF CHEMICAL PAPERS. poisoning in the technical employment of these substances on a large scale. The methods of experiment were those repeakdly employed by Lehmann and his collaborators on previous occasions. The subjects of experiment were submitted to the action of air containing known quantities of the vapour and the time was noted at which the onset of various symptoms took place. The chief symptoms noted were the falling over of the subject light narcosis and heavy narcosis. In nearly all experiments the results were very regular it being possible to plot the times of onset of syruptoms against the quantities of the various vapours in air and to obtain almost regular curves. A few of the cats employed showed idiosyncracies in that they were susceptible to relatively small doses of benzene. The same idiosyncracies apparently occur in man but they were never met with in the case of dogs. Experiments on chronic poisoning with dogs were carried out Two animals could inhale air containing about 9 mg. of Lhe vapour per litre five to nine hours daily for 23.35 days withouc injurious effects. Cats on the other hand showed symptoms of poisoning after inhaling air with only 5-10 rug. benzene per litre for t h e e hours daily generally on the third to the sixth day. The cheaper trade varieties are only slightly more toxic than the more refined varieties. ‘‘ Benzine ” is decidedly less toxic than benzene. S. B. S. The Toxic Action of Trypsin and its Capacity to Digest Living Tissues. LUDWIG KIRCHHE~M ( A r c l ~ exp. Path. I’harrn. 191 1 66 352-386).-0n subcutaneous injection pancreatic juice and various preparations of the pancreas which contain active trypsin cause local edema and haemorrhages followed by necrosis and digestion of the living tissues. Intravenously injected it kills rabbits with acute and pronounced haemorrhages especially in the lungs. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9120205178

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 190 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Assimilation of Ammonia and Nitrates by the Micro- organisms of Soils. J. VOGEL (Cethtr. Bakt. Pa?.. 1912 ii 32 169-179).-Whilst the production of proteins from ammonia and nitrates takes place in liquid cultures it was not observed in soils even in presence of calcium carbonate which in liquid cultures considerably increases fixation of ammonia. The simultaneous presence in soils of ammonium salts and calcium carbonate may result in considerable losses of nitrogen from nitrates produced from the ammonium salts. As regards denitrification in soils kept i n flasks it is pointed out that the conditions of aeration are very abnormal. Different resultsVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii.'1 91 are obtained when access of air from below and from the sides of the soil is made possihle. Variability in the Gas-forming Power of Intestinal Bacteria. N. J. PENFOLD (J. IZygiene 1911 11 487-502).-The gas-forming powers of organisms of the coZi group varies ; the power may be lost of forming gas from sugars whilst the power of gas formation from alcohols remains; probably two enzymes are concerned. The Indole Reaction and Allied Phenomena. HARALD SEIDELIN and FREDERICK C. LEWIS (J. Hygiene 191 1 11 503-51 4). -Curves are presented of the amount of indole (tested by Seidelin's method) formed by several strains of BcccteTium coZi. Tryptophan does not appear to be always an intermediate product. I n some cases the colour reaction obtained mas purple instead of red; the conditions under which the blue admixture occurs were investigated but its cause is not yet clear.The Chief Phases of the Lactic Acid Fermentation and their Practical Significance. MAX GRIMM (C'entr. Bakt. Pm. 191 1 ii 32 65-70).-The fermentation induced by Bcccterium Zuctis acidi shows four sharply differentiated phases Experiments with pure cultures of this organism at 35' showed that during the first four and a-half hours there is no acid produced but vigorous growth takes place. The second phase then begins and continues for about twelve hours. It is characterised by a gradual increase in the rate of acid production and reaches a maximum a t the fourteenth hour from the time of inoculation. This is followed by a period of decreasing activity and terminates at the thirty-second hour.Although individual organisms may grow slightly after this the power of producing acid is lost and the organisms degenerate. The practical significance of these experiments lies in the fact that such organisms must be transferred to fresh media at the end of sixteen hours if the activity of the cultures is to be maintained. N. H. J. M. W. D. H. W. D. H. H. B. H. The Deoomposition of Asparagine by Bacteria in Pre- senoe of Free Oxygen. I. The Course of the Oxidation Processes. TOR CABLSON (Medd. K. Vetensk. Nobelinst. 2 No. 10 1 -32).-An apparatus is described for measuring the oxygen con- sumption under constant pressure where various strains of bacteria are allowed to grow on a medium which contains asparagine as the source of nitrogen. 'l'he results in the various experiments are plotted with the oxygen consumption as ordinates against the times as abscisse and the results obtained are analysed by Arrhenius.After a certain time there is a bend in the curve which corresponds with the disappearance of the nutrient medium throngh consumption by the organism. If 9 represents the oxygen consumption this after a time reaches a maximum ym. It mas found by Arrhenius that dy/dt = ke-@(y - y)n which on integration and neglecting certain terms gives 13-3ii. 192 ARSTRAC’J’S OF CHEMICAT~ PAPERS. where p2 y1 represent the oxygen cousumptions at intervals t t respectively; ?z was found to be 2/3. This equation was found to hold good in several cases. The vdue q/2*3026 (K) was calculated in the case of several strains of bacteria and was found to vary K x 10-2=6*0 and K x 10-2=15.2. The method of determining pa by interpolation is described.s. B. s. Protein Synthesis in the Lower Plants. KONSTANTIN A. PURIEWITSCH (Biochem. Zeilsch. 1912 38 1-13). -The method of experiment consisted in growing Aspergillus niger in media containiug the necessary mineral salts together with either dextrose succinic malic or tartaric acids and various substances such as amino-acids urea derivatives peptones proteins and amides as sources of nitrogen. The ratio of carbon dioxide evolved to dried mass of Aspergillus formed was estimated when the mould was grown in the presence of the various substances but the conditions of experiments were in other respects similar.If the carbon dioxide evolved is regarded as a measure of the energy consumption during growth it was found that this was smallest when amino-acids mere employed 5s the source of nitrogen ; with ammonium salts aad especially with nitrates the energy consumption during growth was marked larger. The results confirm generally the conclusions of Czapek. S. B. S. Influence of Calcium on the Development and Mineral Composition of Aspergillus niger. (Mlle.) KOBERT (Compt. rend. 1911 153 11’75-1177).-b:xperirnents on Aspergillus niyer grown in nutrient solutions containing definite amounts of calcium sulphate show that small doses of calcium (1-5 mg. per litre) are almost completely absorbed and retained by the organism. The element appears to be without appreciable influence on the development of the plant.w. 0. w. Is Iron Indispensable to the Formation of Conidia of Asper- gillus niger ? MAURICE JAVILLIER and BENJAMIN SAUTON (Compt. rend. 1911 153 1177-1180. Compare Sauton ibid. 151 gal).- From experiments in which definite amounts of zinc sulphate or of ferrous sulphate were added to cultures of Aspevgiltus niyer the authors found that in absence of iron and in presence of zinc no spores were produced by the organism. Sauton was in error therefore in attributing non-sporulation to the absence of iron since zinc is the active inhibiting agent. Iron is indispensable to the growth of the plant but not to sporulation. w. 0. w. The Formation of Fumario Acid by Moulds. FELIX EHRLICH (Ber 1911 44 3737-3742. Compare Ehrlich and Jacobsen Abstr.191 1 ii 520).-Considerable quantities of fumaric acid are formed during the growth of Rhixopus nigricans in natural or artificially- prepared media especially when a certain amount of carbohydrates and nitrogen compounds is present ; the main condition to success is the presence of an excess of dextrose or laevulose the nature of the accompanying nitrogenous food being immaterial. The fumaric acidVEGIC’I’ABLE PHYSIOLOGY AND AGRICULTURE. ii. 193 appears to be an intermediate product in the disruption of the dextrose or l~vulose molecule and these substances cannot be replaced by alcohol or glycerol. Unduly prolonged action of the mould causes the fumaric acid itself to be attacked. A few characteristic experiments are described in detail.D. F. T. Amylomyces Rouxii. R. GOUPIL (Conzpt. Tend. 1911 153 1172-1 174).-This mould brings about a formation of succinic acid when grown in a dilute sucrose solution corresponding with about 6% of the sugar destroyed Acetic and butyric acids are also formed in small quantity but not oxalic or lactic acid as has been stated by other observers. The production of succinic acid i q favoured by free aeration and becomes negligible if air is excluded. Similar results have been obtained when the organism is grown in solutions of maltose dextrose invert sugar or starch hydrolysed by malt extract. w. 0. w. Behaviour of Yeast Enzymes Free and .Attached to Proto- plasm. HANS EULER (Arkiv. Clwm. Min. Geol. 1911 4 No. 13 1- 1 I).-Attention is called to the differences between zymase maltase and invertase of brewers’ yeast and also t o Monilicc invertase.In the living cell with the exception of yeast invertase the action of the enzymes is checked by antiseptics and greatly retarded by drying ; they cannot he extracted from the cell by water. Yeast invertase only loses half its activity when dried. From dry yeast invertase is almost completely extrwted by water ; zymase and rnaltase are only partly extracted. Invertase is not asected by antiseptics; it is regarded as already split off from the protoplasm in the living cell. The other enzymes are only broken off from the protoplasm on drying or by mechanical means. ikfo?zi&x invertase behaves like mdtase and zymase and is bound up in the protoplasm. Monilia yeast ferments dextrose more quickly than sucrose and maltose more slowly still.E. F. A. Puriflcation of Water by Infusoria. C. S. STOKVIS and N. H. SWELLENGREBEL (J. Hygiene 191 1 11 481-486).-Infusorin only play a part in purifying river water if the temperature is between loo and 30° if the aquatic vegetation is rich enough to supply the necessary amount of oxygen and if the water is not highly polluted by adjoining factories. w. D. II. Atmolysis and an Atmolyser. RAPHA~L DUBOIS (Compt. i*end. 191 1 153 1180-1 183. Compare Abstr. 1884 932).-A note recalling the author’s earlier observations on the aqtion of vapours on vegetable organisms. The paper contains an illustration of the appa,ratus employed. w. 0. w. Transpiration i n Oil-producing Plants ; Influence of Light. LECLERC DU SABLON (Compt.rend. 191 1 153 1236- 1238).-Inii. 194 ABSTRACTS OF CHEMICAL PAPERS. general direct sunlight has a much greater effect in increasing the transpiration of plants than diffused daylight. This is due partly to the effect of a higher temperature and partly to an increased permeability of the protoplasmic membrane. The second cause is unimportant in the case of oil-producing plants which flourish in dry climates and which have been found to behave towards diffused light i n the same way as non-oily plants but to lose water less readily then t.hese when exposed to direct sunlight. The experiments were conducted on Euphorbia Sempervivum Crassula and others. w. 0. w. Metabolism in Ripening Seeds. W. ZALESKI (Bied. Zentr. 1911 40 863; from Bot. Centr. 1911 117 57).-Unripe seeds of Pisum and Zea Muys which were kept for several days in air saturated with moisture showed an increase in the amounts of proteins and a decrease in amides amino-acids and bases.Whilst during germination proteins are broken down with produc- tion of amino-acids the reverse process takes place during ripening. Proteaseq which are supposed to bring about the reversible action were found in ripening pea seeds. Rennin was found in unripe seeds. N. H. J. M. Formation of Hydrogen Cyanide i n the Germination of Seeds. CIRO RAVENNA and C. VECCHI (Atti I<. Accad. Lincei 1911 [v] 20 ii 491-495. Compare Ravenna and Zamorani Abstr. 1910 ii 1099). -When the seeds of ,%sum. usitatissimwm or those of Sorghum szclgare germinate in the presence of ammonium chloride the amount of hydrogen cyanide liberated is considerably greater than when they germinate in the absence of this salt.Experiments with the seeds of Sorghum vulgare show that ammonia is present in the seeds from the beginning of germination but hydrogen cyanide appears only when the plants have attained to a certain development. These results support the view that the hydrogen cyanide is formed synthetically from non-nitrogenous substances and ammonia. A comparison of the amounts of hydrogen cyanide formed when germination takes place in the presence of (1) water (2) ammonium chloride (0*1%) (3) dextrose (0.2%) (4) ammonium chloride (0.1%) and dextrose (0.2%) shows that the greatest amount is formed in the presence of both dextrose and ammonium chloride.R. V. S. Origin and Function of Calcium Oxalate in Plants. IOANNES POLITIS ( A t t i B. Accad. Lincei 1911 [v] 20 ii 528-!534).-The author discusses the hypotheses which have been put forward on this subject and calls attention to the connexion between the deposition of calcium oxalate raphides and the occurrence of glycogen and amyloids which has been established by his recent work (compare this vol. ii 83). He is of opinion that the oxalic acid is formed in the cells by oxidation of these substances. R. V. S. Micro- and Macro-chemical Detection of Carrotene. M. TSVETT (Rer. Deut. bot. Ges. 1911 29 630-636)-The authorVEGETABLE eHYsIoLmY AND AGRICULTURE. ii. 19.5 examines in some detail three micro-chemical teats commonly employed for carrotene namely Moiisch's potash test Frank and Tschirch's acid test and his own resorcinol test and concludes t h a t none of them is trustworthy.Nor could any simple macro-chemical test be devised. The only safe method is actually to isolate the cnrrotene and as this has not generally been done i t follows that many of the state men& about the distribut'ion of carrotene need revision. E. J. R. The Carbon-like Substance Occurring in Compositae. FRANZ W. DAFERT and R. MIKLAUZ (Delnhchr. Zath-Naturw. Klasse K. Akad. IViiss. Wien 1911 87 143-152).-An account of the isolation of deep brown or black substances which the author designates " phyto- rnelanes," from the so-called '' Kohleschicht " of the heads of certain plants of the natural order Compositae. The amounts (varying from 0-7-3.8%) obtained from different members of the order are stated whilst analysis indicates t h a t the chemical composition of phytomelnne also varies in different species (C 67-76% H 3.3-4.7% 0 20-28%).The substances are very indifferent to chemical reagents. They are probably formed from cellulose by retrogressive metamorphosis (@A 00 - YH,O)* F. M. G. M. Retrogression of the Active Substance in Medicinal Plants by the Action of Enzymes. PIO LAMI (BoZZ. Chirn. Tarm. 1911 50 S35-842).-1n order to enable medicinal plants to be kept unchanged it is proposed that the substance sbould be heated at about 80" in the vapour of ethyl alcohol or a t 73" in methyl alcohol vapour and then dried in a current of warm air. N. H. J. M. Vegetable Phosphatides. VLADIMI~ NJEGOVAN (Zeitsch.pAysioZ. Chern. 1911 76 1-26. Compare Hiestand ibid. 1907 54 287; Winterstein and Stegmann ibid. 1908-9 58 501).-The phosphat- ides of the seeds of Lupinus dbus which dissolved in alcohol were separated by means of different solvents into phosphatides and non- phosphatides. The three substames A B C which may be considered t o be phosphatides all yield stearic palmitic and unsaturated fatty acids as cleavage products. A and C yielded glycerol-phosphoric acid and C free phosphoric acid. As regards bases choline was obtained from B and from C a base C9H2&N2 to which the name vidine is given. The latter compound is perhaps identical with Lucius's hexamethyltrimethylenediammonium (Abstr. 1907 i 678). The platinichloride m. p. 250-252" and the aurichloride m.p. 269-272* were prepared. N. H. J. M. Chemistry of the Higher Fungi. VII. Hypholoma fascicu- lare. JULIUS ZELLNER (Monatsh. 1911 32 1057-1063. Clompare Abstr. 1909 ii 922).-A renewed investigation of Hppholoma fasciculccra which contains 9.25% of dry matter shows the presence of the following constituents some of which have been previously identified by others a cerebroside an ergosterol solid and liquid fatty acids glycerol lecithin a resin mannitol trehalose dextrose tannin phloba- phen choline a gum a carbohydrate soluble in alcohol chitin,ii. 196 ABSTRACTS OF CHEMICAL PAL'EKS. protein and enzymes which hydrolyse protein stmarch maltose and glucoaides. E. F. A . Chemistry of the Higher Fungi. VIII. Wheat Rust. (Tilletia levk and.T. tritici.) JULIUS ZELLNER (Monatsh. 191 1 32 1065-1074).-The analyses are based on the investigation of considerable quantities of wheat rust spores separated mechanically from badly infected wheat. The following substances have been identified liquid and solid fatty acids a wax a n ergosterol- like compoiind glycerol a resin a substance insoluble in alcohol mannitol trehalose dextrose a base carbohydrates soluble in water and in alkali protein invertasa lipase and a chitin skeletal substance. I n general these constituents are the same a s those of maize rust but the differences are so marked that they would serve for the differentia- tion of the spores of the two species if this had been impossible inorp hologically. E. F. A. Application of the Biological Method to Kalmia latifolia and Preparation of a Glucoside.EMILE BOURQUELOT and (Mlle.) A. FICRTENHOLZ (Compt. vend. 1912 154 1500-1502 ; J. Ph,ctrrn. Chim. 1912 [vii] 5 49-5b).-The fresh leaves of Kalmia latifolia R plant of the rhododendron family contain sucrose and a gliicoside hydrolysable by emulsin. The latter has been isolated by extraction with boiling 90% alcohol from which it separates in slender needles m. p. about 150° having a chalky taste becoming sweet and then bitter. A solution in 50% alcohol has [a] -59.1'. Ferric chloride produces an intense red coloration. The substance gives dextrose on hydrolysis and in i t s general properties resembles asebotin from Andromeda japonica. w. 0. w. Oils from Different Varieties of Oil-Palm. ALEX ANDRE HEBERT (Bull.Xoc. chim. 19 11 [iv] 9 1083-1 085).-Chevalier has classified the West African oil palms recently into two sub-species Elaeis nigrescens and E. uirescens. each with a number of varieties (Documents sur Ze palmier d huile Paris. Challamel 1910). The author has determined the yield and character of the palm oils yielded by the fruits of these varieties. The yields may vary f r m 41% to 63yA calculated on the pericarp alone or from 16 to 56 calculated on the whole fruit the highest yields being afforded by E. uigvescens var. Pisifera and B. virescens var. Gracilinux in which the n u t is reduced t o a mass of interlacing fibres. The palm oils obtained from the varieties examined differ but little from commercial palm oil (compare Bull. Imp. Inst. 1909 7 357). T.A. H. Rumex obtusifolius Roots. ALEXANDER TSCHIRCH and F. WEIL (Arch. Fharnz. 1912 250 20-33. Compare Hesse Abstr. 1900 i 4 l).-A concentrated alcoholic extract of the roots on distillation yielded a small amount of volatile oil having an odaur of butyric or valeric acid The extract on dilution with water gave (1) a resinous precipitate from which ether extracted a brown residue which probably contained emodin and chrysophanic acid and (2) a liquidVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 1!)7 which did not reduce Fehling's solution but which after boiling with dilute sulphuric acid exhibited this property and contained a precipi- tate from which emodin and clirysophanic acid were isolated; the chrysophanic acid was probably accompanied by emodin methyl ether since it furnished methyl iodide when heated with hydriodic acid.It is probable that emodin methyl ether is the source of the varying quantities of methyl iodide yielded in this reaction by the crude chrysophanic acid examined by various investigators. The liquid after hydrolysis contained in addition Zapnthic acid C,,H,O m. p. 228-229" pale yellow prismatic crystals tannin and reducing sugar ?robably formed by hydrolysis of glucosides of emodin and chrysophanic acid. The ash from the roots contained the equivalent of 0.379% of iron. The dry roots of Rumex a4pinus furnished 13% of sucrose. The Amounts of Hydrogen Cyanide Produced by Different Varieties of Sorghum. JOHANNES SCHRODER and HANS DAMMANN (Chem. Zeit. 191 1 35 1436-1437).-Cases having been observed by the authors (who are working in Xonte Video) of cattle poisoning by sorghum.a number of tests were carried out during the summer season Nov. 1908 to March 1909 to ascertain what quantities of hydrogen cyanide are present in the different varieties of this plant. The highest amounts recorded were about 0.04% in young plants growing on maniired plots ; the amount fell later on t o 0.004%. On nnmanured plots i t was always somewhat lower. Under the con- d I tions ohtaining in the experiments Andropogon sorghum saccharatunz contained more than either the vulgaris or halepensis variety. T. A. H. E. J. R. Respiration of Barley during Germination Especially its Dependence on the Amount of Protein. B. ABRAHAMSOHN (%flied. Zentr. 1911 40 862-863 ; from Diss. Berlin 1910 and Bot.C'entr. 1911 11'7 53).-In the germination of sterilised barley the production of carbon dioxide is less than in seeds which are not sterilised. Small seeds show a more intense respiration than large ones. Comparing seeds with high and low amounts of protein it is shown that respiration is greater in the case of seeds with high percentage of protein. The difference is at first only slight but i t increases as germination proceeds. This is explained on the assumption that the amount of enzyme is only small in ripe seeds and that it increases during germination at a greater rate i n seeds rich in proteins than when proteins are less abundaDt. The Action of Oxygen on the Alcoholic Fermentation of Peas. LEONID IWANOFF (Rer. Deut. hot. Ges. 1911 29 622-629)- The author states that peas contain n zymase similar in many respects to that of yeast but differing in its necessity for oxygen.I t s activity was measured by the rate of evolution oi carbon dioxide and was found to be increased to a marked extent by addition of sodium phosphate and also by the presence of oxygen. N. H. J. M. E. J. It.ii. 198 ABSTRACTS OF CHEMICAL PAPERS. Soluble Substances in the Plasma of Potato Tubers. GUSTAVE ANDR~ (Compt. rend. 191 1 153 1234-1236).-The amount of nitrogen phosphoric acid and potassium existing in the state of simple aqueous solution in potatoes has been determined by immersing the tubers in ether and analysing the aqueous liquid displaced by the ether. In the case of potatoes gathered in March this was found to contain 17.96% of the total nitrogen 19.98% of the phosphoric acid and 27.86% of the potassium.The proportions were smaller in the case of potatoes collected a t maturity. The amount of potassium is considerably more than sufficient to neutralise the phosphoric acid and probabiy corresponds with the existence of soluble organic salts. w. 0. w. Displacement by Water of Soluble Substances in the Plasma of Potato Tubers. GUSTAVE ANDRB (Compt. rend. 1912 154 1497-1500. Compare preceding abstract).-An account of further experiments similar to those already described. When allowed to remain for thirty-three days in water containing formaldehyde potatoes part with only 24.02% of their total nitrogen whereas in tlhe same time 49.79% of the potassium is lost. A preliminary heating for three hours at 120' considerably increases the proportion of potassium subsequently lost by exosmosis whilst it has no effect on the loss of nitrogen.This is probably due to partial hydrolysis of the proteins Changes io the So-called Physical Properties of Soil by Frost Heat and Addition of Salts. WILLY CZERMAK (Lalzdw. Versuchs-Stat. 1912 76 74-1 16).-Frost heat and electrolytes cause a diminution of the soil surface by coagulating the colloids. The soil colloids coagulated by cold absorb to some extent the dissolved nutrients of the soil including nitrogen. Sterilisation by heat increases the solubility of the soil nitrogen. The Distinctive Action of Calcium and Magnesium Oxides in Soils on Higher Plants and Micro-organisms. OTTO LEMMERMANN ALBERT EINECKE and H.PISCHER (Landw. Jahrb. 191 1 40 174-254).-The account of a comprehensive study extending over a period of several years on the result of varying the ratio of calcium and magnesium oxides in soil with an account of its effect 011 plantJs and 02 the bacterial properties and fertility of soil. accompanied by elimination of phosphoric acid. w. 0. w. N. H. J. M. F. M. G. M. The Results of Deficiency of Lime in Field Soils and its Influence on Vegetation. OTTO LEMMERMANN OTTO FOERSTER and ALBERT EINECKE (Lamdur. Jahb. 191 1,40,255-324).-An account of experiments showing the results of lack of lime (in soil) on numerous crops with a discussion on the employment of different extracting reagents in soil analysis and their relative value as indicating the available plant food present.JULIUS STOKLASA (Chem. Z e d . 191 1 35 1425-1427).-B~ological absorption differs from purely F. M. G. M. Biological Absorption in Soils.ANALYTICAL CHEMISTRY. ii. I09 chemical Rbsorption in that all the elements required for growth are taken up and transformed into organic compounds. Experiments in which definite quantities of a solution of monocalcium phosphate were allowed to percolate for twenty-five days through various sterilised and non-sterilised soils showed that appreciable quantities of phos- phates had been absorbed. The amount absorbed was always greater in the non-sterilised soils and varied with the fertility. This is attributed to the action of bacteria and it is claimed that the absorption is a measure of fertility. Similar resnlts mere obtaiued with potassium and ammonium salts and with nitrates. H. 8. H. Amount and Composition of Drainage- Water Collected during the Years 1909-10 and 1910-11. BRYCE U. BURT (Rep. Cawmpore Agric. Stat. for the years ending June 30 1910 and 1911. Compare Abstr. 1909 ii 1049)-In 1909-10 two of the gauges (Nos. 1 and 4) were sown with juar and in 1910-11 with maize after which fifty gallons of water (= 2-21 inches) were added. The amounts of rain and drainage and of nitrogen as nitrates in the drainage from June to May were as follows 1909-1910. 1910-1911. Depth r of soil Rainfall Drainage N per acre Rainfall Drainage N per acre. h 7 r A \ No. inches. inches. inches. lbs. inches. inches. lbs. 1. 72 36-67 12.78 19.85 25'63 4.40 1 '50 2. 72 36'67 16.01 47.15 25'63 7.17 23-30 3. 36 36-67 15.23 36-75 25'63 7.87 34-36 4. 36 36'67 15.75 23-71 25.63 6'05 1 -00 The yields of juar in 1909 amounted to (1) 6945 and (4) 3487 lb. per acre N. €3. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9120205190

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. ii. I09 Quantitative Treatment of Small Quantities of Precipitate. JULIUS DONAU (MonatsJh. 191 1 32 11 15-1 239. Compare Abstr. 191 1 ii 225).-Improvements are described i n the Nernst micro- balance and in the filtering crucible in which the asbestos fibre is now replaced by spongy platinum. The technique of preparing the filter precipitation and filtration is described in detail. The full experi- mental results are given for the determination of twenty-six inorganic metals or acids made by the usual mothods but using only a few milli- grams of substance. The accuracy of tibe method appears to be satisfactory. E. F. A. Qualitative Analysis of Complex Mixtures by Boiling with Sodium Carbonate. A. A. IWANOFF (J. Russ. Pilys. Chem. SOC.191 1 43 1258-1261).-For the qualitative analysis of complexii. 200 ABSTRACTS OF CHEMICAL PAPERS. mixtures of salts the author recommends the preliminary separation of the acids and bases in the following mamner. q'he mixture is first treated with sufficient saturated sodium carbonate solution t o cause complete precipitation a certain amount of the solid carbonate being tben added to keep the solution saturated. The mixture is then boiled for a greater or less time according t o its amount; this is best effected by means of a current of steam which prevents bumping and ensures thorough mixing. It is advantageous to suspend the boiling two or three times and to filter off' the precipitate which is then again treated as above. After the final filtration the filtrate is acidified w i t h nitric acid the excess of which is neutralised with ammonia solution the excess of the latter being expelled by boiling.The precipitate thus formed is added t o that previously obtained. This procedrire leads to almost complete separation of the acids and bases; the precipitate contains all the metals and the silicic acid whilst the solution contains a small pro- portion of the silicic acid arid the whole of the other acids. The in3oluble residue containing AgC1 PbCI Hg and H,SiO is analysed without fusion with potassium and sodium carbonates there being no metals of the second group present. If the mixtures contain no tin the presence of metallic mercury in the insoluble residue indicates the occurrence of univalent mercury in the mixture the mercurous carbonate formed readily decomposing into carbon dioxide mercuric oxide and mercury.The metals being obtained in the form of carbonates readily soluble in hydrochloric acid the use of nitric acid and consequent oxidation of the hydrogen sulphide are avoided. App1ic;ition of the method to various mixtures gave good results. T. H. P. Laboratory Apparatus for Estimating the Absolute and Full Water-holding Capacity of Soils. FR. MARSHALL (Landw. VersucldYtat. 1912 '76 125-1 34).-The apparatus of which sketches are given consists of (a) a U-tube of which the one arm terminates in a bulb and (6) a graduated 100 C.C. cyliuder for holding the soil the lower end of which is closed by wire gauze covered with a paper filter. When in use the lower end of the soil cylinder is inserted in the bulb of the U-tube which is filled with water.For soils which take u p large amounts of water both arms of the U-tube have bulbs so t h a t the soil can be left overnight. The processes employed for the different estimations are described. N. H. J. M. Fluorescein as an Indicator of Bromine. HENRI BAUBIGNY (Bull. Soc. chim. 1912 [iv] 11 12-17. Compare Abstr. 1898 ii 13S).-Polemical. A reply to Pribram (Abstr. 1907 ii 111). The author also criticises Labat's modificixtion of his method (Abatr. 1911 ii 533) and maintains the correctness of his view as t o the method of employing the test with a paper soaked in a strong solution of fluorescein. W. G.lodometric Method for the Quantitative h t i m a t i m of Small Quantities of Selenium in Sulphur and Pyrites.PEma KLASON and HJALMAR MELLQUIST ( A ~ k i w Kern. Min. Geol. 1911 4 No. 18 l-l4).-The authors first show that selenium when in the form of the dioxide may be accurately estimated by making use of the reaction SeO -I- 4HI = Se + 2H,O i- 21,. The dioxide is dissolved in water in a flask the solution diluted to 100-300 c.c. and then 2-10 drops of hydrochloric acid (U= 1.19) added. The flask and its contents are then heated on the water-bath the air replaced by carbon dioxide and 2-5 grams of potassium iodide added. After well corking the flask it is shaken to dissolve the iodide cooled and then kept in the dark for one hour. The liberated iodine is then titrilted with standard thiosulphate. Great care must be taken t h a t the hydrochloric acid used is free from chlorine and that the potassium iodide contains no iodate.I n contradiction to the statements of other investigators tho authors find that selenic acid is not reduced by hydriodic acid. The thiosulphate method (Norris and Fay Abstr. 1897 ii 70; 1900 ii 272) for the estimation of selenious acid is not so accurate as the iodometric method; the results &re always low and the error increases with increasing weight of selenium. For the conversion of selenium into the dioxide the authors find that the best method is to burn it in a current of oxygen. The selenium is conta,ined in a porcelain boat situated between two asbestos plugs in a hard glass tube. The selenium dioxide is repeatedly sublimed backwards and forwards between the two plugs until it is quite white after which it is dissolved out with water and estimated as above.Experiments showed that no selenium is lost in these operations. If the selenium is present as a suspension in water it may be filtered on to one of the asbestos plugs using a tube similar t o fhat used in sugar analyses. For the estimation of selenium in sulphur the sulphur is burned iu r?. similar manner to that described above. The selenium dioxide so produced is then dissolved from the asbestos and tube by means of a warm solution of potassium cyanide and the selenium precipitated froin this solution by means of hydrochloric acid and sulphur dioxide The precipitated selenium is then collected on an asbestos-plug as described above converted into the dioxide again which is then dissolved in water and estimated iodometrically.Various specimens of Japanese sulphur contained 1 *1-20*3 grams of selenium per ton whilst a specimen of Sicilian sulphur contained 0.9 gram of selenium per ton. Eor the estimation of selenium in pyrites 20-30 grams are dis- solved in concentrated hydrochloric acid (D = 1-19> and potassium chlorate. After filtering from the gangue the iron is reduced to the ferrous state by means of zinc more hydrochloric acid added the solution boiled and the selenium precipitated with stannous chloride. Since the selenium may contain arsenic it is collected on an asbestos filter dissolved in potassium cyanide and then again precipitated with hydrochloric acid and sulphur dioxide. The further treatment is similar to that described for the estimation of selenium in aulphur,ii.202 ABSTRACTS OF CHEMICAL PAPERS. 89*5-90.1 Grams of selenium per ton were found in some specimeas of Falu pyrites. Simply roasting the pyrites in a current of oxygen does not convert all the selenium into oxide. T. S. P. Kjeldahl’s Method [of Nitrogen Estimation 1. MAX SIEQFRIED and 0. WEIDENRAUPT (Xeitsch. physiol. Clmn. 19 12 76 238-240).- According to Andersen and to Kjeldahl when permanganate has been added to the oxidation mixture in a Kjeldnhl estimation the liquid should not be subsequently boiled otherwise loss of ammonia may take place. Experiments are now quoted to show that further heating causes no such loss of ammonia even when heating is prolonged for two or three hours after the last addition of permanganate; in some instances namely the oxidation of tryptophan the heating is essential.E. F. A. Detection of White Phosphorus in Presence of Hypophos- phites and Arsenic. ANDRE LECL~BE (J. Phacrm. Chim. 1912 [vii] 5 15-18).-The method depends on the fact that hydrogen liberated from aluminium and potassium hydroxide solution in presence of phosphorus forms phosphorus hydride which blackens paper coated with ammoniacal silver nitrate. Hypophosphites are not reduced under these conditions and the formation of hydrogen arsenide is prevented by adding a small quantity of sodium persulphate to the solution. One part of phosphorus in 10,000 may be detected in this way. The liquid may be used for the detection of arsenic by oxidising it with nitric acid then reducing the arsenate formed by means of sulphur dioxide boiling off the excess of the latter and applying the test without adding persulphate.T. A. H. Separation of Phosphomolybdates from Silicomolybdates PETR G. MELIKOFF (Compt. isend. 1912 154 1478-1479).- Ammonium moly bdate is liable to precipitate silicomolybdates in the estimation of phosphates in minerals. To avoid this difficulty the use of hydrogen peroxide is recommended since this converts the silico- molybdates into permolybdates which are insoluble in hydrogen peroxide whilst the phosphomolybdates go into solution. The precipitate obtained with ammonium molybdate is digested with a mixture of equal volumes of hydrogen peroxide (30%) and an 8% solution of ammonium molybdate in nitric acid.In micro-chemical analysis the precipitate may be treated with a few drops of 30% hydrogen peroxide and allowed to remain for twenty-four hours when solution of the silicomolybdate is complete. w. 0. w. Gravimetric Estimation of Phosphorus in Milk. E. ROLL MILLER (Analyst 1911 38 579-583).-Estimations of phosphoric acid in numerous samples of milk ash were made the following processes being used (1) Precipitating as ammonium magnesium phosphate after removal of the lime as oxalate ; (2) precipitating as ammonium magneaium phosphate in the presence of lime the latterANALYTlCAL CHEMISTRY. ii. 203 beiug held i n solution by the addition of ammonium citrate; (3) pre- cipi tating as ammonium phosp tiomolybdate dissolving arid re-precipi - tating as ammonium magnesium phosphate.I n every case the precipitate was ignited and weighed as magnesium pyrophosphate. The phosphorus in the milk was also estimated in the dry milk solids by Carius’ process. Provided t h a t the ash was heated previously with nitric acid the results obtained by the first three methods agreed closely with those yielded by Carius’ method the difference being about 0.01%. In the case of condensed milk and milk-powder this difference was larger and it is evident that Carius’ method should be employed for the ebtimation of phosphorus in these products. The results obtained show that there is no appreciable loss of phosphorus during the incineration of milk (compare Abstr. 1911 ii 438). w. P. 8. The Estimation of Arsenic in Organic Substances especially Organic Arsenic Gompounds (Salvarsan etc.).PAUL BOHRISCH and F. KURSCHNER (Pharm. Zentr.-h. 191 1 52 1365-1371 1397-1400).-The distillation of organic materials with hydrochloric acid in presence of hydrazine and potassium bromide (Jannasch arid Seidel Abstr. 1910 ii 546) followed by titration with iodine (Ney Abstr. 1911 ii 932) gives the best results when slightly modified. It is inapplicable to metallic arsenic and arsenious sulphide which are incompletely converted into the chloride by hydrochloric acid. Satisfactory results are obtained from atoxyl aud salvarsan or from milk or urine containing these compounds. Prom 50 to 75 C.C. of the liquid to be examined are distilled with 100 C.C. of fuming hydrochloric acid 4 grams of hydrazine sulphate and 2 grams of potassium bromide the receiver containing 75 to 100 C.C.of water. about one hour is required for t*he distillation which is carried almost t o dryness. The distillate is neutralised with concen- trated sodium hydroxide and titrated with N/lO-iodine after adding 3 grams of sodium hydrogen carbouate. C. H. D. Estimation of Arsenic as Ammonium Arsenomolybdate. HENHI PELLET (Anal. Chirn. anal. 1911 16 455-456).-8 reply to Maderna (Abstr. 1910 ii 896) who states that the relation between arsenic trioxide and molybdic acid is as 1 24 whereas Champion and the author found the relation 1 21%. The difference which is not very appreciable is 110 doubt caused by a different method of working. L. DE K. Rapid Estimation of Carbon Monoxide. LEONARD A.LEVY ( J . SOC. Chem. I72d. 1911 30 1437-1440).-The process which is based on Gautier’s iodic anhydride method is briefly as follows The gaseous mixture is drawn by meam of an aspirator through a solution of bromine in potassium bromide to fix unsaturated hydrocarbons and then through aqueous potassium hydroxide (1 1) to remove bromine vapours and also any carbon dioxide. After removing aqueous vapours by passing the gas over phosphoric oxide the carbon monoxide is oxidised to carbon dioxide by passing it through a U-tubeii. 204 ARSTRACTS OF CHEMICAL PABERS filled with a mixture of asbestos and iodic anhydride and heated in a n air-bath at 160-180°; to the U-tube is sealed anothey one filled with copper ttirnings which completely absorb the iodine liberated.The carbon dioxide is now absorbed in a specially constructed apparatus resembling a Winkler coil in a known volume of standard solution of barium hydroxide coloured with phenolphthalein and the operation is continued until the liquid is decolorised ; a simple calculation then gives the carbon monoxide. When the amount of carhon monoxide is but very srr1a11 the excess of bar@ may be titrated with oxalic acid after a certain volume of the ,ails has passed through without waitiug for complete decolorisation. L. DE K. Estimation of Hydrated Silicic Acid in Clay. FORREST K. PENCE (Yruns. Amer. Ceram. Xoc. 1910 12 49-53).-A discussion of various methods employed in estimating hydrated silica i n clays with an account of experiments for the purpose of finding a chezper reagent than methylamine or diethylamine and n more accurate one than the 10% sodium hydroxide employed by von Piedzicki and considered valueless by the author.The prepmation of a prire hydrated silicic acid is described a known amount of which wa4 evaporated to dryness a t 45Owith a prepared kaolin previously freed from silicic acid and attempts then made to again separate this ingredient by means of different concentrations of sodium carbonate. The following procedure gave results accurate to within 0.1 -03%. Five grams of the prepared kaolin containing 0,1765 gram Si02 are boiled in a platinum basin for ten minutes over a free flame with 120 C.C. of a 5% solution of sodium carbonate the basin being kept in motion to prevent bumping ; the solution is decanted through a filter paper and the treatment with sodium carbonate repeated twice the are-idue transferred to the filter paper and washed with hot dilute sodium carbonate ; the whole of the silica is recovered subsequently from the liquid by known methods.The author suggests the advisability of determining the solubility of quartz mica and felspar in sodium carbonate when in a finely divided condition but from experiments with a flint fire clay u stratified kaolin and a red-burning clay he considers that the solubility is not sufficiect to introduce a serious error. . F. M. G. M. Variation of the Cathode Potential during Electrolysis. P. ERCULISSE (BuIZ. Xoc. chim. Be@ 1911 25 427-436).-A theoretical paper in which the author criticises the theory put forward by Fischer (ElectroanccZytische SchneZLmethoden Stuttgart) as to the variation of the cathode potential and its application to quantitative analysis by electrolytic methods.W. G. Estimation of Small Amounts of Potassium. EILHARD A. MITSCHEHLICH K. CELICHOWSKI and HEHMANN FISCHER (Land w. Versuchs-Stat. 1912 76 139-155).-In estimating potassium in soils 250 C.C. of soil extract with about 5 C.C. of strong nitric acid andANALYTICAL CHEMISTRY ii. 205 5 drops of sulphuric acid (I 3) are evaporated until about 20 C.C. remains transferred to a platinum or quartz glass dish evaporated to dryness and ignited. The residue is treated with a drop of a concen- trated solution of sodium carbonate and a few C.C. of warm water and again evaporated t,o dryness and heated until the carbonate melts.It is then approximately neutralised with dilute nitric mid evaporated to dryness dissolved in about 5 C.C. of hot water treated with 3 C.C. of 10% cobalt chloride solution and 5 C.C. of 10% sodium nitrite solution and slowly evaporated to dryness a t 80-90° care being taken to avoid the formation of crusts. The cold residue is then rubbed with 3 C.C. of 10% acetic acid to dissolve the excess of sodium cobaltinitrite diluted with 10 C.C. of water and filtered through hardened filter paper in a Gooch crucible. The dish and crucible are washed with the smallest possible amount of 2.5% sodium sulphate solution. The crucible and precipitate are next added t o a nearly boiling mixture of water (100 c.c.) and N/5O-potassium permanganate (about 20 c.c.).After separation of the manganese dioxide about 2.5 C.C. of dilute sulphuric acid are added drop by drop. The beaker is then removed from the water-bath the contents treated with an excess of Nl50-oxalic acid and titrated back with iV/50- permanganate 1 C.C. oh which corresponds with 0.1571 mg. K,O. ' N. H. J . M. The Estimation of Calcium and Potassium in t h e Ash of Cereals. FIRMAN THOMPSON and H. H. MoRaaN (J. Ind. Eng. Cliem. 1911 3 398- 400).-The high percentage of potassium phosphate in the ash of wheat grains and other cereals renders the estimation of calcium and potassium somewhat difficult and the authors after numerous experiments suggest the following method. CuZcium.-Fifty C.C. of the hydrochloric acid solution of the ash (corresponding to 0.5 gram ash) are boiled rendered slightly ammoniacal acidified with acetic acid using an excess of about 10 C.C.of 50% acid and bringing the total volume t o not more than 75 C.C. The pre- cipitate is boiled allowed to settle and the combined phosphates of iron and aluminium collected and thoroughly washed wit'h hot water; the filtrate while hot is treated with 10 C.C. of a saturated ammonium oxalate solution and the calcium thus precipitated determined by any known method. Potussium.-A modification of the method of Adie and Wood (Trans. 1900 77 1076) was found to be rapid and accurate and is carried out as follows. After separating the iron and aluminium phosphates as previously described the filtrate is concentrated to 75 c.c. cooled and treated with 25 C.C. cobnltinitrite solution (prepared by Adie and Wood's method) left overnight the precipitate collected on asbestos felt in a Gooch crucible and washed with cooled 10% acetic acid aud finally once with water.The asbestos and precipitate are transferred to a beaker heated with 40 C.C. of a saturated barium hydroxide solution boiled and the precipitated cobaltic hydroxide collected whilst the filtrate and washings paqs into a 200 C.C. graduated flask are cooled and made up to volume. A solution of 25 C.C. standard potassium permanganate is treated in a basin with 25 C.C. VOL. CII. ii. 14ii. 206 ABSTRBCTS OF CHEMIOAL PAPERS. of 50% sulphiiric acid and 150 C.C. of hot water into which the alkaline nitrite is slowly run from a burette until the colour disappears.The use of barium hydroxide is found to ensure the complete precipitation of cobalt the presence of which would interfere with the titration whilst the titrating for disappearance of colour is compensated for by the elimination of the danger of losing nitrous acid. A 0.1274N- solution of potassium permangnnate in which 1 C.C. is equivalent t,o 1 mg. K,O is found to be a convenient concentration t o employ in this estimation. F. M. G. M. Estimation of Mercury ia Hydroxyphenylenedimercury Acetate and Mercurisalicylic Acid. RXCHARD BRIEGER (Arch. Pharm. 1912 250 62-'71).-Trials of the iodometric method of estimation prescribed for mercurisalicylic acid in the German Phsrma- copeia and for hydroxypherl ylenedimercury acetate gave variable results. The variation was found to be due to the use of too much acetic acid in dissolving the compound.The solution in acetic acid should be almost nentralised with potassium hydroxide solution the iodine solution added and the titration with sodium thiosulphate com- pleted after one hour Variable results are also obtained when the method is applied to mercurisalicylic acid due to the fact that cornmercial preparations of this compound contain marcurysalicylntesalicylic acid. The following method of estimation is recommended Half R gram of the substrince is dissolved in 30 C.C. N/10 potassium hydroxide solution then diluted with 100 C.C. of water and a few drops of o-nitrophonol solution ;:ddotl. Thirty C.C. of N/lO-hydrochloric acid are then added the mixtiire shaken and then titrated back with N/lO-potassium hydroxide solution The diffeirnce between 30 and the number of C.C.of alkali used multiplied by 0 0138 gives the amount of salicylic acid present in the impurity and the difference between 100 and t h e percentage of salicylic acid so present multiplitd by 0.5952 gives the percentage of mercury which should correspond with that found Gy the following method 0.3 gram of the compound dissolved in 10 C.C. N-potassium hydroxide solution is diluted with 25 C.C. of water containing 5 C.C. of 30% acetic acid shaken mixed with 25 C.C. N/lO-iodine solution and after fifteen hours titratetl with 3/10 thiosulyhate solution. Each C.C. of iodine solution used corresponds with 0.0100 gram of mercury. T. A. H. Micro-chemical Reaction for Manganese.M. WAQENAAX (Pharm. Weekblad 191 1 40 14-l5).-Potassium chromate is recommended as this forms an insoluble crystalline double chromate with manganese. Viewed under the microscope the dark brown crystals are found to be grouped into beautiful rosettes and in the case of great dilution they are united to bundles. The solution should be neutral or but faintly acid. At the commencement the rosettes appear like black dots which grow to very characteristic bundles. The cryYtals show double refraction. 0.005 rng. of manganese may be recognised. The presence of zinc does not interfere as zinc chromate is not crystalline. If however the zinc preponderates t o the extent of 10 1 or more a preliminary separation of the manganese should beANALYTICAL CHEMISTRY. ii. 207 effected by hydrogen peroxide in ammoniacal solution.below 0.1 mg. however can then no longer be detected. Quantities L. DE K. Estimation of Manganese by the Sodium Bismuthate Method. WILLIAM F. HILLEBRAND and WILLIAM BLUM (J. Ind. E ~ J . Chem. 1911 3 374-376).-The author points out an error by Brinton (this vol. ii 93) who used an incorrect factor for the ratio of 5Na,C,04 2Mn ; after recalculating Brinton's results and from expari- ruents couducted at the Bureau of Standards the author considers that more evidence is required to justify the adoption of the suggested empirical instead of the theoretical factor and exhibits tabulated analytical data in support of his contention. I?. M. G. M. Estimation of Manganese by the Sodium Bismuthate Method. PAUL H. M.P. BRINTON (J. Ind. Eng. Chem. 1911 3 376).-The correction of an error (this vol. ii 93) when the fachr 0.16024 instead of 0.16397 was taken to represent the ratio 5Na,C,O 2Mn ; it is pointed out that this mistake does not influence the correctness of the empirical factor 0.1666 suggested by the author although it diminishes the necessity for its employment neither does it affect the analytical results described in the previous communication. F. M. G. M. Analysis of Technical Ferro-Boron. GASTON RAUL~N (Mon. Sci. 191 1 [v] 1 ii 434-438).-'l'he volumetricj estimation of boric acid i n the presence of a poljtiydroxy-alcohol (such as glycerol) W H S first employed by Thorusou (Abbtr. 1894 ii 38) and by Barthe (J. l'/m-m. CIL'L~~L. 1894 29 163) and is now adapted for technical analysis.The mineral (0.6-1. gram) is decomposed by boiling with 3-4 C.C. of concentrated sulphuric acid cooled 20 C.C. of methyl alcohol added and the boric acid distilled into 20-25 C.C. of a 2% sodium carbonate solution; the distillation is repeated four or five times with addition of 15 C.C. of methyl alcohol each time. The distillate is freed frorri rnethyl alcohol by evaporation just acidified with dilute hydrochloric acid boiled neutralised with sodium carbonate treated with glycerol (2 parts) and alcohol (1 part) and finally titrated w i t h standard sodium carbonate using phenolphthalein as indicator. F. M. G. &I. The Analysis of Ferro-Uranium. 11. WOLDEMAR TRAUTMANN (ZeitsclL. argew. Chem. 1912 25 19).-By an error in the former paper (Abstr.1911 ii 157) aluminium was directed to be extracted from the alloy by fusion with sodium peroxide instead of from the residue from the treatment with ammonium carbonate. As traces may remain in solution even after twenty-four hours it is now recommended that the fully oxidised solution should be saturated with solid ammonium carbonate and mixed with a slight excesg of ammonium sulphide. After shaking an aliquot part is filtered and the uranium separated from the filtrate by boiling. Pruticleu of ailicon carbide may remain insoluble when the alloy is dissolved in aqua regia. C. H. D.ii. 208 ABSTRACTS OF CHEMICAL PAPERS. Assay of High Grade Alloys of Tungaten. T. KUCZYNSKI (Bull. Acad Sci. Crucow 191 1 A 542- 544).-Chlorine Method.-The coarsely powdered sample is placed in R porcelain boat and introduced into a combustion tube connected with a Peligot tube filled with dilute hydrochloric acid (1 5).A rapid current of chlorine is passed and when the air is completely expelled the combustion is started as usual until only n little carbon remains in the boat. When cold the tubes are disconnected and after emptying the Peligot tube both are washed first with warm dilute hydrochloric acid and then with dilute ammonia. The mixed liquids measuring about 500 c.c. are mixed with 5 C.C. of hydrochloric and nitric acids in excess and boiled until 60 C.C. are left. The tungstic acid is then collected and washed but as some remains in solution it is necessary to recover this by evaporating to dryness and heating the residue a t 120' ; the mass is then boiled with dilute hydrochloric acid and the undissolved tungstic acid is collected.Should the tungstic acid contain iron it may be freed from this by dissolving in dilute ammonia and reprecipitating by boiling with excess of dilute hydrochloric acid (1 10) ; the traces remaining in solution are then again recovered by evaporation as directed. The precipitate is finally dissolved in ammonia evaporated to a small volume in a quartz crucible acidified with nitric acid evaporated to dryness and then ignited to the trioxide. HydroJEuoric acid amethod.-The sample in small lumps is treated in a platinum crucible with 5 C.C. of uitric acid (D 1.4) and 2 C.C. of water f o r every 0.2 gram taken from the assay. 0.5 Gram (or more) of ammonium fluoride is added and the whole is heated on the water- bath until dissolved ; sometimes it is necessary to add a few drops of sulphuric acid.Finally 2 to 3 C.C. of sulphuric acid are added and the fluorine is expelled by heating on the water-bath. When cold the contents are rinsed with water into a beaker ; traces of tungstic acid adhering to the dish are dissolved in dilute ammonia. The solution measuring about 60 c.c. is then boiled with 20 C.C. of hydrochloric acid etc. as in the chlorine method. L. DE K. [Separation of Columbium and Tantalum.] OTTO RUFF and EMIL SCHILLER (Zeitsch. anorg. Chern. 191 1 72 329-%7).-See this vol. ii 168. Eetimation of Small Quantities of Methyl Alcohol [in Presence of Ethyl Alcohol]. CHARLES SIMMONDS (Amalyst 19 12 37 16-18).-The liquid (a medicinal tincture for instance) is hub- mitted to distillation and if necessary purified by the method of 'L'horpe and Holmes (Trans.1903 83 314) or by other suitable means. It is then diluted with water or ethyl alcohol until it contains 10% of alcohol by volume. To 5 C.C. of this liquid placed in a wide test-tube are added 2.5 C.C. of permanganate solution (21 grams per 100 c.c.) and then 0.2 C.C. of sulphuric acid. After three minutes 0-5 C.C. of oxalic acid (9.6 grams par 100 c.c.) is added followed by 1 C.C. of sulphuricacid; 5 C.C. of Schiff's reagent are now added and a violet oolour which takesANALYTICAL CHEMISTRY. ii. 209 some time to develop according to the amount of methyl alcohol originally present will then be noticed (formaldehyde reaction). The colour may be matched by means of solutions treated as above and containing the formaldehyde produced from 0.001 to 0.004 gram of methyl alcohol.L. DE K. Systematic A n a l y s i s of Phenols. JEAN A. SANCHEZ (Bull. h'oc. chim. 1911 [iv] 9 1056-1059).-A system of detecting phenols by means of colour reactions and precipitates is given. To 1 C.C. of the liquid to be examined 1 C.C. of mercuric nitrate solution is added ; a slate-black precipitate indicates catechol. Two C.C. of the original liqtiid are mixed with 4 C.C. of lead acetate solution. The precipitate (a) is separately examined and the filtrate is divided into two parts ( b ) and ( c ) . Formaldehyde and hydrochloric acid give on boiling a gooseberry-red flocculent precipitate with ( b ) if resorcinol is present and ammonium sulphomolybdate solution produces an indigo-blue coloration with ( c ) if quinol is present.The precipitate ( a ) gives a red coloration changing to violet-red with formaldehyde and hydrochloric acid if pyrogallol is present. The original liquid with formaldehyde and hydrochloric acid gives a green coloration if i t contains phloroglucol; (2) a ruby-red tint with potassium cyanide if it contains gallic acid ; (3) a white precipi- tate with solution of nicotine hydrochloride if tannic acid is present ; and (4) a ruby-red tint with phloroglucinol and hydrochloric acid if it contains vanillin. For the detection of salicylic acid the original liquid is treated with lead nitrate solution and 2 drops of ammonia and to the filtrate acidified with 2 drops of hydrochloric acid ferric chloride is added.A bluish-violet coloration is produced if salicylic acid is Dr eaent. Directions are given for the preparation of the various reagents. T. ,4. H. New Method .for the Estimation of Sugar. FRANZ VON FXLLINGEX (Zeitsch. Nahr. Genussm. 191 1 22 605-607).-Two solutions are required in the process described one containing 250 grams of potassium thiocyanate 250 grams of potassium carbonate and 25 grams of potassium hydrogen carbonate per litre and the other containing 4-278 grams of crystallised copper sulphate per litre. Twenty C.C. of each of these solutions are placed in a flask the latter being then closed with a rubber stopper through which passes the lower end of the burette containing the sugar solution under examina- tion. A side-tube on the neck of the flask is connected by means of a T-piece with two wash-bottles containing alkaline pyrogallol solu- tion the I ubes in which are so arranged that all air entering or leaving the flayk passes through one or the other wash-bottle respectively.The solution in the flask is now boiled to expel the dissolved and free oxygen and the sugar solution is then added gradually to the boiling contents of the flask until the colour is discharged. The percentage quantity of sugar in the solution is found by dividing 1 by the number of C.C. of the solution required for the titration. The hugar d u t i o u should contaiu approximately 0.1% of sugar w. B. s.ti. 210 ABSTRACTS OF CHEMICAL PAPERS. Sugar Analysis.CARL NEUBER~ and MI~AKU ISHIDA (Zeitsch. uer. deut. Zuclcerind 191 1 11 13-1 1 39).-Carbohydrate solutions are precipitated first with mercuric acetate in 50% solution and then with phosphotungstic acid in 25% solution. The precipitates settle quickly and are easily filtered. These reagents do not affect carbohydrates a t all but completely precipitate all purines alkaloids nucleic acids phospbatides and dyes as well as all protein decomposition products ; the clear almost colourless sugar solutivns remaining are polarised directly. Excess of the reagents is avoided and t h e mercuric acetate precipitate is filtered off before the addition of the phosphotungstic acid. The reagents have no influence on the rotatory power of the sugars. Glucosamine solutions can be purified in the same manner and the method is particularly suited for the analysis of molasses of which several examples are quoted.E. F. A. The Estimation of Sugar in Urine. IVAR BANG (Biochem. Zeitsch. 1912 38 168).-In view of the recent publication of Andersen (this vol. ii 101) that the pigment can be removed from urine by charcoal in the presence of acetic acid the author stat’es that he has successfully employed alcohol instead of the acid using 2 C.C. of alcohol to 18 C.C. of urine. The urine should be diluted if it contains more than 0.5% of sugar. S. B. S. Stability of Different Types of Smokeless Powder Towards Ultra-violet Light. DANIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 19 11 153 1220-1223).-Exposure to ultra-violet light considerably accelerates the spontaneous decomposition of emoke- less explosives and t,his can be made the basis of a useful stability test.The explosives examined were cut into cylinders weighing 0-25-0.45 gram placed over mercury in a quartz tube containing nitrogen or carbon dioxide and exposed to the radiation from a quartz mercury lamp at a distance of 78-80 mm. for six hours. In all cases rapid decomposition occurred with production of carbon monoxide or dioxide nitrogen and frequently ni.trous and nitric oxides. Powders consisting only of nitrated cellulose were found to be more stable than those containing nitroglycerol. An English cordite containing 30% of the latter and 5% of Vaseline exposed in 1 C.C. of carbon dioxide gave a mixture composed of the following volumes of gases CO 1 c.c.;CO 0*17c.c.;NO 0-l0c.c.; N20,0~02c.c.;N2,0~10c.c. Numerical results are also given for the French A arid €3 powders arid for balistite of different ages and with different stabilisers.W. 0. W Estimation of Citral iu Lemon Oil. J. R. RIPPETOE and Lours E. WISE (Amer. J. Phccrm. 1911 83,558-562).-A method proposed originally by Hiltner is recommended as being trustworthy; it depends on the coloration produced when citral is treated with m-phenylenediamine hydrochloride. The reagent solution is prepared by dissolving 1 gram of the salt in 100 C.C. of alcohol and filteriug the solution through bone-charcoal. From 2 to 4 C.C. of a 3% alcoholic solution of the lemon oil are placed in a graduated cylinder 10 e x . ofANALYTIOAL CHEMISTRY. ii.211 the reagent are added and the mixture is diluted with alcohol to a volume of 25 C.C. The coloration is theri compared with that obtained Estimation of Acids in Wine with a View to Discover Adulteration. FERDINAND REPITON (MOD,. Sci. 1911 [v] 1 i 379-382).-The acidity of wine can be represented by the formula where At is the total acidity Af the fixed acidity A volatile acidity and A gaseous acidity; the author discusses their relationship and transformations by the action of disease and organisms and describes methods of estimating and distinguishing between them. with mixtures containing known amounts of citral. w. P. s. At = Af + A + A F. M. G. M. The Estimation of Volatile Acids in Wines. FRITZ KOCZIRZ (Zeitsch. Zandw. Wesert. Oesten.. 191 1 14 866-871).-A diecussion of numerous methods employed in the estimation of volatile acids in wine with a sketch and description of a distilling apparatus which the author considers to give satisfactory results.Estimation of Acids in Oils and Fats. HEINRICH LOEBELL (Xeifensied. Zeit. 1911 38 501-502 530-532).-A method for the estimation of the acidity of fats and machine oils in which the presence of any acid is undesirable. The titration is carried out in iL flask fitted with a tap a t the base and three openings at the top into which are fitted respectively a tube packed with soda-lime n burette from which the standard alcoholic sodium hydroxide (or barium ‘hydroxide) is delivered and a droppiug funnel containing about 100 C.C. benzyl alcohol and 8 C.C. of a 2% solution of alkali-blue. Analysis of Lactic Acid.W. KLAPPROTH (Chem. Zeit. 2911 35 1409).-In replying to criticisms by Besson (compare A bstr. 1911 ii 1140) the author points out that the method described by himself (Abstr. 1911 ii 1038) is not a new method but one which has been in general use for some time. Whilst heating the neutralised lactic acid solution after the addition of an excess of standard alkali accelerates the hydration of the anhydride it is better to avoid boiling at any stage of the estimation. The methods described by Eesson and the author are similar in principle and after further investigation will DIOSCORIDE VITALI (BoZZ. Chim. If’arrn. 191 1 50 799-803. Compare Ganassini Abstr. 1909 ii 100).-The author substituted a number of other oxidisers for the potassium persulphate employed by Gnnassini in his reaction for the detection of uric acid but sodium peroxide was the only one with which the reaction could be effected. No other metallic salt was found capable of replacing the zinc salts used by Ganassini but the behaviour of some of them towards the solution containing alkali urate and sodium peroxide was characteristic.Copper sulphate gave a green precipitate (blue with larger quantities) cobaltous chloride a bluish-violet precipitate and nickel salts a green precipitate having a F. M. G. M. F. M. G. M. probably be equally trustworthy. w. P. s. New Reaction for Uric Acid.ii. 212 Al3STRACTS OF CHEMICAL PAPERS. yellow tinge. Neutral lead acetate in the wrne cnnditiotis gkve a red peci pitat e. R. v. s. A New Ureometer. ESPINOZA TAMAYO (Ann Chim amcl.191 1 16 453-454).-The appantiis figured in the original is a modifica- tion of that constructed by Esbach and consists of a gas burette connected a t tho upper end with a gouerC\ting bulb arrangement a t the bottom of which are placed 2 C.C. of urine. A kind of separatory funnel containing hypobromite solution is ground into the neck of the bulb and the ground joint is also arranged to act as a tap to admit or cut off air from the bulb. After placing the whole in a water trough. the funnel is turried so a4 to stop the communication with the air and by opening the stopcock the bulk of the hypobromite is allowed to flow into the urine The nitrogen collecting in the burette is then measured with the usual precautions.L. DE K. A Modification of Riegler’s Method of Estimating Urea in Urine. THOR EKECRANTZ and K. A . S~DEHMAN (Zeitsch. plqsiol. Chew. 1912 76 173-1 T(i).-Riegler’s method con&Is in warming the urine with nitric an> nitrous acids which decomposes the urea so that i t yields equal volumes of carbon dioxide and nitrogen. J f this is corn bined with Dumas’ method for esti tnating nitrogen the method is simple and accurate. The details of the suggested modification are described and the appzratus employed is figured. w. I). 1-1. Estimation of Cinnamein in Balsam of Peru. FRANZ TmIMANN and A. MULLRE ( A ~ c h . Pharm. 1912 250 1-5).-Tlie following met,hod is recommended Five grams of water are mixed with 2.5 grams of balsam of Peru in a 75 C.C. bottle and to this 30 C.C. of ether are added and the whole shaken during one minute. Five grams of sodium hydroxide solution are then added and the mixture again shaken during one minute. The Lottle is securely corked and set aside bottom upwards during ten minutes. The cork is then carefully loosened and about 3 C.C. of tbe aqueous layer run off. Half a gram of tragacanth gum is then added to the contents of the bottle and the whole shaken. After five minutes the clear ethereal solution is run into a tared wide-mouthed flask and its weight ( w ) noted. The solvent is then distilled off the residue dried at 100” during thirty to forty-five minutes and its weight (w’) determined. The percentage x of ciunamein in the balsam is given by the following equation x = (30w’/w - w’)40. T. A. H. Coagulation of Albumin by Heat. Consequences in Connexion with the Estimation of Urinary Albumin. LUCIEN VALLERY (Compt. rend. 191 1 153 1243-1244).-The filtrate from alburninoun urine which has been acidified and coagulated by heat in presence of ammonium chloride still gives a precipitate with Tanret’s reagent. The use of Tanret’s or Esbach’s reagent is therefore recommended for the accurate estimation of urinary a1 bumin. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9120205199

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 213 General and Physical Chemistry. Proposed System of Notation for Physico-chemical Quantities. ARTHUR A. NOYES (J. Amer. Chem. Soc. 1912 34 1-6).-An outline is given of a system of notation for physico- chemical quantities which is intended to serve as a basis for further discussion. An endeavour has been made to formulate a rational and consistent scheme and at the same time to retain as far as possible the specific symbols at present in general use. E. G. Determinations of Refractive Indices of Gases Under High Pressures. I. The Dispersion of Hydrogen. L. H. SIERTSEMA and M. DE HAAS (Proc. K. Akad. Wetensch. Amsterdam 1911 14 592-603).-The refractive index of hydrogen has been measured at pressures from 40 to 80 atmospheres and for different wave-lengths by the interferometer method.From these data it i s found that the dispersion constant of hydrogen is independent of the pressure within the above limits. The constants for the different wave-lengths are compared with the values obtained by calculation or graphical interpolation from the results of previous observers. The natural vibration of hydrogen is found to correspond with the wave-length X = 0*08703p which agrees with the values calculated by Koch and by Natanson. H. M. D. Spectrochemical Investigations. KARL AUWERS (AnnaZen 19 12 387 165-166. Compare following abstracts).-The investigations of the author and Eisenlohr (Abstr. 1910 ii 365 367 ; 1911 ii 781 782) have materially increased the dependence which can be placed on the constitution of an organic substance determined by refractometric measurements.These investigations are being continued of aromatic and of nitrogenous compounds by Eisenlohr of acyclic and of hydroaromatic substances by the author. c. s. Refraction and Dispersion of Organic Substances containing Several Isolated Double Linkings. KARL AUWEXS and W. MOOSBMJGGER (Anncden l912,387,167-199).-The generally accepted view that acyclic dienes containing isolated double lirikings are optically normal rests on a very narrow experimental foundation The authors therefore have determined the moltcular refracbions and dispersions of a number of hydrocarbons alcohols ketones acids and esters containing two or more isolated (not conjugated) double linkings and have established with practical certainty the fact that such substances exhibit normal optical behaviour.The substames which have been examined are /3-methyl-4Pe-hexadiene Pc-dimethyl-Ape- heptadiene PC- dimethyl -Aac-heptadiene /3l-dimethyl- Ape-octadiene /lg-dimethyl-APee-nonatriene eethyl-Aase-nonatriene au-diallylacetone s-diallylacetone diailylacetic acid and its ethyl ester ethyl diallylmalonate triallyl tricar ballylate and triallyl citrate. VOL. CII. ii. 15ii. 214 ABSTRACTS OF CHEMICAL PAPERS. The positions of the double linkings in the preceding dienes and trienes (which have been obtained by dehydrating the corresponding alcohols) have not been determined with certainty. Their absolute position however is immaterial for the authors’ purpose because the optical (and also the thermal) behnviour of the hydrocarbons is independent of the relative positions of the double linkings provided they are not conjugated.c. s. Spectrochemical Differentiation between Hydroaromatic Compounds with Endocyclic and with Semicyclic Double Linkings. KARL AUWERS and PHILIPP ELLINGER (Annalen 19 12 387 200-239).-See this vol. i 187. Constitution of Camphene. KARL AUWERS (Annalen 19 12 387 240-253).-The author calls attention to the necessity of expressing densities as Di not as D in the calculation of specific and molecular refractions ; in the latter case the error exceeds 4% a t looo. The exaltations of the specific refractions Z of terpenes containing a semicyclic double linking (sabinene dl-fenchene terpinolene P-terpinene P-pinene) vary from 0.3 to 0.5 and therefore are just what is to be expected from a comparison with theexaltations of 2 of the alkylidenecycloparaffins (this vol.i 187). The vexed question of the constitution of camphene appears to be settled definitely in favour of Wagner’s methylene formula by the fact that the exaltation of 2 is 0.37 thus indicating that campbene also contains a semicyclic double linking. c. s. Spectroscopic Investigations in Connexion with the Active Modification of Nitrogen. 11. Spectra of Elements and Compounds Excited by the Nitrogen. (Hon.) ROBERT J. STRUTT and ALFRED FOWLER (Proc. Roy. Xoc. 1912 A 86 105-117. Compare Abstr. 1911 ii 482 6’78)-As a result of the examina- tion of the spectra obtained when various elements and compounds are subjected to the action of the active modification of nitrogen it is found that these spectra do not differ fundamentally from those obtained by other methods of excitation.I n many cases however the band spectra are better displayed in the nitrogen after-glow and the more refrangible parts of the spectrum are more completely developed. In the case of metallic substances the spectra resemble closely those obtained in the arc or are intermediate between the arc and flame spectra. The D lines of sodium are nearly extinguished and the maximum intensity in the principal series is found a t X = 3303. The spectra exhibited by iodine stannic chloride and mercuric chloride are more completely developed in the more refrangible region than the corresponding vacuum tube spectra. Cuprous chloride sbows a similar behaviour when the after-glow and flame spectra are compared the former giving an additional series of bands in the ultra-violet. Sulphur hydrogen sulphide and carbon disulphide exhibit band spectra which are quite different from thoseii.215 GENERAL AND PHYSICAL CHEMISTRY. afforded by sulphur in a discharge tube but resemble the bands of the carbon disulphide flame in air. The cyanogen spectrum which appears when various organic com- pounds are subjected to the after-glow is appreciably different from that of the cyanogen dame or carbon arc. The after-glow spectrum shows a new set of bands near the more refrangible edges of the violet groups. The after-glow is not only generated by discharge with spark-gap and condenser but can be obtained from the electrodeless ring discharge if the presence of the nitrogen is suitably adjusted.The destruction of the after-glow by small amounts of oxygen has been found to be due to the formation of a small quantity of nitric oxide the effect of which is to suppress the a-group of bands leaving the rest of the after-glow spectrum unaltered. The Less Refrangible Spectrum of Cyanogen and its Occurrence in the Carbon Arc ALFRED FOWLER and HERBERT SHAW (PTOC. Roy. Soc. 1912 A 86 118-130).-Wave-length measure- ments have been made in the less refrangible region of the cyanogen spectra afforded by ( I ) the flame of cyanogen burning in air ; (2) the discbarge through exhausted tubes containing cyanogen and (3) the interaction of certain carbon compounds with active nitrogen. The data show that the heads of the bands can be arranged in regular series similar to those forming the first positive band spectrum of nitxogen.According to the method of producing the spectrum con- siderable variations are found in the relative intensities of the various bands. A comparison of the spectra of cyanogen and of the carbon arc shows that the bands in the red and yellow regions of the arc spectrum are almost entirely due to cyanogen. H. M. D. H. M. D. Comparison of Spectra in the Oxy-Hydrogen and Chlorine- Hydrogen Flames. ALFRED HARNACK (Zeitsch. wiss. Photochern. 1911-12 10 281-31 2 313-346).-Photographs have been obtained of the spectra of calcium strontium barium magnesium copper manganese lead nickel and cobalt in the oxy-hydrogen and chlorine- hydrogen flames. By means of these it has been possible tocompare the emission spectra in the two flames over the visible and ultra-violet regions.I n general the chlorine-hydrogen flame spectra are charac- terised by the presence of relatively few lines. Bands are present in both series of spectra but apart from those which are attributable to the chlorides of the metals it is found that the spectral bands in the two flames are quite different. Bands characteristic of the nitrates of the metal were not found i n any single case. In addition to the bands which are attributed to the metals and their oxides calcium and strontium exhibit certain bands which are considered to be the result of oxidation in the oxy-hydrogen flame. I n appearance these oxida- tion bands are quite different from the oxide bands and disappear completely when the oxy-hydrogen flame is replaced by the chlorine- hydrogen flame.I n the same circumstances the oxide bands are replaced by a new series of bands. The presence of comparatively few lines in the hydrogen-chlorine 15-2ii. 216 ABSTRACTS OF CHEMICAL PAPERY. flame spectrum is supposed to be due to the effect of the strongly electro-negative chlorine the action of which is compared with the influence of electro-negative gases on the fluorescence of iodine vapour. Wave-length measurements of bands which have not been previously described are recorded in detail in the paper. H. M. D. Emission Spectra of Aromatic Compounds Exposed to Ultra-violet Light Cathode Rays Radium Rays and Canal Rays. EUGEN GOLDSTEIN (Bey.Deut. physikal. Ges. 1912,14,33-42). -It has been shown previously (compare Abstr. 1911 ii 560) that solid aromatic substances emit the principal spectrum on exposure to ultra-violet light if previously subjected to the action of cathode rays. I n some cases for example cuminic acid o-toluic acid acenaphthene and aceto-p-toluidide this property is retained for months after the cathode ray treatment whilst in others such as phenylacetic acid the principal spectrum is no longer observable after an interval of a few days. The question as t o whether the change produced by cathode rays is chemical or physical in nature has been examined. If the substances after t,reatment with cathode rays are melted sublimed or dissolved and recrystallised the principal spectrum is no longer emitted and these observations seem to be in favour of the view that the change is a physical one.In addition to cathode rays the P-rays from radium meso- thorium and actinium as well as canal rays are able t o bring about the transformation which is characterised by the emission of the principal spectrum. During exposure to canal rays it has been observed that the initial luminosity fades away gradually and none of the substances examined recover their original properties on keeping either in the dark or exposed to light. The same behaviour is exhibited by diamond powder and since a chemical change is improbable in this case the obaervations point to a physical change as the cause of the alteration in the optical properties. H. M. D. Absorption Spectra of Comparatively Rare Salts.XXXV. Spectrophotography of Certain Chemical Reactions and the Effect of High Temperature on the Absorption Spectra of Non-aqueous Solutions. HARRY C. JONES and W. W. STRONG (Amer. Chem. J. 1912 47 27-85 126-179).-A continuation of woIk described in earlier papers (Abstr. 1907 ii 147; 1909 ii 359 ; 1910 ii 8 7 ; 1911 ii 166 168). A detailed account is given of the absorption spectra of salts of gadolinium dysprosium and samarium and additional observations are recorded of the spectra of neodymium and uranium salts in various solvents. It has been found that the spectra of dysprosium and samarium salts have sharp characteristic bands. The effect of oxidising agents on urinous chloride bromide and sulphate has been further investigated by the spectrophotographic method.GENERAL AND PHYSICAL CHEMISTRY.ii. ‘217 The absorption spectra of solutions of salts in methyl and ethyl alcohols have been studied at various temperatures up to 195’. The absorption bands become wider as the temperature increases and coloured solutions therefore gradually become more nearly opaque. The effect of a rise of temperature on the spectra of neodymium salts in mixtures of alcohol and water in which both the ‘‘ alcohol bands ” aud ‘‘ water bands ” appear simultaneously has been investigated. The (6 water bands” are more affected than the “ alcohol bands,” and the ‘‘ hydrates ” are therefore less stable at high temperatures than the ‘‘ nlcoholates.” A discussion is given of a theory of absorption spectra based on the conception of the existence of aggregates composed of one or more moleciiles or ions of the dissolved salt and one or more molecules of the solvent.E. G. Spectrophotographic Investigation of Urobilin. LOUIS LEWIN and E. STENGER (PJfiger’s Arcl~iv 1912 144 279-286).-A11 the substances described as urobilin show an absorption band in the green- blue region the centre of which is X494; this is the case for alcoholic and aqueous acid solutions ; on the addition of alkali the band shifts towards the red end of the spectrum. The same shifting takes place when the fluorescent reaction is obtained by adding zinc chloride and ammonia to the alcoholic solution and is due to the alkali. Hydro- bilirubin and the material prepared from hsmatoporphyrin by Nencki and Sieber give a band between A580 and X628.W. D. H. Phosphorescence of Organic Compounds at Low Tem- peratures JOSEPH DE KOWALSKI (Arch. Sci. phys. m t . 1912 [iv] 33 5-27).-A r8sum8 of the author’s work on this subject (Abstr. 1907 ii 727 ; 1908 ii 79 ; 1909 ii 282 845 ; 1910 ii 371 1016). The introduction of one or more groups into the benzene nucleus produces the following effects on the absorption spectra the number of doublets and triplets diminishes the bands become less distinct those in the extreme ultra-violet are displaced towards the red and the extent of the phosphorescence spectrum is reduced. Those substituents which displace the limit of the phosphorescence spectrum towards the violet a re termed hypsophoaphic whilst those which displace the limit towards the red are bathophosphic.Batho- phosphic mono-substituents are particularly cyano CN also amino NH and carboxyl C0,H. All other mono-substituents are hypso- phosphic. In the case oi di-substituents the difference between the extent of the phosphorescence spectrum when these are in the ortho- and para-positions respectively is a constant. The influence of a second substituting group on the mono-substituted compound is specific. CN and CO,H are always bathophosphic methyl is bathophosphic in the para-position and may be hypsophosphic in the ortho-position. Hydroxyl is strongly hypsophosphic. The more negative t h e radicle the greater its bathophosphic action. Cyano and (CH,) also influence the nature of the phosphorescence spectrum converting doublets into triplets.Each absorption band corresponds with a group of bands in theii. 218 ABSTRACTS OF CHEMICAL PAPERS. phosphorescence spectrum and this group only differs from the absorption band by a practically constant number of oscillations. E. F. A. Rotatory Dispersion and Mutarotation of the Carbobydrates in Water Pyridine and Formic Acid. HERMANN GROSSMANN and F. L. BLOCH (Zeitsch. ver. deut. Zuckerind. 1912 19-74).-The dispersion coefficient violet/red for solutions of the simple carbo- hydrates in water pyridine or formic acid is usually between 2.2 and 2.4. Abnormal values were found for rhamnose in water 2.03 and for lactose in pyridine. The change of rotation of the carbohydrates usually for red light has been studied in water pyridine and formic acid; in the last solvent the change is probably due to the formation of formyl compounds; it is usually in the opposite sense to the mutarotation changes.Xylose in water changes horn +SOo to 18.2'. In pyridine the rotation increases from + 117' to + 3 22' during the first ten minutes and then falls steadily to + 40.6'. I n formic acid it changes from + 40' t o + 66.6'. Rhamnose changes in water from - 4.43' to + 8.6' ; in pyridine from -41.39' to -45.12' during the first half-hour and finally to - 33'. The rotation of galactose in water falls from + 141' to + 80.2'; the initial rotation in pyridine is probably 200° falling to 59.8'. In formic acid the change is from 89.1O to 127.3'. Dextrose in water changes from 111' to 52.6O; in pyridine from 149.6' to 74*8' and in formic acid from 73.8" to 123.1'.Laevulose changes very rapidly in water from - 101.9' to - 90.46' ; in pyridiae from - 160' to - 35' and in formic acid from - 86.5' to - 46.i'. N/S-Sucrose has a rotation + 66.5' in water ; + 84-37' in pyridine and changes from + 2-64' to + 39-95' in formic acid. Lactose alters from 83*1° to 52.5' in water; the final value in pyridine is 41-33' For this carbohydrate a change in the concentra- tion has almost no influence. I n formic acid the rotation changes from +68.2' to +96.6'. Maltose in water varies from 121.6' to 130.5' (hydrate) ; in pyridine from 103.5' to 123.5' and in formic acid from 129.1' to 17201~. Raffinose has the rotation 105.2' in water and 117'2'in pyridine for N/16-solutions ; in formic acid the value changes from 72.3') to 109.4'; during the first few minutes the rotation diminishes.All the values cited are affected considerably by alterations of the concentration of the carbohydrate. E. F. A. The following values refer to [a]:. Photochemical Studies. IV. Photochemical Temperature- coefflcienb of Bromine. JOH. PLOTNIKOFF (Zeitsch. ph ysika?. Chem. 1912 78 573-581. Compare hbstr. 1911 ii 462).- The temperature-coefficients for 10' for three light reactions in which bromine is concerned are as follows the addition of bromineGENERAL AND PHYSICAL CEEMISTRY. ii. 219 to cinnamic acid in benzene as solvent 1.37 ; the same reagents in carbon tetrachloride as solvent 1.41 ; the action of bromine on benzene 1.40. It is shown that the temperature-coefficients for 10' for the light reactions hitherto examined can be referred to one of three groups of values 1 *04 k 0.03 1 *20 + 0.03 and 1.39 f 0.03.a. s. Influence of Gas Pressure on the Bleaching of Dyes in the Visible Spectrum. P. LASAREFF (Zeitsch. physikaz. Chem. 1912 '78 657-660. Compare Ann. Physik 1907 [4j 24 661).-A colloidion film stained with a particular dye was arranged in such a way that it was in contact with air under different pressures up to atmospheric and the rate of bleaching was measured with a spectro- photometer. As dyes cyanine pinachrome and lepidinecyanine were used. The bleaching is the more rapid the greater tbe oxygen pressure. When the rates of bleaching at constant absorption are plotted against the corresponding pressures cz straight line is obLained which does not p s s through the origin so that the velocity of bleaching must have a definite value in a vacuum.P. LASAREFF (Zeitsch. physikal. Chern. 1912 78 661-666).-Methylene- blue is bleached on exposure to a fairly intense light most rapidly in absence of oxygen but the colour returns when the bleached material is kept for a long period in the dark provided that oxygen is present. I n the experiments films of gelatin coloured with methylene-blue were exposed to light from a Nernst lamp and examined with a spectro- photometer. After exposure to light of wave-length 6 2 0 ~ ~ ~ the film regains its original properties in the dark ; with light of wave-length greater than 6 8 8 p the absorption does not regain its original value in the dark. These results can be explained on the assumption that the bleached substance becomes oxidised in the dark to products which for short waves have an absorption identical with for long waves and Some Relations Existing between the Radio-elements.RICHARD SWINNE (Physikal. Zeitsch. 1912 13 14-21).-The relation between the logarithm of the period and the velocity of the a-particle expelled (compare Geiger and Nuttall Abstr. 191 1 ii 953) is discussed in detail and slightly different relations are proposed. The period of ionium calculated from the range of its a-particle is 3.3 x lo5 years. Taking in each of the three series the range of the last a-ray producing member and subtracting this from the range of the a-rays of corre- sponding members in the three series it is found that the differences are the same for several pairs.In the single series a relation between the period of the member and the velocity of the p-particle expelled is found to exist similar to that obtaining for the a-particle. J. DANYSZ (Le Radium 1912 9 1-5).-This paper contains a description in full of the methods employed together with remarkable reproductions of the photographs obtained in the work already published (this vol. ii G. S. Bleaching of Methylene-blue in the Visible Spectrum. absorption different from that of methylene-blue. G. s. F. S. The @ R a p of the Radium Family.ii. 220 ABSTRACTS OF CHEMICAL PAPERS. 113). Twenty-three beams of P-rays have been observed making with two more each from radium radium-B and radium-D observed by others 29 in all for the radium family and rendering the hypothesis that each beam corresponds with a particular radio-element very improbable.F. S. The P-Rays of the Slow-changing Active Deposit of Radium. J. DANYSZ and J. GOTZ (Le Radium 1912 9 6).-An old tube containing radium-l) and products was examined two months after it had been filled with emanation precautions being taken t o remove any still adhering emanation. The photographs obtained were entirely different from those previously obtained with the emanation. Two wide beams of which the neighbouring sides alone are sharp and correspond with velocities of 0.963 and 0.944 (light = l) are easily distinguished. The fast side of the faster beam is difficult t o determine and corresponds with a velocity of 0.995. The slow side of the dower beam is not sharp but two maxima of intensity at 0.67 and 0.48 are distinguishable. The slow beam gives a very intense image bnt the rapid beam is very feeble.The very feeble beams obtained previously with the emanation were not observed with radium-l). F. S. The Growth of Radium-C from Radium-R. KASIMIR FAJANS and WALTER MAKOWER (Phil. Mag. 1912 [vi] 23 292-301).-The object of the experiments was to find out whether radium-C1 as well as radium-C2 emits P-rays by observing the rise and fall of the @radiation through 1 mm. of aluminium from a plate covered with pure radium-B obtained hy recoil from radium-A. It mas found as Schmidt had stated that radium-B emits some P-rays capable of traversing 1 mm. of aluminium which observation Hahn and Meitner have called in question.Allowing for these the curves agreed with the theoretical ones drawn on the assumption that the whole of the P-rays are due to radium-C1. The proportion contributed by radium-C2 was too small to be detected in these experiments hence the ratio of the number of atoms of radium-C2 to that of radium-C1 in equilibrium must be very small which supports the view that radium-C is in a branch series. lT7ith regard t o the P-rays of radium-B similar experiments through a variety of thicknesses of aluminium gave data for calculating t h e absorption of the /3-rays of radium-B in that metal. The absorption coefficient for the main soft P-radiation was found to be 91(cm.)-l but 18% of the ionisation was due to P-rays of absorption coefficient 13(cm.)-1 identical with the rays of radium-C. No evidence of any rays of absorption coefficient 890(crn.)-l as found by Schmidt was obtained.F. S. 7-Radiation from Radium-B. H. G. J. MOSELEP and WALTER MAKOWER (Phil. Mag. 1912 [vi] 23 302-310).-It was to be expected since radium-B emits some @rays as penetrating as those of radium-C that radium-B should emit some y-rays as penetrating asGENERAL AND PHYSICAL CHEMISTRY. ii. 221 the y-rays of radium-C. Investigation showed that radium-B does emit ?-rays which have hitherto escaped detection of much greater absorption coefficient than those of radium-C. The method was the same as that used for the P-rays of radium-B (preceding abstract) except that sufficient lead to absorb all the P-rays instead of aluminium was employed as absorbing material ; 12.7% of the ionisation produced by the y-rays of radium-B and -C in equilibrium was found to be due to radium-3.The absorption coefficient for these rays was 4(cm.)-l between 3 and 6 mm. and 6(cm.)-l between 0.97 and 1.72 mm. of lead. The rise of y-radiation from a tube containing initially pure radium emanation when taken through various thicknesses of lead agreed with the above conclusions. Through 2.3 cm. of lead the amount of ionisation if any contributed by the y-rays of radium-B is less than 1% of that contributed by radium-C. F. S. Nature of 7-Rays. T. H. LABY and P. W. BURBIGE (La Radium 191 1 8 464-465).-The ionisation currents in two similar ionisation chambers placed symmetrically with regard t o a source of y-rays of radium were arranged to balance one another over long periods so that the electrometer showed no appreciable deflexion.Variations in the balance first in one direction and then in the other were observed which are due either to variations in the number of ions produced by a constant source of y-rays from instant to instant or to a von Schweidler variation in the radiation itself such as would be produced if the y-rays were corpuscular rather than of wave-form. F. S &Rays. 11. NORMAN CAMPBELL (Phil. Mag. 1912 [vi] 23 46-64. Compare Abstr. 191 1 ii 841).-The previous experiments have been repeated with soot-covered electrodes for Baeyer has shown that the reflexion of the rays from a soot-covered surface is very small. The theory used previously has been shown to be quite incapable of explaining the results.The differences obtained when electrodes of various metals are employed are probably due to surface difference rather than to differences of speed of the electrons generated from the metal. A minimum estimate of the speed of the &rays generated is that corresponding with a P.D. of 3 volts. B u t neither the method employed nor other methods of various investigators gives information as to what the maximum limit of speed may be. So far as is known the speed may be independent both of the velocity of the exciting a-rays and of the nature of the material generating the 8-rays. There is no such difference between the &rays emitted for example by gold and by aluminium as there is between the secondary X-rays from these metals.With regard to the quantities of incident and emergent &radiation there is no evidence that these may not be equal nor is there evidence that polonium emits a &radiation other than that generated by the a-rays it expels. Mobility of the Positive and Negative Ions in Gases at High Pressures. ALOIS F. KOVARIK (Proc. Roy. Soc. 1912 A 86 154-162).-The mobilities of the positive and negative ions in dry F. S.ii. 222 ABSTRACTS OF CHEMICAL PAPERS. air dry hydrogen and moist carbon dioxide have been determined from observations of the current flowing between two plates at the surface of one of which an intense ionisation was maintained by means of an ionium preparation. I n dry air and hydrogen the mobility varies inversely as the pressure up to 75 atmospheres which was the highest pressure used.I n moist carbon dioxide the same relationship holds up to 40 atmospheres but a t higherpressures the product of pressure and mobility decreases as the gas approaches the liquid state. The mean values of this product over the range for which it is constant are for the positive and negative ions respectively 1.346 and 1.89 in air 6.20 and 8-19 in hydrogen and 0.705 and 0.67 in moist carbondioxide. Mobilities are here referred to cms. per second and a potential gradient of 1 volt per cm. H. M. D. Ionisation in Gaseous Mixtures by Ronfgen Radiation. CHARLES G. BARKLA and L. SIMONS (Phil. Mi. 1912 [vi] 23 3 17-333).-Experiments under a great variety of conditions showed that the relative ionisation in hydrogen sulphide is about 1.24 times that in sulphur dioxide although the absorption of the rays in the latter gas is greater than that in the former.Characteristic X-radiations varying enormously in penetrating power from that characteristic of chromium to that characteristic of antimony were employed. The ionisation in a mixture of hydrogen sulphide and oxygen was 1.17 times as great as in a mixture of the same composition of sulphur dioxide and hydrogen. The conclusion is drawn that ionisation by X-rays is not fundamentally atomic but depends to some extent on chemical corn binations equal absorptions of the X-rays and their secondary radiation being accompanied by unequal ionisations. The results so far attained point to the relative ionisation in different gases byX-mys being the same as for the corpuscular rays generated by X-rays.Preliminary experiments indicate that much of the ionisation by X-rays is not produced by the secondary corpuscular radiation. F. S. Ionisation by Radioactive Recoil Products. LOUIS WERTEN- STEIN (Le Radium 1912 9 6-19).-The active deposits from the radium emanation twenty minutes after preparation (radium-B and -C) emits in addition to the known radiations a relatively intense ionisa- tion very easily absorbed due to radium-C. The radiation consists of a small proportion easily deviable in a magnetic field ($rays excited by the a-rays of radium-C) and of a more important part of the same penetrating power not so deviable. The product of the pressure (mm.) and the range (mm.) is about 110 which is nearly the value found (90) for radium-B recoiled from radium-A.The value of this part is much affected by the nature and state of the surface made active and is greatest with platinum when it gives in favourable circumstances over the initial part of its range five times as much ionisation as is produced by the a-rays. The range is about 1/500th of that of the a-rays of radium-C or 1/7th mm. of air at atmospheric pressure so that in all ordinary experiments the total ionisation itGENERAL AND PHYSICAL CHEMISTRY. ii. 223 gives is less than 1% of that due to the a-rays. The effect of change of pressure on the ionisation and of change of distance between the source the rays of which were canalised by means OF a bundle of short narrow tubes and a shallow ionisation chamber were studied in a special apparatus analogous to that employed by Bragg for the range of the a-rays.The radiation of low penetrating power which is uninfluenced by a magnetic field is attributed to the particles of radium-l) recoiling from radium-C. The ionisation per mm. of path decreases as the distance traversed from the source increases which is the opposite of that found for tha a-rays. It was proved that the ionisation due to these new rays decayed with the period of radium-C and was given also by pure radium-C as well as by radium-B and -C. F. S. The Emanation Content in the Sea-Water and the Active Deposit from the Air between the Chilian Coast and the East Indies. I. and 11. WALTER KNOCHE (Physikal. Zeitsch. 19 1 2 13 112-115 152-157).-1.The mean in Mache units of thirty estimations of the emanation content of sea-water t-aken during a round voyage in March to May 1911 between Valparaiso and the East Indies gave a mean content of 0.05 the extremes varying from 0.00 to 0.20 as compared with a mean of 0.12 (0.00 to 0.29) found in September and October 1908 by Engler and Sieveking for the Atlantic Ocean. Twenty-one results were below 0.05 two were between 0.05 and 0.10 and five were between 0.15 and 0.20. The activity of the water changes extraordinarily with the locality. The source of the emanation cannot be the atmosphere for no relation exists between emanation content and the atmospheric active deposit. The emanation content increases with the sp. gr. of the water and with its temperature.11. The active deposit on a wire five metres long elevated seven- teen metres above the sea-level and charged to -2000V after two hours' exposure was measured at various intervals after being placed in the electroscope. After fifteen to twenty-five minutes the curves showed that only the radium active deposit was present. A resume is given of the results in connexion with the numerous data publis'hed by other investigators and are discussed with the view to showing that the active deposit in the air over the ocean is derived from the land. A chart is given showing the proportion of such active matter remain- ing after having been transported various distances by various winds and it is shown that there is no difficulty in ascribing the results observed to active matter carried from the land.F. S. The Dependence of the Penetrating Power of Rtintgen Rays on the Pressure and Nature of the Contained Gas. CHABLES L. LINDEMANN and F. A. LINDEMANN (Physikal. Zeitsch. 1912 13 104-l06).-Tables of measurements are given of the penetrating power of X-rays on the Wehnelt scale and by the Bauer qualimeter when a constant current of 1.5 milliamperes was passed through a properly prepared X-ray bulb filled with air hydrogen,ii. 224 ABSTRACTS OF CHEMICAL PAPERS. oxygen chlorine carbon dioxide argon and helium at known various pressures. It is considered to be possible with a suitably calibrated bulb to determine the gas pressure by means of a Wehnelt scale. F. S. Explosion of Radium Bromide through the Action of Water. €3.JOST (Chem. Zeit. 1912 36 138).-In order to transfer some radium bromide from the capsule containing it to a spinthari- scope a needle the point of which had been slightly moistened was used for picking up the small particles of the salt. In two cases the particles exploded during the act of transference. Such explosions seem to be connected with the purity and age of the salt,and with the amount of moisture present. T. S. P. Radioactivity of the Rocks of the St. Gothard Tunnel. JOHN JOLY (Phil. Mag. 1912 [vi] 23 201-211).-A new series of measurements has been carried out by means of the electric furnace fusion method of the radium in thirty-six rock samples from the St. Gothard tunnel together with measurements of the thorium content also. The following table gives the mean results for four sections of the tunnel Ra per gram Th per gram ( x 1012).( x 105). Granite and gneiss of the Finsteraarhorn massif 7.2 1 '85 6-0 2-64 Altered sediments of the Usernmulde ............ 4'9 0.97 2.6 1-70 Schists etc. of the St. Gothard massif ............ 3.9 1'18 2.8 1-10 Altered sediments of the Tessinmulde ............ 3 '4 0.51 2.0 0.44 The figures in italics refer to the new determinations the others being those previously obtained for the fifty-one original specimens examined. There is about double as much of the radioactive sub- stances in the granite as in the schists and the heat derived from these substances agrees with Stapff's measurements of the temperature gradients 20.9 metres per 1' in the granite and 46.6 metres in the schists.The radioactive hypothesis of t h e origin of the abnormal heat in the St. Gothard tunnel is the most probable. F. S. Radium Content of Secondary Rocks. ARNOLD L. FLETCHER (Phil. Mag. 1912 [vi] 23 279-~91).-Tbe radium in eighty-two specimens of secondary rocks has been determined by the fusion method. With the exception of the small and relatively unimportant class of calcareous rocks all the secondary rocks were found to contain very nearly the same quantity of radium namely 1.4( x 1O-I2 gram per gram). The mean found for the calcareous sediments was 0.8. The coarce detrital sediments contained somewhat higher amounts of radium on the average than the fine classed as Argillaceous and Schistose. I?. s.GENERAL AND PHYSICAL CHEMISTRY. ii. 225 Dielectric Constants of Binary Mixtures and their Refrac- tivity for Long Waves. ALFRED SCRULZE (Zeitsch.Elektrochem 1912 18 77-93. Compare Dolezalek Abstr. 1909 ii 22).-The dielectric constants of the four binary mixtures ether-chloroform benzene-carbon tetrachloride benzene-chloroform and benzene-ether have been determined a t a series of temperatures by the bridge method and from the results the molecular refractivities for long waves have been calculated by the known formula. If two liquids mix without alteration of properties the molecular refractivity of the mixture expressed according to the method of Lorentz must be repre- sented by a straight line. I f the liquids enter into chemical combina- tion it is plausible to assume that the refractivity will increase with the size of the molecule and therefore that the experimental curve will be above the straight line for an ideal mixture.If on the other hand the molecular complexity of one of the components diminishes on mixing with the other component the refractivity of the mixture should be less than the mean refractivity of the components. On this basis the equilibrium constants or association constants are calculated as already described in connexion with the vapour pressures of binary mixtures (Zoc. cit.) and it is shown that ether and chloroform form a compound containing one molecule of each that carbon tetrachloride is associated that benzene and chloroform mix with very slight alteration of properties and that benzene and ether enter into chemical com- bination. The results confirm in all respects those deduced from the vapour-pressure measurements. G.S. Some Electrical Properties of Sodium and Potassium and their Alloy. EDWIN F. EOKTHRUP (T~ans. Amer. Electrochem. Soc. 191 1 20 1 S5-204).-The electrical resistance of metallic sodium increases proportionally with the temperature. There is a sudden and large increase at the melting point and the reeistance of the liquid sodium then increases in linear proportion. At 20" the specific resist- ance is 4873 x Potassium behaves in a similar manner the specific resistance being 7116 x 10-9 at 20' and 15306 x The liquid alloy containing equal volumes of sodium and potassium has a much higher specific resistance 33792 x at 20' and 37872 x at 100'. C. H. D. and at loo' 9724 x at 100".The Conductivity of Mixtures of Copper Sulphate and Sulphuric Acid. HENRY K. RICHARDSON and FLOYD D. TAYLOR (Yrans. Amer. Electrochem. Soc. 19 11 20 179-184).-Addition of copper sulphate increases the conductivity of a solution of sulphuric acid containing less than 3 grams per 100 c.c. and diminishes the conductivity of the mixture if more sulphuric acid is present. C. H. D. Potential of the Potassium Electrode. GILBERT N. LEWIS and FREDERICK G. KAYES (J. Amer. Chem. Soc. 1912 34 119-122).-The potential of the potassium electrode has been determined by the method employed by Lewis and Kraus (Abstr. 2910 ii 127) in the case of the sodium electrode.ii. 226 ABSTRACTS OF CHEMICAL PAPERS. The results show that the potential of potassium in a N-solution of potassium ions at 25' is 3.2084 volts against the normal calomel electrode taken as zero.This value is the sum of (1) 2.1603 volts the potential of potassium amalgam (containing 0.2216% K) against an aqueous solution containing potassium ions in N-concentration and (2) 1.0481 volts the difference of potential between potassium and 0.2216% potassium amalgam in a solution of potassium iodide in e t hylamine. The temperature-coefficient of the latter E. M.T. is 0.000272 volt per degree and hence the heat of solution of 1 gram-atom of potassium in 0.2216% potassium amalgam is 26,050 cal. Preliminary experiments have been made to asoertain the extent to which this method is applicable in t h e case of lithium rubidium cmium and the alkaline-earth metals. Galvanic Cells with Carbon Anodes.P. BECHTEREFF (Chern. Zentr. 1912 i 106-108 ; from Iwiestja Petersburg Polytech. 1911 15 443-526).-Measurements have been made of the E.M.E. electrode potentials and polarisability of cells with a carbon anode a metal cathode and fused sodium hydroxide as electrolyte at tempera- tures between 300' and 1400". The influence of the addition to the fused electrolyte of selenium selenium dioxide sodium selenate aud sodium nitrate was also examined for the temperature interval 320-650'. A t 400' the carbon anode becomes less electro-positive to the extent of 0.3 volt on the addition of 6% sodium nitrate. I n contact with a fused mixture of the carbonates of lithium sodium and potassium the anode potential differs from that for carbon in contact with fused sodium hydroxide by 0.8 volt. These changes indicate that the carbon electrode behave8 as a gas electrode. The behaviour of different passive metals such as iron cobalt nickel platinum gold silver and copper as well as that of constantan and tho oxide Fes04 is exactly the same according to electrode potential measurements.It follows from this observation that the measured cathode potential is that of air in contact with fused sodium hydroxide. Sodium nitrate chlorate and perchlorate potassium permanganate selenium and tellurium were found to act as depolarisers for the carbon anode. Platinum and silver are less readily polarised than iron and nickel and the tendency towards cathodic polarisation is diminished by the addition of sodium peroxide The E.M.B'.of the cell C I fused NaOH I Fe increases with rising temperature to a maximum of 0.9 volt and then diminishes when the electrolyte begiris to boil. Cells of the type C 1 fused B,O I Pt were also examined a t high temperatures oxygen compounds oi iron cobalt nickel copper and silver being added to the fused electrolyte. Such cells at high temperatures have an E.B.P. which in some cases exceeds I volt. E. G. H. M. D. A Generalisation of van't Hoes Formula. EDOUARD HEBZEN (Bull. Xoc. chim. BeZg. 1912 26 15-18).-From a consideration of the equilibrium between two electrolytes having an ion in common and the solution saturated with respect to both the author deduces anii. 227 GENERAL AND PHYSICAL CHEMISTRY. expression from which the ionisation of each electrolyte in the common solution may be calculated.The data required are the concentration and degree of ionisation of each electrolyte in its own saturated solution and the concentration of both in the common solution. H. M. D. Conductivity and Photoelectric Hysteresis of Isomorphous Mixtures of Sulphur and Selenium and of Selenium and Tellurium. LAVORO AMADUZZI and MAURIZIO PADOA (Nuovo O h . 1912 [vi] 3 i 66-70).-Isomorphous mixtures of sulphur and selenium containing respectively 88.99 and 95.884 atomic "/o Se show photoelectric sensibilities expressed as the ratio of the conductivities in darkness and under illumination of 1.20 and 3.6. The second mixture shows considerable sensitiveness to variations of strong light whilst the first hardly responds to such variations.Hysteresis is observed of different character in the two mixtures. Isomorphous mixtures of selenium and tellurium from 0.887 to 10.081 atomic % Te give a curvo of sensibility which falls rapidly at first and then slowly with increasing tellurium content. Mixtures of sulphur and tellurium are devoid of photoelectric proper ties. C. H. D. The Hallwachs Effect and Phototropy. LAVORO AMADUZZI and MAURIZIO PADOA (Nuoao Cim. 1912 [vi] 3 i 41-50).-The substance to be examined is connected with a negatively charged electroscope ultra-violet light is allowed to fall on i t from a mercury lamp and the time taken to discharge the electroscope is observed. I n order to examine the effect a t different temperatures the substance is attached to the surface of a copper cube which may be filled with warm oil.The experiment is repeated with the same substance after it has undergone phototropic change of colour under the influence of sunlight. The examination of a number of arylhgdrazones of various aldehydes shows that the change of colour corresponds with a change of photo- electric power the latter being usually increased but occasionally diminished. Exposure to ultra-violet rays changes the photoelectric power even when a change of colour is not produced. Fatigue is observed. The photoelectric power of benzaldehydephenylhydrazone varies greatly with the temperature whilst piperonaldehyde- o-toly losazone and aniealdehyde-/3-naphthylosazone vary very little. C. H. D. Thermomagnetic Properties of Elements. MORRIS OWEN (Proc.K. Akad. Wetensch. Amsterdam 191 1 14 637-644. Compare Honda Abstr. 1910 ii 686).-Further measurements have been made of the magnetic susceptibility of the elements a t temperatures between that of the room and - 170". The new data indicate that the connexion between the magnetic susceptibility and the atomic weight is more intricate than was formerly supposed although a general periodic relationship is still observable. The influence of polymorphism is very pronounced and this introduces difficulties intoii. 228 ABSTRACTS OF CHEMICAL PAPERS the comparison of the susceptibilities of certain elements. According to the variation of the susceptibility with the temperature the elements fall into six different groups. Researches on Magnetism. IV. Para-magnetism at Very Low Temperatures.H. KAMERLIPI'GH ONNES and ALBERT PERRIER (Proc. K. Akud. Wetensch. Amsterdulm 191 1 14 674-678. Compare Abstr. 1911 ii 694).-It has been found previously that the magnetic Eusceptibility of solid oxygen does not follow Curie's law :st. liquid hydrogen temperatures. Data are now recorded which show that the susceptibility decreases slightly as the temperature is lowered from 20.3' (absolute) to 13.9'. The change i u the magnetic suscepti- bility when oxygen pass$rs from the solid to the liquid condition is found to be about four times as large as the change indicated in previous experiments with a different form of apparatus The discrepancy between the two results is attributed to the magneto- crystalline properties of solid oxygen and if this is the correct explanation i t is probable that the new method of determination affords a more exact value of the change in susceptibility at the melting point. Some experiments with ferrous sulphate (anhydrous) show that tho susceptibility increases as the temperature falls from 293' to 20.3' (abs.) and then diminishes as the temperature falls from 20.3 to 13.9'.The susceptibility has a maximum value a t a certain temperature and the behaviour is quite similar to that of solid oxygen. The Magnetic Susceptibility and the Magneton Number of the Oxides and Sulphides of Vanadium. EDGAR WEDEKIND and C. HORST (Ber. 19 12 45 262-270).-The specific magnetic suscepti- bility (x) and the magneton number (n = uw~/l123.5 where cry1 is the molecular saturation compare Abstr.191 1 ii 250 367 694) of the various compounds are as follows TO. V,O,. VO,. V,O,. VS. V,S,. V,S,. VOC1. VN. X X ~ O - ~ ... 50.06 13.88 3-73 0'86 7'22 8-95 12.55 27-18 4.13 n ............ 13.90 10.92 4.19 2.99 5.86 10.00 11.90 13.18 3-92 It is noteworthy that whilst the magnetic susceptibility decreases from the monoxide to the pentoxide it increases from the monosulphide to the pentasulphide. The second component may thus exert a decisive influence on the susceptibility of simple compounds of paramagnetic metals. The curve showing the relation between the magnetic susceptibility and (a) the sulphur content is a straight line on which the point for vanadium itself lies; (a) the oxygen content has a break corresponding with the position of each oxide. The magneton numbers differ very little from whole numbers and increase or decrease with the susceptibility without proportionality existing; they are smaller than those which have been found for chromium manganese or iron salts.The following special methods of preparation of vanadium monoxide and monosulphide are given. The monoxide is best prepared by heat- ing the solid oxychloride VOC1 to a red heat in a current of pure hydrogen until the brown mass has become quite black in colour and H. M. D. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 229 no longel. gives the test for chlorine; the reaction takes twelve to sixteen hours. Vanadium monoside forms a black amorphous powder D14 5,758 Which dissolves in dilute acids to a blue solution without gas being evolved In the compressed condition it conducts electricity.The pure monosulpl-iide could not be prepared by heating the trisulphide V,S in a current of hydrogen even at 1100-1200° (compare Kay Trans. 1880 37 728). Better results were obtained by heating the monoxide to a red heat in a current of hydrogen sulphide although even then the monosulphide was not quite pure. It forms a dark brown powder which is insoluble in alkalis and in hydrochloric acid but soluble in cold concentrated or in warm dilute nitric acid. T. S. P. Magnetic Properties of Manganese and Nickel Steels. SIEGFRIED I~ILPERT and WALTER MATHESIUS (Zeitsch. EZektrochem. 1912 18 54-64. Compare Abstr. 1911 ii 1057).-The effect of heating to different temperatures followed by more or less rapid cooling on the magnetic properties of the following alloys has been determined nickel steel containing 12% nickel ; mangmese steel containing 5 10 and 20% of manganese and manganese-carbon steel containing 10% of manganese and 1 or 2% of carbon.All steels show a maximum of magnetic power when quenched from about 450". Steels quenched from 1200' are more magnetic than those quenched from 900° or slowly cooled frdm 750". The manganese- carbon steels are practically non-magnetic when quenched from 900". From the behaviour of the steel quenched from 1200' when cooled in liquid air the conclusion is drawn that it coutains several magnetic constituents. With steels containing 5% of manganese or 12% of nickel the coercive power diminishes as the magnetic power increases whereas with 10% of manganese the coercive power and magnetic power increase concurrently.A steel containing 20% of manganese cannot be made magnetic by thermal treatment. From the magnetic behaviour of iron alloys conclusions can be drawn as to their previous thermal treatment. Photomicrographs of some of the quenched steels are given. G. 8. Use of the Magnetic Field in Determining Constitution. XII. PAUL PASCAL (Bull. SOC. chim. 1912 [iv] 11 111-121).-A further selection of compounds showing anomalous magnetic suscepti- bility is dealt with (compare Abstr. 1911 ii 850 1058). Whilst the -GO- group in ketones and aldehydes is associated with reducing power in these substances this property is less marked in acids amides etc. probably becauae the residual affinities of the group are saturated in these cases.I n harmony with this view i t is found that whilst in the aldehydes and ketones the influence of the -GO- group on the magnetic susceptibility is + 66 x 10-7 it falls to + 13 x 10'7 for acids and esters to + 32 x 10-7 for monoamides and to +26 x 10'7 for diamides and imides. I n carbamide the influence disappears entirely. In the acid chlorides on the con- VOL. CII ii. 16ii. 230 ABSTRACTS OF CHEMICAL PAPERY. trary the effect of the 40- group is normal probably because the supplementary valencies of chlorine do not affect oxygen since these two elements do not easily combine. Among halogen compounds the magnetic susceptibility is not abnormal so long as the group containing the halogen is not so situated that the halogen can easily be eliminated as hydrscid but where this latter condition enters the magnetic susceptibility shows a decrease ; thus for methyl chloride Sa is 333 in place of 363.5 calc.For alkyl chlorides the depreciation is about 31.5 x 10-7 and for alkyl bromides or iodides about 42.5 x the difference corresponding with the greater ease with which the bromides and iodides lose their halogen atoms as hydracids as compared with the chlorides. These deprecia- tions in value it is assumed are due to deformation of the molecule in the direction of an ethylene linking and it is argued that the amount of the depreciation may be taken as a measure of the tendency of the alkyl haloid to become an ethylene derivative and by taking account of all possible linkings in the substance in this way it is shown that the depreciation can be calculated fairly approximately and a number of examples are given.T. A. H. New Thermodynamic Theories (Nernst's Heat Theorem and MAX PLANCK (Bey. 1912 45 5-23).-A Quanta-Eypothesis). lecture delivered before the German Chemical Society. T. S. P. A Simple Relation between the Expansion Coefficient of Liquids and Temperature. MARCEL OSWALD (Comnpt. rend. 191 2 154 61-63).-The author develops the expression a= 1/(2Tc - T) where a is the coefficient of expansion of a liquid at absolute temperature T the absolute critical temperature being T,. This is similar to an equation given by Thorpe and Rucker (Trans. 1884 45 135). On applying it in the generalised form a = l/(M; - T) to 15 simple organic and inorganic liquids satisfactorily constant values for X were obtained the mean being 1.967.Liquids containing polymerised molecules show some departure from the rule. The anomalous case of water is discussed; at 100" the calculated value for T.. is 322.5'. The formula may be useful in calculating approximate values for critical temperatures. w. 0. w. The Measurement of Very Small G a s Pressures. CLARENCE F. HALE (Tmns. Amer. Electrochem. SOC. 191 1 20 243-258).-The low pressure manometer devised by Pirani (Ber. deut. physikal. Ges. 1906,8 686) depends on the fact that at low pressures the thermal conductivity of a gas is a function of its pressure. The sensitiveness has been greatly increased by the following improved construction. A platinum wire 0.028 mm. in diameter and 450 mrn.long is looped and attached to glass supports sealed into a glass bulb provided wich a side-arm for connexion with the system of which the pressure is to be examined. The compensator is identical in form but without the side-arm. Both bulbs are immersed in a bath at constant temperature. The manometer and compensator form two arms of a Wheatstone bridge and the current from five cells is regulated so as to be 0.00925GENERAL AND PHYSICAL CHEMISTRY. ii. 231 ampere which keeps the platinum wires a t about 125' a t the lowest pressures. The manometer is calibrated against a McLeod gauge with the same gas as that for which it is to be used. Trustworthy measurements are given down to 0.00001 mm. of mercury. C. H D. Elastic Force of Saturated Vapours. F.OLLIVE (Compt. rend. 1912 154 188-190).-When the temperature of a vapour is raised by increments in arithmetic progression the elastic force of the vapour should rise in geometrical progression. The correctness of this con- clusion is shown by applying it to the case of water vapour at tem- peratures between Oo and looo employing the formula A = (;4pqL-l where a and q are constants and h represents the successive rncre- ments in pressure. Between 0 and 40° a = 0.32 mm. Q = 0.36/0*34 ; between 40 and SO0 a = 3.2 mm. q = 3*3/3*2 ; at 50-70' a = 4.6 mm. q = 4-8/4*6 ; at 70-loo" a = 10.5 mm. q = 1.033. For other liquids a and q vary to a less extent with temperature. w. 0. w. Thermal Conduction and Convection in Gases at Extremely High Temperatures. IRViNG LANGMUIR (Trans. Arner.Ekctrochem. Soc. 191 1 20 225-242).-Former experiments with a Nernst filament (Abstr. 1906 ii 848) led to some unexpected conclusions as to conduction and convection in the neighbourhood of the filament these properties increasing very rapidly at high temperatures. The range of temperature over which the Nernst filament can be used is very limited and experiments have now been made with ductile tungsten wires in hydrogen. The energy required to heat the mire to any given temperature is nearly independent of the size of the vessel containing the hydrogen. The fraction of the current carried by the hot gas near the wire is inappreciable even at the highest tempera- tures when the wire is straight but becomes considerable a t 2900' (abs.) when loops are used. The loss of energy at first increases pro- portionally to a power of the temperature between 1 and 2 but then much more rapidly and at 3400' (abs.) is increasing with the tenth power of the temperature.I n a vacaum the loss is proportional to the 4.8 power of the temperature and this exponent is constant over a wide range. The melting point of tungsten is at least 3450' (abs.). C. H. D. Thermal Conductivity of Graphite and Diamond. JOHANNES KOENIGSBEBGER (Ber. deut. physikal. Ges. 19 12 14 9).-The marked contrast bet ween the thermal and electrical conductivities of graphite is also found in the case of diamond. The high thermal conductivity of carbon (and silicon) is supposed to be connected with the rapid diminution of the specific heat which is exhibited by these substances when the temperature is lowered.H. M. D. The Thermal Conductivity of Graphite and Copper Sulphide at Various Temperatures. ICOLE (Ann. Chim. Phys. 1912 [viii] 25 137-144).-The thermal conductivity of graphite 16-2ii. 232 ABSTRACTS OF CHEMICAL PAPERS. has been measured by placing a cylinder 18 mm. in diameter and 7.9 mm. long between the ends of two copper rods each of the slime diameter and 50 cm. long the temperature of the copper being read by means of thermo-couples i n transverse holes. The conductivity is expressed by the formula K= 0,0384 - 9 x 10-5t + 9.3 x lO-7t2. The conductivity of synthetic copper sulphide determined in the same manner is very nearly proportional to the temperature and may be expressed by the formula K= Os0O106 + 4.3 x lo-".Specific Heat of Gases. 11. NIELS BJERRUM (Zeitsclb. Elektro- chem. 1912 18 101-104. Compare ibid. 1911 1'7 731).-Jn the previous paper (Zoc. cit.) formulz for the specific heats of a number of gases we1e deduced on the basis of the quanten theory the constants being calculated from the results of Pier's determinations of specific heats by the explosion method (compare Abstr. 1909 ii 789 ; 1910 ii 1031). A slight correction rendered necessary by loss of heat during the explosion is now applied. Some of the recalculated molecular heats a t constant volume are 8s follows hydrogen 5.23 a t 1461" 5.57 a t 1916' 5.79 a t 2368'; nitrogen 5.43 at 1519' 5.93 at 2367O ; argon theoretical 2.978 found 2.93 ; water vapour 8.13 a t 1734O 8.52 at 2134O; 9.39 a t 2375'.The corrected results are compared with those calculated from the formulz ; the agreemcnt is Specific Heat Measurements at Low Temperatures. ALEXANDER 5. RUSSELL (Physikal. Zeitsch. 191 3 13 59-64).-The results of measurements of mean specific heats over the temperature ranges + 45' to Oo Oo t o - 7S0 and - 78' t o - 190' are recorded. The calorimeter described by Nerrist and Lindemaun (Ahstr. 1910 ii 263) was used and observations made with the oxides of copper lead magnesium mercury iron chromium aluminium arsenic scandium cerium manganese thorium tungsten and uranium the sulphides of mercury copper cadmium and antimony the chlorides of sodium potassium and thallium and also with metallic thallium amorphous and crystalline quartz and silicon carbide.I n general the data show that t h e molecular heats at low tempera- tures diverge considerably from the values calculated by adding together the atomic heats of the component elements. By reference t o the Nernst-Liudemann formula for the molecular heat this means that the characteristic vibration frequencies of the elements in their compounds are different from the frequencies of the free elements. In the case of metals such as lead tungsten and mercury which have low vibration frequencies the differences are comparativoly small and for these metals the observed molecular heats of the oxides and sulpbides are in fairly close agreement with the requirements of the additive law. The behaviour of oxygen at low temperatures does not depend t o any appreciable extent on the metal with which it is corn bined. H.M. D. Molecular Heat of Hydrogen at Low Temperatures. ARNOLD EUCKEN (Siizungsber. K. Akad. Wiss. BerEin 19 12 141-151).-A form of apparatus is described for the determination C. H. D. good throughout. a. 8.GENERAL AND PHYSICAL CHEMISTRY. ii. 233 of the specific heat of compressed gases at constant volunie and at any desired temperature. With this measurements have been made of the specific heat of hydrogen at temperatures between 35' and 273" (absolute). The data thus obtained when reduced to the ideal gas condition show that the molecular heat falls from 4.84 at 273' t o about 3.0 at 60' (abs.). Below 60° the molecular heat remains constant. The observed temperature variation of the molecular heat at constant volume can only be accounted for qualitatively on the basis of existing theories and the additional hypotheses necessary for its in terpretat,ion are discussed.H. M. D. A General Law of Dissolution. MILE BAUD (Compt. rend. 1912 154 195-201. Compare Abstr. 1910 ii 268-689).-The equation At = Klogx.T2 deduced to express the depression of the freezing point of binary mixtures where x is the concentration of a component A in a mixture depositing pure A at a n absolute temperature Y2 does not hold for incompletely miscible liquids In such cases the more general equation T2 = TI. (1 - q/Q)/( 1 + klogx) deduced from Clapeyron's equation is applicable. 1; represents the freezing point of the solvent and k the ratio RT,/E& q being the heat of dilution that is the heat developed by the addition of one molecule of A to a large qvantity of solvent.This expression has been tested experimentally i n the case of mixtures of acetic acid with benzene or ethylene dibromide with sat iaf ac t ory results. w. 0. w. Fused Salts as Solvents. I. Cry oscopic Investigations. 11. Solubility Determinations. OTTO SACKUR (Zeitsch. physikal Chem. 1912 '78 550-563 564-572).-I. As solvents the chlorides of sodium potassium calcium strontium and barium and sodium sulphate were used and a s solufes a number of alkali and alkaline-earth salts. The investigation shows that as a rule the laws of dilute solutions are approximately valid u p t o concentrations of 1 mol. per litre. Dissolved salts which have an ion in common with the wlvent have either the normal molecular weight or show a slight dissociation independent of the concentration.This result is probably to be explained by considerable ionkation of the solvent itself. Salts which have no ion in common with the solvent produce nearly double or nearly three times the normal depression according as they are binary or ternary electrolytes. A number of biuary mixtures of salts form solid solutions and therefore the laws of dilute solutions do not apply to cryoscopic measurements with such mixtures. When for example strontium carbonate is a,.Jed t o fused potassium o r sodium carbonate t h e melting point rises a t first with increasing concentration of the strontium salt and then gradually diminisheg so t h a t a flitt maximum is obtained. Flat maxima are also obtained with strontium carbonate and barium sulphnte in sodium sulphate as solvent.11. Jn the soliibility determinntions the same fused salts were used ac solvents and as criterion of sohibility the effect of the substance added on the melting point of the solvent was used. It was found t h a t all those substances which can readily dissociate int two or moreii. 234 ABSTRACTS OF CHEMICAL PAPERS. stable ions are readily soluble whereas those substances which do not readily ionise (for example the aliiminates and ferrites of the alkalis the oxides of the alkaline earths and heavy metals and the sulphides of the heavy metals) are practically insoluble. The only exception to these rules are the oxides of the alkaline earths which are readily soluble in fused chlorides with a common ion; for example calcium oxide is readily soluble in fused calcium chloride.G S. Cryoscopy in the Fused Pentahydrate of Sodium Thio- sulphate. CH. LEENHARDT and A. BOTJTARIC (Compt. rend. 1912 154 113-114. Compare Abstr. 1911 ii? 106l).-The latent heat of fusion of the salt Na2S,0,,5H20 at the melting point 48*5O is found to be 47.9' as the niean of three concordant determinations. Employing van't Hoff's formula this gives K 42.8 as the molecular lowering of the freezing point a number which agrees well with that found by dissolving cazbamide in the fused salt. Trentinaglia's values (Wlien Ber. 1876 72 669) are considered to be untrustworthy owing to the possibility of his salt containing water. To avoid this it is necessary to dry the pentahydrate in presence of the dihydrate.w. 0. w. Improvements in the Ebullioscopic Method. ERNST BECKMANN [with WALTER WEBRR] (Zeitsch. physikal. Chern. 1912 78 725-740. Compare Abstr. 1908 ii 663).-The irregularities in ebullioscopic measurements which are especially pronounced when the solution froths are not got rid of by using wire of other metals instead of platinum for internal electric heating; of the different metals used only gold gave rather better results than platinum. The introduction of a stream of a permanent gas such as hydrogen air or carbon dioxide is also not satisfactory as among other drawbacks the end of the tube through which the gas enters tends to get choked up by the entry of solution and evaporation of part of the solvent.The usual device of introducing filling material gives the best results. A considerable improvement is obtained by so modifiying the apparatus that part of the solvent (containing traces of volatile substances especially moisture) can be distilled off a current of dry air being introduced a t the bame time to prevent the condensation of moisture in the upper part of the apparatus. The fraction passes OE through tbe side-tube used for introducing the solid; for this purpose the usual stopper is replaced for the time by another connected with a long bent tube as condenser. The use of an aneroid barometer has been recommended to correct for variations in atmospheric pressure during an observation but it is shown that a control boiling-point apparatus gives much better results G.S. Fractional Distillation with Steam. A. GOLODETZ (Zeitsch. physikal. Chem. 1912 78 641-656).-1t is shown that a mixture of low-boiling liquids insoluble in water can be more effectively separated by distilling with steam than by ordinary fractional distillation underGENERAL AND PHYSICAL CHEMISTRY. ii. 235 the same conditions. The advantages of steam distillation are much less for the separation of high-boiling liquids. Young’s law according t o which the amount of the mixture which distils up to the middleof of the temperature-interval between the boiling points of the two components is approximately equal t o the amount of the more volatile component is confirmed. I n the course of the experiments binary mixtures of benzene and toluene of amyl formate and acetate of mono- and di-ethylaniline were fractionated and several types of fractionating column were used G.S. Heats of Formation of Certain Silicates. D. TSCHERNOB~FF and L. WOLOGDINE (Compt. rend. 1912 154 206-208. Compare Abstr. 1905 ii 678).-M ixtui-es of calcium carbonate with silica or kaolin or with silica and alumina were heated with a definite amount of carbon in the Mahler bomb calorimeter. From the heats of reaction thus determined the following values for the heats of combination were calculated the numbers being in CalorieR CaO + SiO 17.4 ; 2Ca0 + SiO 28.7 ; 3Ca0 + 2SiO,,Al,O + 50.2 ; 3Ca0 + 2Si0 + Al,O 38.2 ; SiO + Al,? - 12.0. The heat of formation of anhydrous kaolin A1,0,,2S~0~ is therefore negative. These results are not in harmony with those previously published. w.0. w Heat of Combustion and Heat of Transformation of the Cinnamic Acids. W. A. .ROTH (Zeitsch. h’lektrochem. 1912 18 99-100).-The heat of transformation of altocinnamic acid to cinnamic slightly exceeds 6000 cal. per mol.; the heat development accompanying the cbange of the aEZocinnamic acid melting at 4 2 O to that melting a t 58’ is about 100 cal. The heat of com- bustion of cinnamic acid a t constant volume is 7025 cal. per gram. G. S. Method of Measuring Absolute Viscosity. HAROLD P. GURNEY (J. Amer. Chem. Soc. 1912 34 24-28).-Apparatus is described for the determination of absolute viscosity. The method is simple rapid and extremely accurate requires only a very small qnantity of the liquid and enables opaque liquids to be tested.Into the neck of a small flask are fitted three glass tubes one connected by a stopcock to the vacuum pump the second by rubber tubing to a vertical glass tube of capillary bore whilst the third carries a stopcock opening to the air. The capillary tube has three rings etched round it at different heights and its lower end dips into a small cup with vertical walls which contains the liquid. If determinations are to be made a t other temperatures than that of the air the tube must be jacketed. In carrying out an experiment the liquid is poured into the cup until it rises just within the capillary tube up to the lowest ring. It is then sucked up the tube by means of the pump until it is above the level of the highest ring. The stopcock connecting the apparatus with the pump is then closed and that opened which is in communicationii.236 ARSTRACTS OF CHEMICAL PAPERS. with the atmosphere so that the air above the liquid in the tube is under atmospheric pressure. The liquid in the capillary descends with but slightly diminishing velocity and the time taken by it t o pass from the highest ring to that next below it is observed with a stop-watch. A mathematical discussion is given leading to the development of a formula for calculating the results. E. G. Viscosity of Solutions of the Metal Ammonia Salts. ARTHUR A. BLANCHARD and HAROLD B. PUSHEE (J Anier. Chem. Isoc. 1912 34 28-32).-Blanchard (Abstr. 1904 ii €305) has shown that when ammonia is added to solutions of salts of copper silver and zinc a phenomenon similw to negative viscosity is produced.This was explained on the assumption that the ions combine with a certain number of molecules of the solvent. Determinations have now been made of the viscosities of solutions obtained by adding succes$ive quantities of ammonia to solutions of ammonium chloride calcium chloride and lithium sulphate a t 25" and to solutions of lithium chloride a t lo. The results show that in these cases instead of a negative viscositly a slight increase in the viscosity occurs. It is evident therefore that such unstable complexes as are formed between ammonia and salts of lithium ammonium and calcium are somewhat more viscous and hence either larger or less symmetrical than the ordinary complexes of the same salts with water in simple aqueous solutions.E. G. Adsorption. 111. GERHARD C. SCHMIDT (Zeitsch. physikal. Chem. 1912 '78 667-681).-The adsorption formula [(a - z)S]/v = KxeA(s-z)s (x representing amount adsorbed a the amount of solute originally present v the volume 8 the maximum amount adsorbed and A and K (:onstants) ttlyeady deduced by t.he author (compare Abstr. 1911 ii 969) is shown to representwith great accuracy the results of Titoff (Abstr. 1910 ii 1041) on the adsorption of gases by cbarcoal and with fair accuracy the corresponding measurements of Homfray (Abstr. 1910 ii 771 1041). Neither of these observers determined the maximum adsoqtion and the author has estimated it by extra- polation. The simpler adsorption formula recently suggested by Arrhenius (this vol. ii 139) does not represent satisfactory the author's results on the adsorption of acetic acid from aqueous solution by charcoal whereas they are represented with great accuracy by the above formula (Zoc.cit.). G. S. Adsorption in Solutions. 111. Relations between the Adsorbability and other Properties. GEORG VON GEORGIEVICS (Monutsh 1912 33 45-62. Compare Abstr. 1911 i 537 ; ii 1070). -The distribution of nitric hydrobromic propionic and butyric acids between water and wool has been examined and it is shown that the data are in agreement with the exponential adsorption formula. The adsorbabilit'y of different acids appears to have no connexion with the degree of ionisation although in general the stroDg acids are moreGENERAL AND PHYSICAL CHEMISTRY. ii. 237 readily adsorbed than the weak acids.Experiments with hydrochloric and sulphuric acids indicate that the adsorption of these is not influenced to an appreciable extent by the addition of small quantities of the corresponding sodium salts although larger quantities give rise to increased adsorption. The influence of other factors on the adsorption is discussed and it is shown that in certain groups of acids the adsorbability appears to be connected with the surface tension the compressibility and the viscosity of the solutions. H. M. D. Adsorption. IV. Thermodynamics of Irreversible Procesees and Chemical Hysteresis. ADAM W. RAKOWSHI (J. Russ. Phys. Chem. Soc. 1911 43 1762-1784. Compare Abstr. 1911 ii 470 4'71)-This is a mathematical paper the principal conclusions drawn by the author being as follows If in nuhem's theory of chemical hysteresis (Abstr.1900 ii 538) the variable x is rejected and the hysteresis attributed to the specific volume and degree of hydration of the colloid a fundamental equation is deduced completely analogous to Duhem's equation the difference lying merely in the physical significance of the constants. The formula derived by Duhem to express the influence of variation of the pressure on the velocity of hydration and dehydration of colloids corresponds with all the phenomena observed experimentally. Duhem's theory explains satisfactwily the various phenomena of chemical hysteresis. The isothermal equation of the natural state of an aqaeous colloid represents a sine curve. Gels possess a complex isotherm representing the sum of the sine curves charscterising the two '' solutions " which constitute the gel; physical explanations can be given of all the constants in the equation of such a complex sine curve.T. H. P. A Method of Investigating the Transpiration of Gases Through Tubes. JOSEPH H. T. ROBERTS (Phil. Mag. 1912 [qi] 23 260-255).-A method is described of obtaining the viscosity coefficients of gases from comparative measurements of the rates of transpiration. The transpired gases are allowed to escape into the atmosphere through short capillary tubes the pressure in the apparatus being only slightly greater than atmospheric. This pressure is automatically kept constant and the times required for the tran- spiration of the same volume of different gases are measured.With this apparatus the following viscosity coefficients were determined air 0.0001 80 at 11 -75" ; hydrogen 0.0000864 a t 12.25' ; carbon dioxide 0*000145 at 12.6'; coal-gas 0.000133 at 12.9O. H. M. D. Mechanism of the Semi-permeable Membrane and a New Method of Determining Osmotic Pressure. FREDERICK T. TROUTON (Proc. Roy. SOC. 1913 A 86 149-154).-A method of measuring the osmotic pressure of an aqueous solution is described which consistfl in determining the pressure to which a suitable liquid must be subjected when in contact with the solution in order that the liquid may take up as much water from the ,solution as it takes up from pure water at atmospheric pressure.ii. 238 ABSTRACTS OF CHEMICAL PAPERS From experiments in which the amount of water taken up by 100 grams of ethyl ether from a solution containing 600 grams of sucrose per litre was determined it has been found that this increases in a continuous manner from 0.939 gram a t atmospheric pressure to 1.143 gram at a pressure of 110.5 atmospheres. From the curve representing the variation of the amount of water taken up by the ether with the pressure it is found tbat the water taken up from the solution at a pressure of 79 atmospheres is equal to that taken up from pure water a t a pressure of 1 atmosphere (1.0545 gram per 100 grams of ether).This value of the osmotic pressure is in good agreement with that interpolated from the results of measurements with a copper ferrocyanide membrane by Lord Berkeley and Hart ley (Sl atmospheres). H. M. D.Theory of Dissolutions Compared with Experience (Case of Nitrogen Peroxide). ALBERT COLSON (Compt. vend. 1912 154 276-279. Compare Abstr. 1911 ii 710 1066-1071).-Polemica1 against Urbain and others (Abstr. 1911 ii 861). If the dissolved particle is in the same condition as the gaseous particle the gas equation Sm log C = K should hold for the same substance whether in solution or in the gaseous state. Cundall has shown for the equilibrium N,O 2NO in chloroform solution that the expression does not give a constant value for K. By measuring the partial pressures of the two gases in equilibrium it has now been found that the equation does not hold for the gaseous phase. w. 0. w. Theory of Solubility. DAN TYRER (J. Physical Chem. 1912 98 69-85. Compare Trans 1911 98 871).-The formation of a solu- tion is due to (l) molecular attraction of the solvent for solute and (2) mechanical diffusion of the solute molecules away from the parent solute by reason of their kinetic motion.Except with gases and easily volatile liquids the factor (2) is negligible. The intensity of the molecular attraction (1) depends on the nature of the solvent and the temperature. I n the case of liquids above their critical temperature when T is maintained constant and C is altered by altering the external pressure the solubility is proportional to the concentration (C) of the solvent. Below the critical point C depends on the pressure the temperature and the presence or absence of neutral molecules and of solute molecules. The ordinary solubility curve is without theoretical value since it refers to an arbitrary pressure (1 atmosphere) and a continuously varying solvent concentration. When both solvent and solute are normal tbat is free from the disturbing influences of dissociation association and solvate formation the conditions at saturation can be deduced.I f the attraction between two solute molecules varies inversely as some power of the distance between them the total force holding a molecule of solute to its parent crystal is K/vn where K is a constant and v the specific volume of the solute. ‘l’he forces tending to draw a solute molecule into solution are (1) the attraction of the solvent That is to say the solubility S=+(C,T).GENERAL AND PHYSICAL CHEMISTRY. ii. 239 ( = K,/Vn) and (2) the attraction of the solute molecules already dissolved (= R 2 N " / P ) where Kl K2 are constants and V the total volume of a solution containing a constant weight of fiolvent plus N molecules of solute.Now iV=X/~tl where X is the solubility and M the molecular weight of the solvent. It follows that X.=a(V/v)n-b where a b and n are constants. This equation cannot be tested experimentally since n is unknown but it is evidently in qualitative agreement with the general phenomena attending the dissolution of normal substances whether gaseous liquid or solid in normal solvents. The author works out the conditions for complete miscibility of pairs of normal liquids. I n practice all normal liquids are miscible in all proportions that is the solubility is intinite. It follows that normal solids become infinitely soluble a t their melting points.The '' molecular solvent power " of a solvent is the amount of solute dissolved at a given temperature when unit volume contains 1 gram- molecule of solvent The molecular solvent powers of chloroform toluene benzene and hexane for naphthalene are deduced. A t saturation K/v" = K l / P + K2Nm/Vn. R. J. C. Miscibility of Liquids. J. P. KUENEN (Proc. K . Akad. Wetertsch. Amsterdam 191 1 14 644-649).-The influence of temperature on the miscibility of n-butane with methyl alcohol has been found t o vary in a marked manner with the method of preparation of the hydrocarbon. For butane obtained by the action of magnesium on butyl halides the critical temperature and pressure were found to be 1 5 0 .8 O and 3 7 ~ 5 ~ atmospheres and this becomes completely miscible with methyl alcohol a t 17.0'. When the butane is prepared by the action of sodium dissolved in liquid ammonia on butyl halides its critical temperature was found to be 148*7O and the criticd pressure about 39 atmospheres In spite of the close agreement in the critical data the second sample of butane behaved quite differently from the first in regard to its miscibility with methyl alcohol. The surface of separation appears to vanish a t about 22' but it reappears as the. temperature rises and the definite critical end-point is not reached until 38O. It is supposed that the phenomenon is due to the equality of the refractive indices of the two liquids in the neighbourhood of 2 2 O and that the difference in behaviour of the two samples of butane is due to the presence of a very small quantity of some impurity in the butane prepared by the action of sodium.The following critical end-points are also recorded methyl alcohol and isopentane 10.5O; methyl alcohol and n-pentane 1 9 . 4 O ; ethyl alcohol and iuopentane - 30°. H. M. D. Neutralisation Curve of Sulphuric Acid. JOHANNES E. ENKLAAR (Chem. Veekblad 1912 9 28-31. Compare Abstr. 1911 ii 1 U7 I).-The a.uthor has studied the step-by-step neutralisation of sulphuric acid effected by addition of successive quantities of N/10- sodium hydroxide to 10 C.C. of N-sulphuric acid and dilution of the mixture to 100 C.C. a t 18". For each addition the values of the total E.M.F. the E.M.P. of the gas-electrode the concentration of theii.240 ABSTRACTS OF CHEMICAL PAPERS. hydrogen ions and the values of Pa are summarised in a t.tble. A curve is plotted with the number of C.C. of sodium hydroxide as abscissae and the values of Ph as ordinates. This curve indicates that tho dissociation is in great measure ternary and in accordance with the scheme H2S0 2&+60,. The valuo found for the con- centration of the hydrogen ions in N/lO-sulphuric acid is 0.0523. The value for K2 is 0.013 and not 0-01s as given in the previous paper. A. J. W. A Colour Effect of Isomorphous Mixture. HORACE L. WELLS ( A m . J. Sci. 1912 [iv] 33 103-104).-Mixed crystals as a rule take a colour intermediate between those of their component salts ; for example the yellow salt Cs,PbCI and the deep blue salt Cs,S bC1 6 give mixed crystals of a green colour.An exception to this ruIe is afforded by the salts Cs,PbCI and Cs!,TeCI both of which crystallise in regular octahedra with a yellow colour. These salts are iso- morphous and mix in all proportions but their mixed crystals possess the peculiarity of showing a bright orange-red colour. L. J. S. Crystalloids and Colloids. Basic Ferric Chloride. GTOVANNI MALFITANO (Ann. Chim. Phys. 1911 [viii] 24 502-553).-To a large extent this is a summary of work published previously (compare Abstr. 1905 ii 459 ; 1906 ii 450 526 647 ; 1907 ii 94; 1909 ii 473). From the general behaviour of the colloidal ferric hydroxy- chlorides the author draws the conclusion that the properties of the micelles are closely similar to thoee of molecules and that there is no eesential difference between the micellar and molecular states. H.&I. D. Colour and Degree of Dispersity of Colloidal Solutions WILLIAM HARRISON (Zeitsch. Chem. Ind. Kolloide 1912 10 45-49). -The colour changes which are observed when colloidal acid and basic dyes are acted on by acids and bases in aqueous solution are examined in reference to Ostwald's view (Abstr. 1911 ii 868) that increase in the degree of dispersity of a colloidal solution is accompanied by a shift of the maximum absorption towards the ultra- violet end of the spectrum The colour changes are not generally in agreement with this theory and a modification is suggested. Accord- ing t o this it is necessary that the reduction in the degree of dispersity must be accompanied by an increase in the molecular weight of the disperse substance if the maximum absorption alters its position in accordance with the above rule.H. M. D. Fractional Coagulation. Relationship between the Size of Particles and the Stability of Disperse Systems. SVEN O D I ~ (Zeitech. phy&hZ. Chem. 191 2 78 682-707).-Ttie results described in the early part of the paper as t o the preparation of sulphur hydrosols containing particles of uniform size by the method of fractional coagulation have already been published (compare Abstr .,GENERAL AND PHYSICAL CEEMISTRY. ii. 241 1811 ii 971). The same method has now been applied to the separation of silver hydrosols into fractions of differeut degrees of dispersion and the properties of these solutions are described.The yellow ar,d red hydrosols contain only amicroscopic particles ; the purple and lilac sols contain submicrons. The polychromatic appearance of some silver hydrosols under the ultramicroscope described by previous investigators is not observed in fre.sh or carefully kept solutions but is observed when the hydrosols are kept in beakers of inferior glass or when ordinary tap water is present. The phenomenon is probably due to chemical changes on the surface of the particles. In the case of reversible coagulation the results show that under conditioiis otherwise equivalent the electrolyte concentration required to produce coagulation is the greater the smaller the colloidal particles. Experiments designed to find whether this rule also applies to irreversible coagulation did not lead to definite results.G. S. Theory of Dyeing. W. G. SAPOSHNIKOFF ( J . Rws. Phys. Chem. Soc. 1911 43 1565-1587).-The author has iuvestigated the effect of varying the concentration of the brth and the proportion of material taken on the dyeing of cotton mercerised cotton and artificial silk by a number of substantive dyes. The relation between p the number of mgs. of the colouring matber and P the number of grams of the dry fibre taken is given by the expression 10k.P where k is a coefficient termed the “modulus of the d;ey’ In the author’s experiments the propor- tions between the weights of colouring matter and fibre varied from 0.5% to 10%. The quantity of colouring matter in the bath per gram of fibre is represented by 10k which is termed the “limiting dyeing.” If the initial concentration of the dye in the bath is repre- sented by 10k/Kw the magnitudes P k and Kw must be regarded as the principal factors or the numerical characteristics of every substantive dyeing independently of the nature of the fibre or coloun ing matter and these magnitudes determine both the course of the dyeing and its final results If tc is the quantity of dye fixed by the fibre Cj=x/P the final concentration of the dye on the fibre may be termed the ‘‘ effective dyeing.” The final concentration of the bath is given by Cb = ( p - x)/&P.It is found that under similar conditions the final concentration of the bath is proportional directly to the difference between the limiting and effective dyeing and inversely to the water-modulus of the bath (Xw) independently of the nature of the colouring matter.In two substantive dyeings with identical moduli of bath and dye the ratio of the difference between the effective dyeings to the difference between the final concentrations of the baths is equal to the water-modulus of the baths. The substantive dyeing of cotton (cellulose) always follows one m d the same law no matter whether the natural structure of the fibre is unaltered (pure cotton) or ruptured (mercerised cotton) or completely destroyed (artificial silk).ii. 242 ABSTRACTS OF CHEMICAL PAPERS. Structureless celluloses such as artificial fibres prepared from solutions of cellulose and mercerised cellulose obtained from cotton are allied more closely to one another than to the original cellulose.The influence of mercerisation on the structure of cellulose fibres is hence as profound as that caused by their complete solution. Under the conditions employed in the author’s experiments mercerised cotton takes up on an average 10% more dye than pure cotton this increase being due to the loosening of the fibres on mercerisation. The degree of mercerisation should hence be indicated by the extent of the increase in the effective dyeing. The ratio between the effective dyeings of cotton produced by two different substantive dyes is very nearly equal to the ratio between the molecular weights of the dyes. T. H. P. Relation be tween the Photosensitiveness and Constitution of Dyes. KURT GEBHARD (J. pr. Chem. 1911 [ii] 84 561-625).-A theoreticdl paper in which the author gives an explanation of (1) the phenomena of substitution in the benzene nucleus (2) the diiferences in the reactivity of groups and atoms (3) the colour of organic compounds (4) the photosensitiveness of nitro-compounds and dyes based on the theory of ionisable and partial valency. F. B. Theory of Vat Dyeing. KURT GEBHARD (J. pr. Chein. 1911 [ii] 84 625-633).-An application of the author’s views on ionisable and partial valency (preceding abstract) to the theory of vat dyeing. From the difference in the behaviour of indigotin in the free condition and on the fibre Bins and Mandowsky (Abstr. 1911 i 497) have drawn the conclusion that the dye is not mechanically attached to the fibre but exists in some kind of union with it.The author has arrived a t the same conclusion from a study of the behaviour of helindone-yellow-3GN (2 2’-dianthraquinonyl- carbamide). Fibre dyed with this substance becomes brown or violet when treated with alkalis-a change not shown by the original dye. This difference is supposed to be due to an alteration in the distribution of the ionisable and partial valencies in the molecule. Formulae illustrating the nature of the combination of the dye with the fibre are given. F. B. Three-phase Lines. I. ANDREAS SMITS (Zeitsch. physikal. Chem. 1912 78 708-724).-8 theoretical paper. Van der Waals’ theory of the three-phase equilibrium solid-liquid-gas is extended in some respects and a mathematical and graphical diacuseion is given of the case where the triple point pressure of the cornpound is smaller than those of the components (compare Abstr.1905 ii 683; Leopold Abstr. 1910 ii 190). G. S . Gamium Nitrate and the Law of M a ~ s Action. WILHELM BILTZ (Zeitsch. Elektrochem. 1912 18 49-51. Compare Washburn and McInnes Abstr. 1911 ii 794).-The previous results of the author (Abstr. 1902 ii 310) and the recent measurements of Wash- burn and McInnes both show that in concentrations exceeding 0 . W -UENERAL AND PHYSlCAL CHEMlSTKY. ii. 243 czesium nitrate follows Ostwald’s dilution law. The few results of the latter observerd are not sutKcient to show mhether or not the law is obeyed in more dilute solutions. G. 8. Hydrolysis. I. Hydrolysis of Carbonates. FERNANDO AUENO and E. VALLA (Atti R. Accad. Lincei 1911 [v] 20 ii 706-712).- The authors have calculated the degree of hydrolysis of the carbonate8 of manganese nickel zinc and lithium by Bodlander’s method (Abstr.1900 ii 715) from measurements of the solubilities of these compounds in water in an atmosphere of carbon dioxide. The percentage hydrolysis of these salts at 25’ is found to be as follows manganese carbonate 99-99 nickel carbonate 98.92 zinc carbonate 96-75 lithium carbonate 42.53. The value for lithium carbonate is apparently too high in view of the known percentage hydrolysis of the carbonates of magnesium and sodium. The Velocity of Hydration of Some Cyclic Acid Anhydrides. JACOB BOESEKEN A. SCHWEIZER and G. F. VAN DER WANT (Pvoc. X.. Akad. Wetensch. Amsterdam 19 11 14 622-624. Compare Abstr. 1911 ii 197).-A theoretical paper in which a parallelism is traced between the hydration constant of the acid anhydride and the dissociation constant of the acid formed by union of the anhydride with water.H. W. R. V. S. Kinetics of Chemical Reactions of Combination Deoxida- tion and Oxidation. E. I. ORLOFF (J. Euss. Phys. Chem. Xoc. 1911 43 1524-1554).-The author brings forward an explanation of the time-relations ol the apparently irregular process of slow oxidation by permanganate referred to in N. A. Schiloff’d book on “Conjugated oxidation reactions.” In spite of their external differences all the examples of oxidation and deoxidation there given are processes of the second order their velocities being delermined from the differential equations dx/dt = k(A -fx) and dxldt = h(Bf+ .)(A -fx) where the magnitude x determined by titration of the iodine liberated from potassium iodide solution is multiplied by the coefficient f correspond- ing with the particular oxide of manganese formed on deoxidation of the Mn207 up to the moment of observation.Some thirty-four different examplev (there may be more) of the deoxidation of Mn207 to various lower oxides of manganese are given together with the corresponding values of f calculated from the amounts of iodine liberated. For instance Mn20? = 2Mn0 + 50 f = 1 ; 3Mr.1~07 = 6Mn0 + 30,f= 0.2 and so on. All the cases of slow oxidation of formic oxalic and tartaric acids considered are reactions of corn bination the first product being formed by addition of hydroxyl or oxygen to the acid; the compounds thus formed under go subsequent decomposition.Thus for oxalic acid Mn207 + 5H20 = 2Mn0 + 5H@2 and C02H*C02H + H202 = 20H*CO*OH = 2C02+ 2H,O ; for formic acid 2H*C02H +O = 20H*CO*OH = 2C0 i- 2H20 and for tartaric acid C02H*CH(OH)*CH(OII)*C02H + 0 = C0,H*C(OH),*C(0H),*CO2H a CC),H*CO*OO*CO,H +- 2H20.ii 244 ABSTRACTS OF CHEMICAL PAPERS. The reaction may proceed with or without formation of an inter- mediate oxide of manganese and in the former case this oxide may be Mn,O or MnO for example (1) Mn20,+8Mn0 = 5Mn203 and 5Mn20 + 5C,H20 = 10141n0 + I OCO + 5H,O ; (2) Mn,07 + 3Mn0 = 5Mn0 and 5Mn0 + 5C2H20 7 5Mn0 + 10C0 + 5H,O. Those reac- tions proceeding by way of an intermediate oxide are characterised by an incubation period. That is for some time only part of the oxidising agent (Mn,07) takes part in the oxidation the other part being held in reserve in combination with the oxalic or tartaric acid and set free only gradually.Hence the value of A,in the differential equation is not constant but increases to the final value A represent- ing the initial coucentration of the potassium permanganate. I n cases where the two stages of the reaction for example (1) Mn,O + 8Mn0 = 5Mn20 and (2) 5Mn,03 = lOMnO + 50 do not syn- chroaise intermediate oxides such as 2MnO,Mn,O and 4Mn0,Mn203 are formed. T. H. P. The Reaction Velocity of Reducing Sugars with Fehling’s Solution and its Application to the Study of Urinary Chemistry. J. N. LAIRD (J. Pucth. Bact. 2912 16 398-401).-8t constant temperature using in all cases the same amount of diluted Fehling’s solution the reduction (first appearance of a red precipitate) begins more rapidly the more concentrated the solution of sugar.The times are plotted out in curves for solutions of dextrose and lsvulose of known strengths at temperatures of 60° 65O and 70° respectively. By compariDg the times found for solutions of the sugar of unknown strength with these their concentration is ascertained. Solutions of sugar in urine do not however behave like aqueous solutions the presence of variable amounts of creatinine having a retarding effect. W. D. H. lnfluence of Temperature on Malt Diastase. HENRI VAN LAER (Bul2. SOC. chim. Belg. 1912 26 18-28. Compare Abstr. 1910 ii 839 ; 1911 ii 28 478 ; this vol. ii 148).-In previous papers it has been shown that depending on the conditions of the experiment and using a normal extract of malt in a solution of starch the coeficient expressing the velocity of reaction either remains constant or increases. It is known however that in the case of an extract of malt which has been heated to a temperature at which its activity begins to be markedly lowered its action is slowed down and the ratio between maltose and non-maltose materials decreases in value.The author now finds that with such attenuated extract of malt the coefficient of velocity varies in a special manner. Thus for the same extract of malt acting on hhe same starch solution K increased from 4000 to 6036 for unheated extract from 4230 to 5692 for extract heated to 30° remained almost constant for extract heated to 40’ or 50° diminished from 2483 to 1681 for extract heated to GOO and from 1443 to 463 for extract heated to 70°. The time of heating was thirty minutes and the coefficient was determined over a range of one hundred and eighty minutes in each case.The change is therefore continuous. The change is retarded by the addition of maltose which seems there-GENERAL AND PHYSICAL CHEMISTRY. ii. 245 fore to protect the diastase to some extent. whence it seems likely that not only is an adsorption compound formed between diastase and starch but also between diastase and maltose. It appears likely that the so-called '( optimum temperature " for enzymes is the resultant of two actions namely (1) the normal increase in velocity of reaction due to rise in temperature and (2) the destruction of enzyme due to rise in temperature so that in reality the coefficient of velocity in enzyme reactions tends to diminish with rise of temperature.For diastase the coefficient of temperature Kt + IOIKt of the reaction remains constant and is about equal to 2 between 25 and 35" (at which temperatures the destruction of enzyme by heating is negligible) so long as the other conditions are such that the reaction obeys the logarithmic law. Automatic Pressure Pipette. WLADIXIR SKINDER (Chem. Zeit. 1912 30 166).-The pipette which is used for mixing two liquids at the same tamperature as in calorimetric experiments consists of a hollow glass piston sliding in an outer mantle of one-third its length the upper and lower joints being ground.There is a small hole in the piston in the upper part of the pipette and a groove in the lower ground joint which can be brought into coincidence with a hole in the mantle. The pipette is filled by lowering into the liquid and forcing the piston downwards. When filled it is withdrawn and the excess of liquid allowed to escape by bringing the openings into coincidence. After rinsing the pipette is brought to the required temperature and the liquid can then be expelled by applying air-pressure which lifts the mantle. C. H. D. Substitute for Separating Funnels. HEINRICE KILIANI (Zeitsch. anal. Chern. 1912 51 l02).-A doubly-perforated cork is fitted with a siphon tube and also with a small tube bent a t a right angle. The siphon tube should not fit too tight. The cork is then placed on the bottle containing the two-layer liqilid and after placing the siphon in the proper position gentle blowing through the small tube starts the T.A. H. action. L. DE K. Filtration with Alundum Plates. RAYMOND C. BENNER and WILLIAM H. Ross (J. Amer. Chem. Xoc. 1912 34 51).-Disks or plates of " alundum " (fused aluminium oxide) aro recommended as substitutes for filter-plates and asbestos. An ordinary rubber band stretched round the disk enables it to fit closely t o the funnel when suction is applied by the pump. Alundum disks are obtainable with pores of various degrees of fineness; those with the smallest pores are capable of retaining the finest precipitates. By their use the preparation of asbestos is obviated and the precipitates can be stirred without risk.E. G. Substitute for Kipp's Apparatus. BERTHOLD OPPLER (Chem. Zeit. 1912 30 96).-A wide glass cylinder open at both ends is passed through the cork of a wide-necked bottle the lower end of the cylinder reaching to the bottom of the bottle. The upper end of the cylinder which should be just above the cork is closed by means of a VOL. CII. ii. 17ii. 246 ABSTRACTS OF CHEMICAL PAPERS. second cork through which pass a tapped delivery tube and the stem of a large bulb tube. The material from which the gas is to be evolved is placed on a perforated plate supported on rubber stoppers at the bottom of the cylinder the lower end of the funnel stem reaching below this plate. Perforations are provided in the walls of the cylinder in order that the acid from the bulb tube may circulate in the cylinder and bottle.w. P. s. Universal Apparatus. FRANZ MICHEL (Chem. Zeit. 19 12 36 138).-In appearance the apparatus resembles a large vacuum desic- cator provided with screw-clamps so that the upper and lower portions can be firmly fixed to each other. The upper portion is of Jen% resistance glass the lower being of copper nickel cast iron or porcelain; the joint is made tight by means of an asbestos ring which has been soaked with rubber solution. The apparatus can be used for treating volatile and easily decomposable substances in a protecting atmosphere. T. S. P. An Early Physical Chemist M. W. Lomonossoff. ALEXANDER SMITH (J. Arner. Chern. Xoc. 1912 34 109-119).-A biographical sketch of the Russian chemist Lomonossoff (1711-1765) and an appreciation of his work. Some Lecture Experiments. CONSTANTIN ZENGELIS (Zeitsch. phys. Chern. Unterr. 191 1 24,137--142).-An account of the methods by which the author demonstrates (1) Paraday’s law.-A pair of tubes A and B with taps at the base are joined to each other by another tube containing a tap which can be opened or shut as required wires are connected for the passage of an electrical current and they are filled with an N/lO-solution of an alkali sulphate in the presence of an indicator (such as litmus or phenolphthalein). Another similar pair of tubes A’ and B‘ containing the exact equivalent of another alkali sulphate are placed in series an electric current passed and the change of colour shown by the indicators noted ; the connecting taps are then closed and the contents of A and 13’ and of A’ and B respectively mixed when the original colour of the solutions will be regenerated. (2) Positive and negative catalysis as shown by the interaction of sulphurous acid and hydrogen iodate E. G. 3H,SO + HIO = 3H,SO + HL 5HI + HIO = 3B,O + 31 ; the duration of the reaction is noted in the case of varying concentra- tions and in the presence of different acids the end point being sharply marked by the sudden separation of iodine; with 6.4 grams of sulphurous acid and 17.8 grams of iodic acid each in a litre of water the reaction was completed in 38.28 seconds (compare Landolt Abstr. 1886 658). (3) The ignition of a mixture of nitric oxide and cadon d&uZphide.- A wide-necked flask is filled with nitric oxide a few C.C. of carbon disulphide added closed with a glass plate and heated until ignition takes place. (4) The burning of carbon disulphide in ozggem-A strong bottleINORGANIC CHEMISTRY. ii. 247 closed with a two-holed stopper the larger opening is fitted with a silver or porcelain tube the other one with a narrower brass tube connected outside with a source of oxygen which after entering the bottle bends round into the other tube; carbon disulphide is placed in the bottle heated and the vapour ignited in the stream of oxygen at the mouth of the bottle. ( 5 ) The high temperature produced by burwing aluminium in oxygen. -The aluminium is heated in a Hessian crucible into which a stream of oxygen is introduced (compare Zengelis Abstr. 1904 ii 232 and Elektrochern. Zeitsch. 1903 10 109; see also Abstr. 1905 ii 65; 1910 ii 1106). F. M. G. M.

ISSN:0368-1769    

DOI:10.1039/CA9120205213

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

i. 229 Organic Chemistry. The Autoxidation of Organic Compounds. HERMANN STAUDINGEB ( Verb. Ges. cleut. Naturforsch. Aerzte 191 2 ii [ 13 21 6-21 9).-The autoxidation of compounds containing a double linking involves the formation of two oxides one of which is symmetrical as in the case of diphenylethylene 1 and the other unsymmetrical as with trichloroethylene >O:O which then breaks up into yc12->0 and oxygen. It is assumed that the first product is always the unsymmetrical compound which may then undergo rearrangement. C. H. D. QPh,* 0 CH,-0 QC1,- CHCl CHC1 Action of the Grignard Reagent on Methylethylacraldehyde and the Preparation of Some Diolefines Olefines and Saturated Secondary Alcohols. E. BJELOUSS (Ber. 1912 45 625-632. Compare Abstr. 191 0 i 706).-S-Methyk-AY-octen-~-ol CH,R!e* CH :CMe* CH(0H) CH,=CH,Me prepared from propyl chloride and methylethylacraldehyde is a colourless mobile strongly smelling liquid m.p. 79-81'/10 mm. Di5 0.8468 n 1.4645. The crcetate is a colourless mobile liquid b. p. 87-89'/14 mm.; the chloride has b. p. 59-62'/1 1 mm. y-MethyZ-Aav-hexadiene CH,Me*CH:CMe*CH:CH2 is a very mobile colourless liquid b. p. 101-103" DF 0.7407 n 1.452. 8 - 2CfethyZ - hue - octadiene CH,B.e*CH:CMe-CH:CH*CH,Me is a colourless liquid of characteristic odour b. p. 148-151' DY 0.764 nz 1.4628. y-Meth yZl~exan-,B-oZ CH,Me*CH,*CHMe- CHMe OH is a colourless mobile liquid with an odour of peppermint b. p. 79-81°/52 mm. DF 0.832 ny 1.4307; the acetate is a pleasant smelling liquid b. p. 84-87' ; the chloride has b. p.53-58'/36 mm. 6-MethyZheptan-y-ol CH,Me* CH,*CHMe* CH( OH) CH,Me is an agreeable smelling liquid b. p. 98-99'/75 mm. Di5 0.8268 ng 1.4261 ; the acetate has b. p. 103-104'/75 mm. ; the chloyide b. p. 83-86'/ 79 mm. 8-JlethyZoctan-eoZ is a colourless strongly smelling liquid b. p. 74-76'/9 mm. DY 0,8156 1.4262. Pe-DimethyZoctccn-8-oZ CH,Me- CH,*CHMe* CH( OH)*CH,-C HMe is similarly a colourless mobile liquid b. p. 102-104O/34 mm. DY 0.8125 r&g 1.4259; the phenylurethane crystallises in bunches of needles m. p. 39-40'. PT-DinLethyZnonan-E-ol has b. p. 98-99'/11 mm. Di5 0.8126 rig 1.4295 ; the crystalline phenylurethane has m. p. 43-44". y-Methyl-AP-hexene CH,Me*CH,*CMe CHMe prepared by elimina- tion of hydrogen bromide from methylhexanyl bromide is an exceed- VOL.CII. i. ri. 230 ABSTRACTS OF CHEMICAL PAPERS. ingly volatile liquid of pleasant odour b. p. 85-90' DY 0.7301 n$ 1.4132. 8-Methyl-AY-heptene is very similar; it has b. p. 115-120° DT 0.741 1 n 1.4171. 8-MethyZ-Aa-octene has 'a penetrating odour b. p. 1 33-138' DF 0.73S8 9% 1.4178. p€-Dimet~yZ-A"octene has b. p. 152-157' Di5 0.746 ng 1.4189. 88-Dimethyl-Aa-nonene has b. p. 165-169' DY 0.753 ng 1.4278. By the action of magnesium phenyl bromide on methylethyl- acraldehyde an alcohol is a t first formed but on distillation in a vacuum water is eliminated and a hydrocarbon a-phenyl-P-methyl- AaY-pentadiene (?) obtained ; this is a yellow mobile strong smelling liquid b. p. 22S-23lo/753 mm. DT 0.8986 ng 1.5257. a-Phenyl-P-methylpsntane obtained on reducing phenylmethyl- pentenol is a colourless mobile pleasant smelling liquid b.p. 203-207' Di5 0.8584 n z 1.4827. a-Naphthyl-P- methyl - A ~ Y - pentadiene (1) is a yellow liquid of characteristic odour b. p. 178-181O/12 mm. Dt5 0.9SO1 n y 1,5697. E . F. A. Compounds with Triple Linkings. WILHELM MANCHOT [with 257-293).-Various observers have described additive compounds of acetylene and cuprous chloride but have been unable to show that their substances are initial products of the reaction. The authors using a modified form of the apparatus described previously (Abstr. 1910 i 85) now shorn that the initial product is the white substance C,H,,CuCl. On account of its solubility and of the secondary reaction which occurs in concentrated solutions this substance cannotibe isolated from aqueous solutions; it is obtained however by working in absolute alcoholic solution at 09 At 0' and atmospheric pressure experiments with solutions containing 0.034 gram-molecule of cuprous chloride per litre and varying quantities of hydrochloric acid yield the following results.With 0.6 1 gram-molecule of hydrochloric acid per litre a clear colourless solution is obtained and 22.44 litres of acetylene (per 1 gram atom of copper) are absorbed. With greater concentra- tions of hydrochloric acid the absorption of acetylene diminishes owing to the concurrent reaction CuCl + HC1= CuC1,HCl. When the concentration of the hydrochloric acid is less than 0.61 mol. per litre the absorption of acetylene also diminishes owing to the formation of a dark violet substance C,Cu2,CuCI,H,0.When the concentration of the cuprous chloride in a solution of 0.61 mol. of hydrochloric acid per litre is increased the absorption of acetylene diminishes owing to the formation of a sparingly soluble white substunce 3CuCI,C,H2 ; thus 2(CuCI,C,H2) C,H + 2CuC1,C,H2. For example the absorption of acetylene is 22.4 litres (per 1 gram atom of copper) when the concentration of the cuprous chloride is 0.00561 mol. of cuprous chloride and only 11.43 litres when the concentration is increased to 0.5035 mol. I n its ability to form a compound of the type ~CUC~,C,H,~ acetylene differs from carbon monoxide and ethylene and resembles nitric oxide JOHN c. WITHERS and HEINRICH OLTROGGE] (8n?Zah% 1912 38'7,ORGANIC CHEMISTRY. i. 231 which can form a compound 2FeSO,,NO (hbstr.1907 ii 93 ; 1908 ii 375; 1910 i 85; ii 414 956). The additive capacity of acetylene towards cuprous chloride also differs from those of carbon monoxide and ethylene in the following respect. The latter two gases only form additive compounds in the presence of water ammonia or organic bases ; the presence of alcohol not only retards the addition but causes decornposition of the additive compound when formed. In the case of acetylene the presence of water is unnecessary for the formation of the additive compound CuCl,C,H ; the additive compound is formed as in the case of nitric oxide and ferrous chloride in absolute alcohol. Substituted acetylenes such as phenylacetylene p-anisylacetylene methylenedioxyphenylacetylene behave like acetylene itself towards cuprous chloride.By direct addition of the components colourless additive compounds of the type CE:iCH,CuCl are obtained which are converted by water or ammonia into coloured copper derivatives CRiCCu. Hence the equation CRiCH + CuCl = CRfCCu + HCl expresses only the initial and the final states; the first phase of the process that is the condition for the subsequent substitution is the formation of an additive compound of the two components. These experiments therefore support the views on processes of substitution recently advanced by Werner and by E. Pischer. The presence of the group iCH is not the condition for the forma- tion of additive compounds of acetylenes and metallic salts because although many substances of the type CRiCR do not form additive compounds bromophenylacetylene iodophenylacetylene phenylpro- piolonitrile and phenylpropiolamide react readily with cuprous chloride to form such substances.The authors are of opinion that the degree of unssturation of substances containing a triple linking varies from case to case with the nature of the groups attached to the CiC group. Even if a group R is itself unsaturated it does not necessarily increase the unsaturation of the whole molecule CRiCR' ; thus diphenyldiacetylene di-p-anisyldiacetylene and bis-3 4-me t hy lenedioxy phenyldiacstylene do not form additive compounds with cuprous chloride. The following new compounds are described p-Anisylacetylene forms a canary-yellow coppel. derivative OMe*C,H,*CICCu and a colourless additive compound OMe*C,H,*CiCH,C'uCI and yields by treatment in ether with sodium and subsequently with benzoyl chloride benzoyZ-p-anisy?acetgZene OMe*C,H,*CiCBz m.p. SlO which does not react with cuprous chloride and forms a .dibromide OMe*C,H;CBr*CBrBz m. p. 90'. Di-p-anisgZcEiacetylene m. p. 144O white needles is obtaiied almost quantitatively by shaking the copper derivative of p-anisylacetylene with alcoholic ammonia and oxygen for four days. Bis-3 ; 4-rrtetlr~yZerLedioxy~~~enyZ~iacety~~ C18Hlo04 m. p. 1 9 7 O and diphenyldiacetylene are prepared in a similar manner. c. 8. C2(C*C6H4*OMe) Derivatives of Acetylene. Huao NOEBULINGER (Xleine Hilt. Chem. Fabrik. PZ&sheim No. 37).-The physical constants and properties of the following derivatives of acetylene are given Heptinene (n-amyl- P 2i.232 ABSTRACTS OF CHEMICAL PAPERS. acetylene b. p. 108-110°/745 mm. 26'/10 mm. m. p. below -70° D15 0.7546 D'O 0.7470. Octinene (n-hexylacetylene) b. p. 130-1 3 2 O / 745 mm. 31°/8 mm. m. p. below -70° D15 0.7680. Noninene (n-heptytucetylne) b. p. 160°/745 mm. 51"/8 mm. m. p. - 65' DI5 0.7799. Becinene (n-octylncetylene) b. p. 181-1 82'/745 mm. 69-70'/10 mm. m. p. -36' D15 0.7924. Undecinene (n-nonyl- acetgllene) b. p. 202-204"/745 mm. 91'/8 mm. m. p. - 33" D15 093024. All these compounds are colourless liquids practically insoluble in water soluble in organic solvents. They possess a high refractive index and a characteristic odour which is particularly marked in the cases of heptinene and undecinene With ammoniacal cuprous chloride and silver nitrate solutions they yield yellow and white precipitates respectively.When dissolved in ether and treated with sodium they evolve hydrogen and form highly reactive sodium compounds. H. w. Densityand Thermal Expansion of Ethyl Alcohol and its Mixtures with Water. N. S. OSBORNE E. C. MCKELVY and H. W. BEAECE (J. Wccshington Acad. Sci. 1912 2 95-YS).-The densities of twelve mixtures of ethyl alcohol and water were determined at loo 15" 20° 2 5 O 30° 35' and 40" by the method of hydrostatic weighing. For each mixture the constants a p and y in the equation Dp = D250 + a(t - 25") + P(t - 25")' + y(t - 25')3 and these values are tabulated together with D25". The values of a p and y for each integral % of alcohol between 0 and 100 have been obtained by interpolation.The mean of fifteen determinations of the density of the purest alcohol at 25' was found t o be 0*78506. H. M. P). Action of the Chlorides of a-Alkyloxy-acids on Organo- metallic Derivatives of Zinc. EDMOND E. BLAISE and L. PICARD (Ann. Chim. Phys. 1912 [viii] 25 253-276).-For the most part a resum6 of work already published (Abstr. 1911 i 175 260). The following new data are recorded regarding substances obtained in the general reaction. Zthyl n-anayl ether b. p. 119-120° is a mobile pleasant smelling liquid insoluble in water which on heating with hydriodic acid yields n-amyl iodide from which n-amyl ether b. p. 70°/12 mm. and n-amyl alcohol were prepared. The phenylurethane of the latter has m. p. 46' and crystallises in tablets and the benzoate boils a t 137-138'/ 15 mm.Ethoxymethyl n-butyl ketone OEt*CH2-CO*C,H9 b. p. 79"/ 18 mm. is a pleasant-smelling liquid ; the oxinae b. p. 125'/17 mm. is a colourless liquid ; the sernicarbaxone m. p. 99" forms brilliant colourless spangles. Condensation of ethoxyacetyl chloride with zinc isoamyl iodide furnished ethyl isohexyl ether OEt*CH,-CH,PrP b. p. 68"/67 mm. or 137'/760 mm. and ethoxymethylhexanone (Sommelet Abstr. 1907 i 107). p-Tolylethoxy~net~,~ZethyZcarbinol OH*CEt(CH,*OEt)*C,H,Me b. p. 130°/9 mm. obtained by the action of magnesium ethyl bromide onORGANIC CHEMISTRY. i. 233 p-tolylethoxymethyl ketone already described (Abstr. 191 1) i 175) gives by the application of Sommelet's method (Zoc. cit.) P-p-tolyl- butaldehyde CfiH,Me*CHEt*CHO b. p.l04'/8 mm. The latter furnishes an axzne m. p. 63' (decomp,) a semicarbaxone p-nitrophenyl- hydrazone m. p. 104O and an oxime m. p. 70' all of which are crystalline. T. A. H. Action of Alkyloxides on Esters of Inorganic Acids. I. L. RABTSEVTTSCH-ZUBKOVSKY (J. Izziss. Phys. Chem. Xoc. 1911 44 151-154).-Methyl sulphate reacts with magnesium methoxide accord- ing to the equation 2Me2S04 + Mg(OMe) = 2Me20 + Mg(S04Me)2 and with sodium isobutoxide according to ; Me,SO + CHMe,*CH,*ONa = NaMeSO + CHMe,*CH,*OMe. Magnesium methoxide and methyl phosphate yield methyl ether and magnesium dimetbyl phosphate PO(OMe) + Mg(OMe) = 2Me,O + Mg[O*PO(OMe),] ; so that when alkyloxides react with alkyl salts of polybasic inorganic acids only one of the alkyloxy-groups of the salt is replaced by the metal of the alkyloxide.T. H. P. Preparation of Aminoethyl Alcohol from Egg Lecithin. GEORG TRIER (Zeitsch. physiol. Chew. 1912 '76 496-498. Compare Abstr. 1911 i 771).-/3-Aminoethyl alcohol is obtained as a product of the hydrolysis of egg lecithin by dilute sulphuric acid in not inconsiderable quantity and identified by means OF the aurichloride. E. F. A. Should the Term Protagon be Retained 3 WALDEMAR KOCH (Proc. Amer. Xoc. Biol. Chenz. 1911 xl; J. Biol. Chem. ll).-The term protagon has no longer any chemical significance; the substance so described contains at least three materials namely a phosphatide which contains choline a cerebroside and a combination of a choline- free phosphatide and a cerebroside to which an ethereal sulphuric acid group is attached.W. D. H. New Compounds of Samarium and Neodymium. CHARLES JAMES F. M. HOBEN and C. H. ROBINSON (J. Anzer. Chem. Soc. 1912 34 276-281 ; Chem. News 1912 105 121-122).-1n the course of a search for salts which might be of value for fractionally separating the rare earths the following compounds were prepared and are described. Samarium ethylsulphonate (C2135*S03)68a2,6 H,O mcthylsulphonate (C H 3* SO,),Sa 7H,O propylsulphonate ( C3H7*S03)6Sa2,9 H20 isobzctyl- sulphonate (C,H,*SO,),S.c 7H,O camphorsulphonate methanetriswlphonate [ C H ( S03)3]2Saz 1 6H,O m-xylene-4-szc1p?~onatel (C,H,Me,* S0,)6Sa2,7H20 glycollate (OH CH,* CO,),Sa cacodylate (Me A S O ~ ) ~ S ~ I 6 H,O ethanediszclp~~onate [ C,H,(80,),],Sa2,4H,0 etAyZglycollate (OEt *CH,*CO,),Sa 18H,O citmconate sulpolLoucetcLte (C,H,O,S),Sa and hyd?-oxyethanesuZp?ionate.Neodymium ~me~hyZsuZ~honccte (CH3*S0,),Nd,,7H,O ethylsulphonate (C,(-)H,50*S03)(3Sa2 10H201 (C5H404)3,5a2112 (C,H5*SO3),Ndy6H,O,i. 234 ABSTRACTS OF CHEMICAL PAPERS. popylsulphon ate ( C,H7*S03),Nd ,,GH,O is0 butylsulp?umata ethanedisuZphonate [C,H,( S03),],Nd2 1 OH20 methanetrisuZphonate camphorsuZphonate (C,,H,,O*S.O,),Nd 1 7H,O m-xyZene-4-suZpho~ate ( C,H,Me,*S0,),Nd2 2 H,O m-sulphobenxoate quinate [c,H,( OH)4*C0,],Nd2,1 1H20 anisate (OMe*C,H,*CO,),Nd oxanilate (N H Ph*CO*CO,),N d 2,5 H,O cacodplate (Me AsO,),Nd and hydroxyethanesu2phonate. E. G. (C4H9*S03)6Nd,,8H20 [CH(S0,),J2Nd2,14H20 ( C7H405S)3Wd2,9H20 Reduction of Higher Unsaturated Aliphatic Acids to Saturated Acids by the Action of Zinc and Water on their Halogen Derivatives ; Grignard Reaction Applied to the Latter SERGIUS FOKIN (J.Russ. Phys. Chem. Xoc. 1912 44 155-165).-Experiments with oleic elaidic erucic undecenoic ricinoleic linoleic and linolenic acids show that by addition of hydrogen bromide to these acids and treatment of the monobromo- saturated acids thus obtained with zinc and water in a sealed tube the corresponding saturated aliphatic acids themselves are obtained ; for example (C,7H,4Br*C02),Zn + 2Zn + H,O = (C17H,,-C02),Zn + (ZnBr + ZnH),. Unsaturated hydroxy-acids may be converted into saturated hydroxy-acids in a similar manner. With monochloro- derivatives of saturated aliphatic acids the reaction with zinc and water proceeds partly in tho direction indicated by the above equation but about one-third of the acid formed consists of the original unsaturated acid from which the chloro-derivative of the saturated acid was obtained.As stated by Lewkowitsch ('< Oils Fats and Waxes ") neither dichloro- nor dibromo-stearic acid gives the non- substituted stearic acid when heated with various metals in presence or absence of water or an organic solvent. The following temperatures are those at which fused mixtures of oleic and stearic acid solidify 10% stearic acid (90% oleic) 29.5' ; ZO% 40.2"; 30% 47.7"; 40% 52.9'; SO% 56.8"; 60% 59.8'; 70% 62.3' j SO% 64.P ; 90% 66.3" and pure stearic acid 68.0°. T. H. P. An Anomaly in the Reduction of Ethyl Acetoacetate. JULIUS TAFEL [with FRANZ ANDRE] (Beso. 1912 45 437-452. Compare Tafel and Hahl *Abstr.1907 i 765 ; Tafel and Jiirgens Abstr. 1909 i 545).-The electrolytic reduction of derivatives of acetoacetic esters has been interpreted to take place according to the scheme CH,*CO*CHR*CO,Et -+ CH,*CH,*CHR*CH,. W bilst however the range of the b. p. of the products obtained points to their uniformity the actual b. p.'s do not in all cases agree with those recorded for the expected hydrocarbons and in the cases where R = Et nPr or nC4HSI lie close to those of the isomeric normal hydro- carbons ; similarly Tafel and Jurgens (Zoc. cit.) found for the reduction- product of ethyl isobutylacetoacetate a b. p. 7" higher than that given by Clarke (Abstr. 1908 i 593) for PG-dimethylhexane. The present work was undertaken with the object of explaining these differences,ORGANIC CHEMISTRY.i. 235 and has led to the conclusion that the methyl group formed in the complete reduction of derivatives of acetoacetic esters is transposed and occurs not as a side-chain but as part of the main chain. The reduction of ethyl isobutylacetoacetate whether with lead or cadmium electrodes gave results precisely similar to those obtained by Tafel and Jiirgens (Zoc. cit.) The product which is now regarded as P-methylheptane or y-methylheptane (instead of PS-dimethylhexane) appears to undergo slight decomposition when shaken with concentrated sulphuric acid according to the method previously used for its purification. By the reduction of ethyl sec.-butylacetoacetate with lead electrodes a hydrocarbon b. p. 117.8-118*2°/746 mm.was obtained. This is regarded as y-methylheptane or possibly a mixture of 8-methylheptane and y-ethylhexane. Methyl methylpropylacetoacetate reduced at a cadmium electrode yielded an octane of b. p. 116*1-118*2°/752 mm. This is probably 8-methylheptane possibly y-methylheptane or y-ethylhexane or a mixture of the latter with 6-methylheptane. Methyl methylisopropylacetoacetate when similarly reduced gave an octane of b. p. 110-118°/756 mm. which is presumably a mixture of hydrocarbons. By the reduction of ethyl isopropylacetoscetate a heptane of b. p. 91-92.6O/747 mm. probably slightly impure /3-methylhexane or possibly y-methylhexane was obtained. Ethyl ethylacetoacetate when reduced a t cadmium or lead electrodes yielded a hydrocarbon which after purification by means of con- centrated sulphuric acid had b.p. 68*2-69*loj742 mm. This was unaffected by cold potassium permanganate thereby differing from y-methylheptane which according t o Zelinsky and Zelikoff is rapidly oxidised by this reagent-a statement however which the authors could not confirm experimentally. An explanation of certain of these reactions may be found in the hypothesis that a tetramethylene ring is formed as an intermediate st,ep in the reduction and then broken in the manner indicated by the scheme 4 7% 4 3 7% 7-Q 7% 3 7% -+ F Q - R -+ 3 70 2 VHR To explain the formation of y-methyl derivatives from ethyl iso- butyl- and isopropyl-acetoacetates i t is necessary to assume that the carbon atom of the carbethoxy-group of the ester becomes detached from the a-carbon atom (*) and attached to a terminal C-atom of the alkyl group 2 CH,R 1 2 1 C0,Et * * CH,* COO FH-$!H*CH CH,*CH CH,* ?3*CH,*CH CH3 -+ C0,Et CH This leads to the same result as the above hypothesis in the cases of n-nlkyl derivatives of ethyl acetoacetate and of ethyl diethylaceto-i.236 ABSTRACTS OF CHEMICAL PAPERS. acetate I n the cases of sec.-butyl methylpropyl and methylisopropyl derivatives however two products might be expected whilst only one has been obtained possibly owing to the proximity of their respective b. p.’s. On the whole the second hypothesis explains the fact better than the first but is advanced with caution on account of the difficulty of interpreting the mechanism involved. A third possibility lies in the assumption of a new formulation for the substitution products of ethyl acetoacetate as shown in the following scheme CH,*CO CH,*CO CH,*CO I I CH CR I >O I I >O CH H*C*OEt I >O R*C*OEt R*C*OEt Possibly in ethyl acetoacetate this form may be in equilibrium with the forms generally assumed and may also be the form mainly attacked during alkylation.According to this hypothesis the same hydrocarbons should be obtained from monoalkyl derivatives of ethyl acetoacetate and from ethyl diethylacetoacetate as would be expected from the first hypothesis (see above). Ethyl methylpropylacetoacetate (from ethyl methylacetoacetate) should yield y-ethylhexane whilst ethyl meth y lisopropy lacetoace tate (from ethyl met h y lace to ace tate) and ethyl methylbenzylacetoacetate (from ethyl benzylacetoacetate) should yield p-methyl - y - ethylpentane and a - phenyl - y - methylpentane respectively.H. W. A New Salt of P-Hydroxybutyric Acid. PHILLIP A. SHAFFER (Proc. Arner. Xoc. Biol. Chem. 1911 xi; J. Biol. Chem. 11).-If equivalent parts of zinc and calcium P-hydroxybutyrates (made by treating the free acid with zinc and calcium carbonate respectively) are poured together a double salt ZnCa(C4H703)4 is formed which on the addition to the warmed solution of an equal volume of alcohol crystallises out in needles or long narrow plates. It is useful for the purification of the acid which may be obtained from the double salt by removing the zinc with hydrogen sulphide and the calcium with oxalic acid; or a solution of the salt acidified with sulphuric acid and dehydrated by plaster or anhydrous sodium sulphate may be extracted with dry ether.The salt prepared from the E-acid has a specific rotation [a32 = A 15*1° (5% solution) W. D. H. Syntheses by means of MixFd Organo-metallic Derivatives. Mixed cycZoAcetals. EDMOND E. BLA~SE (Compt. rend. 1912 154 596-598. Compare Abstr. 1911 i 175,26O).-The action of organo- zinc halides on acid chlorides of the type COCl*CHR*O*CO*R is abnormal and leads to the production of cyclic compounds which the author proposes t o term cycloacetals. An intermediate compound is probably decomposed in the following manner ZnI*O*CR,*O*CHR*COCl = ZnICl + C€€R<-O->CR,. coo0 The following new substances have been prepared ; their use in theORGANIC CHEMISTRY. i. 237 synthesis of aldehydes a-ketonic acids and a-halogen ketones wiIl be described in a subsequent communication.CHl\le<-0_>Ch5ePra co.0 b. p. 90°/22 mm. CMe,<-o->CMeEt coo0 b. p. 64Oj13 mm. CH2Me*[CH,12-CK<-o->CMeEt (20.0 b. p. 103"/12 mm. CH,Me*[CH,]~*CL-I<~~~>CMeEt b. p. 115'/12 mm. Ace tylsalico y 1 chloride gives the compound C,H,<E% !>CMeEt whilst acetgl p-h ydroxy benzoyl chloride behaves normally. w. 0. w. F. B. Formation of Cork. SIMON ZEISEL (J. pr. Chem. 1912 [ii] 85 226-230).-Polemical with Schmidt (this vol. i 72). Oxidation Products of Sebacic Acid. EYVIND BODTKER (J,. ?r. Chem 1912 [ii] 85 221-225).-Succinic glutaric and adipic acids together with a small quantity of y-heptnnone-aq- dicnrboxylic acid (Tonnies Abstr. 1579 915) are the only products formed when sebacic acid is boiled with concentrated nitric acid until it completely disappears. For details of the separation of the acids the original should be consulted. Dissociation of Tartrates Malntes and Camphorates of Amines as Revealed by their Rotatory Power.JULES MINGUIN (Ann. Chim. Plys. 1912 [viii] 25 145-159).-The work on tartrates has been published already and the general conclusions then drawn apply t o the other salts now dealt with (Minguin and Wohlgemuth Abstr. 1909 i 11). The malates and camphorates of the aliphatic amiiies exist undissociated in solution but in the case of the 'aromatic amines neutral malates are not formed and the hydrogen malates are dissociated in solution. Camphorates of the aromatic amines do not exist in solution.The hydrogen malates of aniline and of diethylaniline melt at 132' and 67' respectively. Lactonisation of a-Ketonic Esters. Ethyl Pyruvate. HENRI GAULT (Conapt. Tend. 1912 154 439-441. Compare Abstr. 1911 i 709 ; de Jong Abstr. 1904 i 550).-When the lactonisation of ethyl pyruvate is effected by saturating the ester with hydrogen chloride in the cold the ethyl a-keto-y-valerolactone-y-carboxylate first formed undergoes further change and a neutral substance b. p. 176-177°/ 13 nim. is obtained; this is probably the ethyl ether of the enolic '-7' and appears to be CH:C*OEt' form of the above ketone CO,Et*CMe< identical with the compound prepared by Genvresse (Abstr. 1893 i 552) which he supposed to be ethyl a-keto-AP-butene-ay-dicarboxylate. It unites with hydrazine (2 mols.) to form a compound m.p. lSOo (decornp.) the constitution of which has not yet been elucidated. F. B. T. A. H. w. 0. w.i. 238 ABSTRACTS OF CHEMICAL PAPERS. Citrophosphate Solutions. ANTONIO QUARTAROLI (Atti R. Accad. Lincsi 1912 [v] 21 i 130-135).-The author criticises the work of Pratolongo (Abstr. 1911 ii 865) on this subject. The supposed solutions of diammonium citrate used by that author are shown to have contained a mixture of dinmmonium and triammonium citrates with an excess of the latter. The differences between the cryoscopic depressions observed by Pratolongo and the calculated values are not due to hydrolysis because they mould require for instance that not only the diammonium citrate but also three-quarters of the mon- ammonium citrate present should suffer hydrolysis. The present author's calculations (from the dissociation constants of ammonium hydroxide and citric acid) show that even triamrnonium citrate can be but little hydrolysed.The abnormal values obtained for i in the case of the ammonium citrates are therefore due not to hydrolysis but to electrolytic dissociation. It is further shown that the cryoscopic data do in fact support the hypothesis of the formation of complex salts and exclude the possibility of the occurrence of double decomposition. The paper records cryoscopic measurements for various solutions of citric acid monoa.mmonium citrate triammonium citrate (and four intermediate solutions between the two last named) monopotassium citrate dipotassium citrate tripotassium citrate monoammonium phosphate diammonium phosphate triammonium phosphate tri- ammonium citrate + calcium hydrogen phosphate and triammonium citrate + barium hydrogen phosphate.R V. S. The Synthetic Application of Ethyl Methanetricarboxylate. ROLAND SCHOLT~ (Verh. Ges. deut. Naturforsch. Aerzte 1912 ii [l] 213-224).-The usual ethyl acetoacetate and ethyl mslonate syntheses may be performed with ethyl metbanetricarboxylate if alcohol is excluded. The reaction takes place at or above looo and a pure product is obtained. Ethyl mc:tl~anetctrncarboxyZate prepared from ethyl sodiomethanetricarboxylate and ethyl chloroformate is a stable compound b. p. above 290' undccomposed and yielding mnlonic acid with dilute sulphuric acid. C. N. D. New Method f o r the Catalytic Preparation of Aldehydes from Acids.PAUL SABATIER and ALPHONSE MAILHE (Compt. rend. 1912 154 561-564. Compare this vol. i 156 157).-The reduction of aliphatic acids by means of formic acid furnishes a convenient method for preparing the corresponding aldehydes with satisfactory yields. The vapour of the acid mixed with excess of formic acid is passed over titanium oxide a t 250-300O. Under these conditions no ketone is formed but the formic acid decomposes into carbon monoxide and water thus effecting reduction of the acid. The following acids readily give aldehydes the numbers indicating the yield in percentages acetic 50 phenylacetic 75 propionic 40 butyric 55 isobutyric 65 isovaleric 75 y-methylvaleric 80 octoic 95 and nonoic acid 85%.I n the last case a small amount of the corresponding ketone pelargone is also formed. Crotonic acid gives the aldehyde. When thoria is substituted for titanium oxide the yields of aldehyde are lower. w. 0. w.ORGANIC CHEMISTRY. i. 239 Alfalfone a Ketone of the Formula C21H420 obtained from Alfalfa. Alfalfa Investigation. 11. C. A. JACOBSON (J. Anter. Chm. Xoc 1912 34 300-302).-1n an earlier paper (this vol. ii 80) it was shown that myristone is present in alfalfa meal. Another ketone C21H420 m. p. SS*5-SS*S0 has now been isolated in the form of a white amorphous powder and has been termed alfalfone. On reducing this ketone with sodium and alcohol the corresponding carbinol C,,H,,*OH m. p. 86*3-436*5° is produced as a white amorphous powder. E. G. New Anhydrides of Dextrose and Glucosides.EMIL FISCHER and KAEL Zacx (Bey. 1912 45 456-465).-By the action of barium hydroxide on triacetylmethylglucoside bromohydrin (Fischer and Armstrong Abstr. 1902 i 263) the authors have isolated a substance C7H1205 which they provisionally name anhydromethylglucoside. It forms a crystalline hydrade and is not converted into sugar by emulsin. Warm dilute acids convert it into adydrodextrose C6Hlo05 which strongly resembles the hexoses differing from them however in its much greater ability to restore the colour to SchiE's reagent. It yields a Trydruxone and an osaxone. The transformation of acetyldibromodextrose i n to t~*iacely~dextrose bromolqdrirt and in to triacetylrnenlholgluco~id~ bromohydrin is also described together with the formation of anhydyomentholglucoside from the latter substance.An~?/drometr%?/lglucoside was prepared by warming triacetylrnethyl- glucoside bromohydrin with barium hydroxide in aqueous alcoholic solution. After filtration and evaporation the residue was distilled under a pressure of 0.2-0*3 mm. when the anhydride passed over hetween 160" and 165°k(temp of bath) as a colourless syrup. I n aqueous solution it had [a]:; - 136.95'. Under suitable conditions it formed a hydrate which was not obtained free from syrup. A t 56"/12 mm. it still retained wn,ter. When dried over phosphoric oxide at 100°/12 mm. it melted lost all i t a water and left a residue of nnhydrome thy lglucoside. Anhydrodextrose was formed by hydrolysing anhydromethyl- glucoside with 4.5% sulphuric acid.It crystallised in long needles rn. p. 118' (corr.) after slight softening. In aqueous solution it had [u] + 53.89'. It dissolved readily in writer and alcohol with difficulty in ethyl acetate. Anhydrodextrosephenylhydrazone was best prepared by mixing anhydrodextroee with pure phenylhydrazine. The solid mass obtained by gently warming the mixture was washed with ether and crystal- Iised from water from which the phenylhydrazone separated in faintly yellow leaflets m. p. 157-158' (corr.). Anhydrodextrosephenylosazone prepared in the same manner as dextroseplienylosazone crystallised in slender needles. It darkened when heated and had m. p. about 180' (corr. decomp.). Triacetylmenthol - d - glucoside bromohydrin was formed when ethereal solutions of acetyldibromodextrose and menthol were shaken with silver carbonate.It separated from alcohol in long needles m. p. 140' (corr.) and had - 49-62' in chloroform solution. Treat-i. 240 ABSTRACTS OF CHEMICAL PAPERS. ment with sodium hydroxide in alcoholic solution transformed i t into anhydromentholglucoside in. p. 113" (corr.) [u]:; - 96.73' in alcoholic s o h tion. ~~acetylbenzylglucoside bromohgdrin was obtained in the same manner as the above menthol compound. It had m. p. 141' (corr.) after previous softening [a] - 46.76" in chloroform solution. Acetyldibromodextrose when shaken in acetone solution with silver carbonate yielded triacetyldextrose bromohydrin m p. 11 9' (corr,) [a] +23-33' in acetone solution. Mutarotntion has not yet been observed with this compound.H. W. Dextrinisation of Starch by Desiccation. GIOVANNI MALFITANO and (Mlle.) A. MOSCHKOFF (Conzpt. rend. 1912 154 443-446).-The conversion of starch into dextrin is attributed to progressive dehydration of the substance and not to the ordinary hydrolytic action of water. Starch was dehydrated over phosphoric oxide a t the ordinary temperature and at higher temperatures up t o 150° the loss of water percentage of carbon and hydrogen and amount of soluble matter formed being determined from time to time. I n a vacuum at 2 5 O 28.1% of soluble matter was formed after twenty days; this rose to 90% when the material was heated for four hours a t 120'. Some decomposition occurs even a t 50° before dehydration is complete as is shown by the starch turning brown.This however is not the cause of increased solubility for a t 150' solubility is less and analysis shows that no oxidation has occurred. These experiments lead to the suggestion that the starch micro-cells are composed of molecules of C6H1005 linked together by water in a manner represented by the formula or more accurately as ([(C,HIOO,*OH)HI(C6H~O0~*0H)~H 9 6 { [ (C,H,,O,*OH)HIn[ (C,H,,O,- OH)]nHn-,)H 9 Soluble starch amylodextrin erythrodextrin etc. may be regarded as arising by successive removals of C,H,,O groups. When dextrinisa- tion occurs in the ordinary way by heating starch with water the effect is the same but the mechanism is different water between the complexes being removed by ionisation. w. 0. w. Lintner Soluble Starch. ERNEST D. CLARK (Biochem.Bulletin 1911 1 194-206).-A study of the reducing power and erythro- dextrin reaction with iodine on Lintner soluble starch prepared from potato starch. The product can only be purified with the greatest difficulty if at all from the dextrin to which these reactions are due. W. D. H. Action of Tetrabromoethane on Organic Bases. WILLIAM M. DEHN (J. Arner. Chem. Xoc. 1912 34 2S6-290).-When tetra- bromoethane is added to a solution of an organic base in dry ether the hydrobromide of the base is precipitated and tribromoethylene is produced and remains in the solution. The reaction takes place more easily with aliphatic amines than with aromatic bases and more easily with primary than with secondary or tertiary amines. It isORGANIC CHEMISTRY. i. 241 accelerated by direct sunlight The hydrobromides of various amines have been obtained in the pure state by this method and their mercuribromides and auribromides prepared.When piperidine is added to an ethereal solution of tetrabromo- ethane the hydrobromide is instantaneously and quantit atively precipitated and this constitutes a convenient and inexpensive method for the preparation of tribromoethylene. The following salts are described Ethylamine mercu?*ibromide NH,Etl,HBr,HgBr m. p. 9 1". Diethylamine hydrobromide m. p. 20S0 auribromide NH Et,,HBr AuBr3 m. p. 162" and mercuribromide m. p. 120". Friethylamine audwomide m. p. 140° and rnercuribromide m. p. 109". Dipropylantine hydrobromide m. p. 271" auribromide m. p. 119" and mercuribromide m. p. 109". Tripropyhmine hydro- bromide m.p. 1 80° auribromide m. p. 149" and mewuribromide m. p. 104". i s d u t y l a m i n e hydrobromide m. p. 138' auribronzids m. p. 154' and mercuribromide m. p. 164". Di-isobulylamine hydrobromide m. p. 3 13' auribromide m. p. 245" and mercuribromide m. p. 60'. Amglanzine hpdrobromide m. p. 243" auribromide m. p. 105" and mercuribromide m. p. 2 13'. Di-isoantylamine hydrobromide m. p. about 315" auribromide m. p. 220° and mercurihromide m. p. 97'. Allylamine hydrobromide m. p. 91" and mercuribronaide m. p. 1 1 5 O . Benxylumine mercuribronaide m. p. 21 1'. Dibenxylamine awribromide m. p. 165" and rnercuribromide m. p. 145". Pyridine rnercuribromide m. p. 152". Picoline mercuribromide m. p. 88". Piperidine mercuribromide m. p. 143". E. G. Hexabromoselenates [Selenibromides].ALEXANDER GuTBIEnand W. GRUNEWALD (J. pr Chem. 1912 [ii] 85 321-330).-hn account of the preparation and properties of the selenibromides of the alkali metals and a number of aliphatic amines of the general formula R,SeBr,. The general method of preparation consists in the addition of a n aqueous solution of the alkali bromide or of the amine in hydrobromic acid to a n excess of a solution of the compound H2SeBr in hydrobromic acid. The latter solution was prepared by adding bromine t o a mixture of finely divided selenium and strong hydrobromic acid. The selenibromides are stable towards air but are decomposed by water; those of the alkali metals crystallise in octahedra or cubes belonging to the regular system [LENK.]. In addition to the seleni brom ides of sodium potassium caesium rubidium ammonium and of methylamine dimethylamine trimethylamine and ethylamine all of which have been previously isolated (Muthmann and Schafer Abstr.1893 ii 318 ; Norris Abstr. 1898 i 510 ; Lenher Abstr. 1899 ii 18) the following new compounds are described Diethylammonium selenibromide (NH2Et2),SeBr6 lnstrous brownish- red needles of monoclinic habit ; the corresponding propylamine com- pound ( NH3Pra),SeBr ruby-red plates of a metallic lustre and rhombic habit ; buty~ccmmon~um selenibromide (NH,*C4H,)2SeBr forms lustrous orange-red leaflets ; the isobwtylamine compound vivid red hexagonal platolets. l3thyZenediammonium selenibromide forms garnet-red crystals of a metallic lustre belonging t o the (C2HloN2)SeBr,,i. 242 ABSTRACTS OF CHEMlCAL PAPEltS.triclinic system ; the propyzene compound (C,Hl,N,)SeBrG garnet-red Action of Tetraiodoethylene on Organic Bases. WILLrAM M. DEHN ( J . Amer. Chem. Soc. 1912 34 290-293).-In earlier papers (Dehn Abstr. 1911 i 829 ; Dehn and Dewey 1911 i 914) it was stated that carbon tetrabromide and di-iodoacetylene combine with organic bases dissolved in dry ether to form molecular compounds. It is now shown that tetraiodoethylene behaves in a similar manner. Sunlight is generally necessary to promote the reactions. The com- pounds are decomposed by water; in the case of the diethylamine compound the main reaction is NHEt2,C21 -+ NHEt + C,T4 but a large proportion decomposes thus 3NHEt,,C,14 + 3H,O -+ 3NHEt2,HI + 3c,12 + 2HI + HIO,.Although the normal course of the reaction between tetraiodoethylene and organic bases is that indicated secondary reactions take place involving the production of di-iodoacetylene thus SNHEt + ZC,14 -+ 2NHEt,,HI + 2C212 + NHEt,,I and 3NHEt + 3C,14 -+ NHEt,,HI + NHEt,,I + NHEt,,HI,I + 3C,12. The crystalline mass precipitated from the ethereal solution is therefore usually a mixture of two or more substances which are sometimes very difficult to separate. The following compounds are described. The ethylamine compound^ NH2Et,C,14 m. p. 1 5 5 O anti NH,Et,ZC,I m. p. 1 3 P ; ethylamine hydraodide m. p. l67' and mercuri-iodade m. p. 136'. The diethylamine compound NHEt,,C,T m. p. 1 5 8 O ; diethylamine hydriodide m. p. 165' and mercuri-aodade m. p. 115'. The triethylamine compound NEt,,2C,14 m.p. 132'; tricth~lamine hydriodide m. p. 173" (decornp.) and mercuri-iodide m. p. 84O. The isopropylamine compound NH2Pra,2C,1,;m. p. 160O. Ths dipropylamine compound NHPra,,2C21 m. p. 130 ; dipropy2- amine hydriodide m. p. 229' (decornp.) and mercuri-iodide m. p. 81'. The di-isoamylamine compound NH( C5H11)2,C214 m. p. 150' ; di-iso- amylarnine rnercuri-iodide m. p. 1 lo@. The bemylamine compound CH,Ph*NH,,C,I? m. p. 115' ; bemylamine hydriodide m. p. 162' and mercurz-zodzde m. p. 134'. The o-phenylethylamine compound C,H,Ph*NH2,C214,C,I m. p. 138' (decornp.) ; o-pl~enylethyla~~eins hydriodide m. p. 267' and mercuri-iodide m. p. 131'. The piperidine compound C5H,lN,2C214 m. p. 147' ; piperidine hydriodide softening at 172' and rnercuri-iodide m.p. 104'. The quinoline compound C,H7N,C2T4 m. p. 132'. The acetamide compound NH,Ac,C214,1 m. p. 175'. Precipitates were also obtained with pyridine triphenylphosphine triethylstibine p-phenylenediamine collidine and picoline. New Compound of Hexamethylsnetetramine with Ortho- arsenic Acid. GUIDO ROSSI (Giom. Fawn. Chirn. 1911 60. Reprint 8 pp.)-On mixing saturated alcoholic solutions of orthti- arsenic acid and hexamethylenetetramine the compound is obtained. It crystallises in transparent needles m. p. 173-174' and (from experiments with a rabbit) is much less toxic than arsenic acid. R. V S. crystals of rhombic hablt. F. B. E. G. (CGH12N4)3,(H,As04)a,ORGANIC CHEMISTRY. i. 243 Stereoisomerism of Internally Complex Salts Stereo- isomeric Cobaltic Salts of a-Amino-acids.HEINRICH LEY and H. WINKLER (Ber. 191 2 45 372-377).-The electrical conductivity of solutions of the stereoisomeric cobaltiglycines (Abstr. 1909 i 886) is extremely small but still capable of being measured. The results show that the dissociation of these compounds is hardly appreciable. When dissolved in O*OlN-sulphuric acid the conductivity of the solution is practically identical with that of the pure acid indicating that the amino-group is completely saturated by the internal complex formation. Experiments in which the rate of dehydration of the red and violet isomeric cobaltiglycines has been measured show that the violet isomeride loses its water of crystallisation the more readily. Using a method similar to that described for the cobaltiglycines (Zoc.cit.) isomeric cobalti-a-alanines CO(C,I'I,O~N)~ have been prepared from alanine and cobaltic hydroxide. The violet isomeride crystallises in prisms whilst the red isomeride forms microscopic needles. Both forms are vary stable dissolving in acids for example in concentrated sulphuric acid without decomposition. The absorption spectra of the solutions are practically identical with those of the cobaltiglycines. The isomeric dinitrotetramminecobaltic salts (flavo- and croceo- salts) cannot be transformed directly one into the other as is also the case with the above complex compounds. The absorption spectra of dilute solutions of the chloride and. nitrate are also practically identical the only digerenee being that the croceo-salt gives an additional band in the extreme ultra-violet.T. S. P. Internally Complex Salts of Platinum and Chromium. HEINRICH LEY and K. FICHEN (Bey. 1912 45 377-382).-When a solution of potassium platiuochloride is boiled with an excess of glycine colourless crystals of pkatinogkycine Pt(C,H,O,N) are obtained; they are sparingly soluble in hot water and soluble in concentrated sulphuric acid The stability of this compound points to the formation of an internally complex salt namely Ptatino-a-alanine Pt(C,H,O;N) is sirniiarly prepared from alanine and forms glistening white leaflets If however an excess of alanine is not used (1 mol. of potassium platinochloride to 2 mols. of alanine) a yellow solution is obtained after heating for several hours which on precipitation with alcohol gives yellow needles of potassium ptatino- cldoroakani~ze K[~:>Pt<~->C,H J which are fairly readily soluble in water. An analoious glycine compound can also be chained.If 1 mol. of the green or violet chromium chloride is heated in aqueous solutioo with 3 mols. of glycine and 3 mols. of sodiiim hydroxide gradually added a dark red solution is obtained from which violet crystals of chromiglycine Cr(C2H,02N),*OH,$H20 separate. If these are collected from the hot solution and the filtrate coucen-i. 244 ABSTRACTS OF CHEMICAL PAPERS. trated in a vacuum over sulphuric acid a further quantity of violet crystals is deposited together with larger red crystals having the composition Cr(C,f140,N),,H,0. The red are heavier than the violet crystals from which they are readily separated by levigation with alcohol Chromium-perrtammine chloride can be used instead of chromium chloride in the above preparation.Both the red and violet salts are sparingly soluble in water and the usual organic solvents. On prolonged boiling with water the red salt apparently changes into the violet salt. With concentrated sulphuric acid they give red solutions which in contradistinction to those of the cobaltiglycines gradually decompose with the formation of chromic sulphate. The violet salt is either an hydroxoaquo-salt Cr(C,H,O,N),*OH* OH2 or more probably an internally complex salt Similar compounds are obtained when a-alanine is used in place of glycine the red salt being Cr(C3H,02N)3 and the violet salt Cr(C,H,O,N),OH,H,O. Other amino-acids give similar compounds which are to be described Adaline. KARL W.ROSENMUND and F. HERRMANN (Ber. cleut. phavrm. Ges. 1912 21 96-103. Compare Abstr. 1911 i 118; ii ll2O).-It is shown that on treatment with boiling water hot alkaline solution or pyridine adaline (a-bromo-a-ethylbutyrylcarbamide) CEt,*y 0 CBrEt,. CO*NH* CO NH2 yields dieth y Z i i yduntoin colourless crystals m. p. 181-182° and that when alkaline solutions are used some ethylcrotonylcarbcmide CH,*CH:CEt CO*NH* CO-NH m. p. 9l0 is also formed together with a high-boiling oil C,,H200,N b. p. 283-286' which probably contains two adaline residues. in another paper. T'. s. P. NH<CO-NH T. A. H. Reduction of Aliphatic Amides and Esters by the Metal- Ammonias. E. CHABLAY (Compt. rend. 1912 154 364-366).- Aliphatic amides decolorise solutions of sodium in liquid ammonia a t - 50° forming a mixture of sodium alkyloxide and the sodium derivative of the amide.A similar reaction occurs with esters the same products being formed. The reaction in the latter case i s represented by the equations (1) R*CO,R' + 2Na,NH3 = R*CO*NHNa + R'ONa + NH + H ; (2) R°CO*OR + 2Na,NH3 + H = R*CH2*ONa + R'ONa + ZHN,. w. 0. w. Ureabromin. ARTHUR BILTZ (Pharm. 2entr.-h. 1912,53,245-246). -This name is applied to a molecular combination of carbamide and calcium bromide CaBr2,4CO(NH,),,prepared by mixing the two com- ponents in solution. It is readily soluble in alcohol or water insoluble in ether light petroleum or benzene and melts at 1 8 6 O . It gives all the ordinary reactions of its components when dissolved i n water.It is proposed to use it in medicine as a substitute for alkali bromides T. A. H.ORGANIC CHEMISTRY. i. 245 Reactions of Methylene. 111. Diazomethane. HERMANN Abstr. 1911 i 702 751).-During the course of some unsuccessful experiments for the preparation of cyano-isonitrile and of di-iso- cyanogen diazomethane has been obtained in 25% yield by the slow addition of chloroform (1$ mol.) in absolute alcohol to a hot alcoholic solution of potassium hydroxide (4 mols.) and hydrazine (I mol.). A slow stream of nitrogen is passed through the apparatus during the preparation whereby the diazomethane is removed and absorbed in ether. Methylhydrazine is a by-product of the reaction. Pure diazomethane has b. p. - 24' to - 23' and m.p. - 145' and is extremely dangerously explosive spontaneously or by contact with iodine grease etc. I n dilute ethereal solution however it can be ignited without exploding. When carbon monoxide is passed through ethereal diazomethane and the gaseous mixture is heated at 400-500* in a quartz tube the methglene produced by the decomposition of the diazomethane reacts with the carbon monoxide to form keten which is detected by passing the issuing gases into ethereal aniline whereby acetanilide is produced. Benzoylhydrazine potassium hydroxide and chloroform react in hot alcohol to form about 3% of diazomethane the main product being benzoic acid obtained from the intermediately formed phenylketen. Phenylhydrazine is scarcely attacked by potassium hydroxide and chloroform in hot alcohol but as-diphenylhydrazine is converted into A.PIERONI (Gazxettcc 191 1 STAUDINUER and OTTO KUPFER (Bey. 1912 45 501-509. Compare benzophenone in 60% yield. c. s. Urethane and Mercuric Acetate. 41 ii 754-756).-Mcrcurimethylzlret~~~~ hydroxide CO,Me*NH*Hg*OH is obtained by treating an alcoholic solution of equimolecular quantities of methylurethane and mercuric acetate with a slight excess of alcoholic potassium hydroxide. Mercurimuthylurethane acetate CO,Me*NH*Hg*C,H,O is prepared by dissolving equimolecular quantities of methylurethane and mercuric acetate in a little watez at 60'. On keeping the solution over calcium oxide the substance separates out in crusts of microscopic needles. When treated with alcoholic potassium hydroxide it decomposes almost quantitatively according to the equation CO,Me*NH=Hg*C,H,O + 2KI + H20 = HgI + CO,Me*NH + C,H,O,K + KOH.NevcuriethyZurethane CO,Et*NHg is deposited from a solution of ethylurethane and mercuric acetate in water; it forms crusts of microscopic needles containing 1 mol. H,O which it loses in a vacuum over sulphuric acid. iMercus.i-isoccmyZuretlTLccne CO(OC,H1,)*NHg is obtained by keeping an alcoholic solution of equimolecular quantities of isoamylurethane and mercuric acetate; it forms crystalline crusts m. p. about 165' (decomp.). With sodium iodide it decomposes in the same way as mercurimethylurethane acetate. R. V. S. Decomposition of Pyrazoline Bases as a means of Obtaining Derivatives of cycZoPropane. NICOLAI M. KIJNER (J. Buss.Php. Chew. Soc. 1912 44 165-180).-The conversion into the VOL. C I T ii. 246 ABSTRACTS OF CHEMICAL PAPERS. dicyclic hydrocarbon carane of the base obtained by the action of hydrazine on tanacetone (compare Abstr. 1911 i 1028) seemed to indicate that the formation of the trimethylene ring mas related t o the formation of the base. Since mesityl oxide a compound structurally very similar to pulegone also reacts with hydrazine to form a com- pound which gives 1 1 2-trimethylcyclopropane on decomposition it was at first thought that the product of the interaction of mesityl oxide and hydrazine was not a pyrazoline derivative as Curtius supposed but a compound having the structure Further investigation has shown hiwever that this compound is really a pyrazoline derivative as also is the base formed by pulegone with hydrazine this having the constitution >NH yH,-CH,* $?H*CMe CHMe*CH,*C==-N and not that previously given (Zoc.cit.). The decomposition of this compound into carane and nitrogen is exactly similar to that of 3 5 5-trimethylpyrazoline (from mesityl oxide and hydrazine) into 1 1 2-trirnethylcyclopropane and nitrogen the two nitrogen atoms being eliminated from the pyrazole nucleus and the residue closing up to a three carbon-atom ring. Similar decompositions take place with 1-methyl-1 2-diethylpyrazoline which yields 1-methyl-1 2-diethyl- cyclopropane and with esters of pyrazoline-3 4 5-tricarboxylic acid which yield esters of cyclopropanetricarboxylic acids (compare Buchner Abstr. 1888 1274; 1890 736).The author intends to ascertain whether derivatives of cyclo- propanone can be obtained in a similar manner from pyrazolone compounds. 1 1 2-Trimethylcyclopropane C6H1 obtained by heating 3 5 5- trimethylpyrazoline in a sealed tube with potassium hydroxide and platinised porous tile is a liquid b. p. 52.Ei0/752 mm. 52.6'/753 mm. 52*8'/756 mm. DF 0,6949 n 1.3866. The compound described under this name by Zelinsky and Zelikoff (Abstr. 1901 i 657) was apparently not pure the high value of the molecular refraction indicating considerable admixture of ethylene hydrocarbon. The action of alkaline permnnganate on 1 1 2-trimethylcyclopropane i R very slow but much more rapid than with the dicyclic trimethylene hydrocarbons thujane and carane or with the 1 -methyl-1 2-diethyl- cyclopropane described below.Fuming nitric acid readily reacts with the hydrocarbon with development of heat whilst concentrated sulphuric acid polymerises it. The action of bromine on 1 1 2-trimethylcyclopropane in acetic acid solution yields (1) a small proportion of P-bromo-@methyl- pentane CMe,Br*CH2*CH,1Sle b. p. 136-138O/752 mm. DEo 1.1806 n 1.4517 which is the result of a secondary reaction of the hydrogen bromide liberated on the hydrocarbon ; (2) PG-dibromo-/I-methylpentana CMe,Br*CH,*CHMeBr b. p. 87-89'/23 mm. D 1.6242 Di0 1.5979 nu 1.5097 which yields P-methylpentane when reduced with hydrogenORGANIC CHEMISTRY. i. 247 iodide ; thus combination of bromine with 1 1 2-trimethylcyclo- propane takes place a t the least hydrogenated carbon atom.Reduction of 1 1 2-trimethylcyclopropane by Sabatier's method gives PP-dimethylbutane so that hydrogen combines with this hydro- carbon a t the most highly hydrogenated carbon #i ' t om. The action of fuming hydriodic acid on 1 1 2-trimothylcyclo- propane yields (1) P-iod0-/3y-dimethyl butane CMe,I*CHMe b. p. 83-84'/77 mm. 141°/755 mm. (slight decornp.) D;'' 1.4435 n 1 *5035 which seems to be accompanied by a small proportion of another iodo-compound probably /3-iodo-P-methylpentane. The action of fuming hydrobromic acid on 1 1 2-trimethylcyclopropane yields P-bromo-P-methylpen tane (see above). _ - YHEt obtained by heat- CN2<CMeEt' 1- Methyl- 1 2 - diethy Zc yclopopane ing 5-methyl-3 5-diethylpyrazoline (compare Curtius and Zinkeisen Abstr.1899 i 165) in a sealed tube at 240° has b. p. 108-109'/ 742 mm. Di" 0.7382 n 1.4102 It combines slowly with bromine whilst with hydrobromic acid it gives y-bromo-y-methyl~eptarte (O) b. p. 101-102'/53 mm. DP 1.1406 r~ 1.4613 which when distilled with aniline yields an unsaturated hydrocarbon CSH16 b. p. 117-1 19'1 742 mm. D:"' 0.7426 n 1.4210 this forming a liquid bromide. T. H. P. Loschmidt's Graphic Formula History of the Benzene Theory. RICHARD ANSCHUTZ (Ber. 191 2,45,539-553).-Historical. The author gives an account of the graphic formula developed by Loschmidt i n his '' Chemische Xtudien " (Vienna 1861). It is pointed out that the latter ascribed a ring structure to the benzene nucleus four years before Kekule published his benzene theory Stereochemistry of the Aromatic Series.R O M ~ CASARES (Anal. Pis. Quim. 1912 10 14-18).-The author proposes a three dimensional formula for benzene based on an alternate arrangement of tetrahedra in such a way that the projection on a plane is a regular hexagon. The difference from Ladenburg's prism formula is slight and the same diaculty would be experienced in explaining the mechanism of reduction. Naphthalene anthracene phenanthrene and chrysene are formulated on the same principle. F. B. G. D. L. Hydrogenation and Dehydrogenation. HEINRICH WIELAND (Bey. 191 2 45 484-493).-The researches of Sabatier Ipatieff Knoevenagel and others shorn that the addition of hydrogen to an unsaturated organic compound in the presence of finely divided nickel copper palladium etc.at a definite temperature is reversed at a higher temperature. It is to be anticipated therefore t h a t Paal's method of reducing substances containing double linkings by hydrogen in the presence of colloidal palladium a t the ordinary temperature is reversible and that under definite conditions the same state of equilibrium must be reached whether the unaaturated or the hydrogenised substance is employed initially. The author finds that by shaking with palladium s 2i. 248 ABSTRACTS OF CHEMICAL PAPERS. black (carefully prepdred free from oxygen) aqueous quinol is partly converted in to p-benzoquinone and quinhpdrone hydrazobenzene dissolved in benzene is changed into azobenzene and aniline dihydro- naphthalene dissolved in benzene yields naphthalene and tetrahydro- naphthalene and dihydroanthracene in benzene is slowly transformed into an thracene ; acenaphthene and bisdiphenylene-ethane are un- changed under the preceding conditions.In these reactions the palladium plays the part not of a catalyst but of a substance of active mass; by increasing the amount of the metal the equilibrium of the system is shifted in the direction whereby the yield of the dehydrogenised substance is increased. Unsaturated substauces which decolorise potassium permanganate can in general be catalytically hydrogenised but are not necessarily attacked by nascent hydrogen ; naphthalene is unnff ected by hydrogen and palladium but is reduced t o dihydronaphthalene by sodium and alcohol whereas dihydronaphthalene is unaffected by sodium and alcohol but is easily converted into tetrnbydronaphthalene by hydrogen and palladium.It appears therefore t h a t the activation of hydrogen in the presence of a finely divided metal is not due to the production of nascent (atomic) hydrogen but more probably t o the formation of a metallic hydride which additivelyreacts with the unsaturated substance R:R + PdH The probability of the formation of such intermediate additive compounds is supported by the facts that methyl or ethyl alcohol is absorbed by palladium black with development of heat and the alcohol can only be recovered by long keeping in a vacuum ; it then contains a certain amount of the aldehyde. Under R U C ~ conditions propyl alcohol is much more readily converted into propaldehyde whilst benzyl alcohol yields benzaldehyde at once.c. s. RH*R*Pd€€ Z RH*RH + Pd. The Addition of Chlorine to Dichlorobeneenes. T. VAN DER LINDEN (Ber. 1912 45 411-418. Compare this vol. i 174).-The author hoped by the removal of two molecules of hydrogen chloride from any dichlorobenzene hexachloride [octachloroc~cZohexane] to obtain a substance of the composition U,H,CI which might be considered as identical with the assumed intermediate product in the substitution of a chlorine atom into tetrachlorobenzene. The additive compound of p-dichlorobenzene and chlorine was obtsined by passing chlorine into a solution of the substance in carbon tetra- chloride under strong sodium hydroxide solution in sunlight also by exposing to sunlight a mixture of the theoretical quantities of p-dichloro- benzene and chlorine in a closed tube.The main product (from its resemblance to P-benzene hexachloride) is designated P-p-dichlorobenzeno hexachloride and after recrystallisation from nitrobenzene has m. p. 262'; it has already been obtained by Jungfleisch (Bull. Xoc. chiin. 1868 [Z] 9 352). On treatment with alcoholic potash three molecules of hydrogen chloride are eliminated with formation of pentachloro- benzene; the same behaviour is exhibited by all the isomerides described below. The carbon tetrachloride mother liquors of the above substance contained an isomeric hexachloride which on account of its low m. p.ORGANIC CHEMISTRY. i. 249 and considerable solubility is termed a-p-dichloroberzxenze hexachloride ; the rn. p. is 89.6'. Indications of a third isomeride m.p. 110-120° were also observed. o-Dichlorobenzene hexachloride obtained by the sealed tube method has m. p. 147'. m-Dichlorobenzene hexachloride was obtained by the action of chlorine on the dicbloro-compound under a layer of dilute sodium hydroxide solution ; it has m. p. 81.S'. As the above substances even when treated with an insufficiency of alcoholic potash yield only pentachlorobenzene and unchanged substance a- and P-chlorobenzene hexachlorides were prepared by the sealed tube method but alcoholic potash again removes simultaneously three molecules of hydrogen chloride from each molecule of hexachloride. D. F. T. Reduction of Nitrobenzene by means of Ferrous Hydroxide. HERMAN CAMP ALLEN (J. Physical Ciiem. 1912 16 131-169).-The products of reduction of nitrobenzene by ferrous sulphate with slight excess of sodium hydroxide depend on the temperature concentration and order of mixing of the reacting substances.When nitrobenzene is run into a well stirred mixture of ferrous sulphate and sodium hydroxide solutions or when nitrobenzene and ferrous sulphate are stirred together and sodium hydroxide is slowly introduced the reduction takes place in a neutral or slightly alkaline medium and the product is mainly aniline. The yield of aniline varies from 100% at room temperature to 80% at the boiling point. A high yield of aniline is also obtained when the ferrous sulphate is added last if it is run in quickly and in excess. When however sodium hydroxide and nitrobenzene are stirred together and ferrous sulphate is added very slowly the reduction takes place in a strongly alkaline medium and the product is mainly hydrazobenzene. A t 7 5 O the yields were aniline 21% hydrazobenzene 60% azoxybenzene 14%. A t the boiling point the yields were aniline 33% hydrazobenzene 58%.When the ferrous sulphate was restricted to the amount required t o reduce to azoxy- benzene only the yields were aniline IS% azoxybenzene 76%. Both azoxybenzene and azobenzene are reduced by excess of alkaline ferrous sulphate at the boiling point the product being hydrazobenzene with some aniline. Aniline seems to be formed in this may in the alkaline reduction of nitrobenzene at loo' whereas a t the ordinary temperature it is formed by the nitrosobenzene-phenyl- hydroxylamine route.There is a minimum production of aniline at about 75' and the utility of alcohol in the electrolytic productioo of hydrazobenzene and azobenzene is partly due to its solvent action and partly to its favourable boiling point. According t o Haber's scheme for the reduction of nitrobenzene (Abstr. 1900 i ZSl) azoxybenzene is the immediate forerunner of hydrazobenzene as the above results suggest and the oxidation of hydrazobenzene by nitrobenzene gives azobenzene the nitrobenzene being reduced to azoxybenzene at the same time. The author fiuds that the production of azobenzene from hydrazobenzene on boiling for twenty minutes with excess of nitrobenzene is almost quantitative andi. 250 ABSTRACTS OF CHEMIOAL PAPERS. azoxybenzene is formed simultaneously in accordance with Hsber’s view.I n the Elbs method of electrolytic preparation of azobenzene the intermediate stage is probably azoxybenzene since with a low current density in well stirred solutions azoxybenzene is the principal product. I n the author’s experiments 1.2 gram of nitrobenzene was reduced and the filtered liquid was extracted with benzene. It was assumed that the extract contained only aniline hydrazobenzene azobenzene azoxybenzene and unaltered nitrobenzene. The aniline was extracted with dilute sulphuric acid and titrated with bromate The residue was estimated by evaporating until a more or less sharp bend in the time- weight curve indicated that the last traces of benzene had been removed. A similar procedure gave the residue after aniline and hydrazobenzene had been extracted together by 1 3 sulphuric acid; hence hydrazobenzene was calculated by difference.Azobenzene was estimated colorirnetrically in the above residue and nitrobenzene was reduced to aniline and titrated. Azoxybenzene was then calculated by difference. Phenylhydroxylamine was present in traces only. I n nentral or slightly alkaline reductions at the boiling point about 15% of the nitrobenzsne remained unaccounted for. It is suggested that decomposition of the intermediate product phenylhydroxylamine may have given rise to substances not extracted by benzene from the aqueous solution I n strongly alkaline reductions a t the boiling point the nitrobenzene could all bo accounted for. Fission of Phenylethyltrimethylammonium [Chloride]. HERMANN FMDE (Apoth.Zeit. 1912 2’7 18-19).-The reduction of phenylethyltrimethylammonium chloride by means of sodium amalgam (compare Abstr. 1909 i 708 ; this vol. i 20) results in the formation of trimethylamine and styrene instead of ethylbenzene as previously assumed. In this case the action of sodium amalgam is precisely similar t o that of sodium hydroxide. Explicit directions are given for the reduction of crude benzyl cyanide to phenylethylamine and for the transformation of the latter into phenylethyltrimethylammonium chloride by means of methyl sulphate. H. W. New Derivatives of Indene. VICTOR GRIGNARD and CHARLES COURTOT (Compt. rend. 1912 154 361-364. Compare Abstr. 1911 i 193 292).-The action of bromine on magnesium indenyl bromide gives rise to the formation of 1 2 3-tri6romoindanc C,H7Br m.p. 133-134O together with an oily substance containing 1-brromoindcne C,H,Br. The latter is best prepared by adding the organo-magnesium derivative to cyanogen bromide when it is obtained as a yellow liquid b. p. 126’/22 mm. The compound resembles ally1 bromide in its reactions. If cyanogen chloride is used instead of the bromide 1-cyanoindene C,,H7N b. p. 140-142O/14 mm. is formed. When treated by Pinner’s method this yields ethyl indene-1- R. J. C. carboxylate b. p 140°/8 mm. (compare Weissgerber Abstr. 19 11 i 1442). Di-indenyl CH<~j~CH*CH<&>CH prepared by theORGANIC CHEMISTRY. i 251 action of iodine on magnesium indenyl bromide in toluene occurs as colourless crystals m. p. 99-looo; when treated with bromine it forms two tetrcdromides.One of these is soluble in chloroform and has m. p. 138-139O whilst the other is insoluble and has m. p. 222-2 2 4.O. The Influence of the Nitro-group on the Sulphonation of Diphenylmethane. ALFRED KLIEOL ( Ye&. Ges. deut. Naturforsch. Aerxte 1912 ii [l] 225-226).-Wedekind and Schenk (Abstr. 1911 i 190) found it impossible to sulphonate the methylene group of diphenylmethane with chlorosulphonic acid. An attempt has there- fore been made to lessen the liability of the nuclei to sulphonation and at the same time to increase the reactivity of the methylene group by the introduction of substituents. It is found however that nitro-groups increase the readiness with which diphenylmethane is sulphonated. I n all three nitrodiphenylmethanesulphonic acids the sulpho-group occupies the para-position in the un-nitrated nucleus.Triphenglmethane behaves in a similar manner and o-nitrotriphenyl- methane gives a disulphonic acid with concentrated sulphuric acid on the water-bath. p-Aminodiphenylmethane-p-sulphonic acid yields a sparingly soluble diazosulphonic acid which behaves as an internal salt although the two salt-forming groups are attached to different nuclei. HANS KAPPELER (Ber. 1912 45 633-635).-The sulphonation of P-nitronaphthalene with. fuming sulphuric acid is completely analogous to that of P-naphthyl- amine. A mixture of two monosulphonic acids is obtained which were identified by reduction to the corresponding p-naphthylaminesulphonic acids. 2-Nit~onaphthalenc-5-sulphonyl chloride forms large pale yellow prisms m.p. 127' ; the corresponding amide crystallises in yellow four-and six- sided plates m. p. 223-224'. 2-Nitronaphthalene-8-suZphonyZ chloride separates in tiny almost colourless needles m. p. 169-170° ; the ccmide forms colourless crystalline tablets m. p. 261-262'. The free sulphonic acids were obtained as colourless microcrystalline precipitates. E. F. A. Action of Sulphurous Acid on Aldehydoaminic Bases. MARIO MAYER (Gasxetta 1912 42 i 50-56. Compare Abstr. 191 1 i 223).-BenxylideneaniZine. anhydrosulphite (CHPh:NPh),,S02 is an orange-yellow powder m.. p. 115-120° (decomp.) which is obtained when dry sulphur dioxide acts on dry benzylideneaniline and also (more easily) when a benzene solution of benzylidene- aniline is saturated with sulphur dioxide.The substance loses sulphur dioxide when kept leaving benzylideneaniline as the only product. Aniline benzylideneaniline sulphite already obtained by Knoe- venagel can also be prepared by saturating an ethereal solution of benzylideneaniline with sulphur dioxide. When it is heated in a w. 0. w. C. H D. Sulphonation of P-Nitronaphthalene.i. 252 ABSTRACTS OF CHEMICAL PAPERS sealed tube for some hours at 105-llO' aniline and aniline sulphite are formed and in addition benxylideneaniline hydrogen sulphite C,,H,,O,NS. This decomposition renders improbable Eibner's supposition (Abstr. 1901 i 376) that the original compound is d ianilinophen y lme t hane an hy drosulphite CHPh (NHPh) SO,. Benzyl- ideneaniline hydrogen sulphite is best prepared by passing sulphur dioxide through a very dilute aqueous-alcoholic solution of benzyl- ideneaniline; it forms tufts of acicular crystals m.p. 145'. If the solution is more concentrated the salt of m. p. 125' is obtained but when this is removed the liquid slightly warmed and treated with more sulphur dioxide a substance separates in the form of long flat needles m. p. 147' which are identical in behaviour with those above mentioned m. p. 145'. Benzylideneaniline hydrogen sulphite yields the above-mentioned salt of m. p. 125' when treated with aniline. Speroni (Abstr. 1903 i 246) obtained the neutral anhydrosulphite of aniline and benzaldehyde giving the m. p. 138-1409 On repeating this preparation the author obtains a substance m. p. 125' which is identical with Knoevenagel's salt previously referred to If however this compound is treated with warm alcohol the greater part of it then has m.p. 140' (decomp.) and gives the same analytical figures as the salt of m. p. 125' and it is suggested that the two substances are the aniline salts of two isomeric forms of the sulphurous acid. Speroni by treating a neutral aqueous solution of aniline sulphite with benzaldehyde obtained a substance m. p. 130° but the author working under the same conditions always obtains a product m. p. 125-127" identical with the salt of m. p. 125' already mentioned. When the three compounds above described (of m. p. 115-120° 145O and 125' respectively) are treated with a cold saturated alcoholic solution of picric acid the first two yield benzylideneaniline picrate whilst the third gives also aniline picrate.I n regard to the constitution of the sulphites described in this and in the earlier paper the author rejects Eibner's view (Zoc. cit.) that all compounds formed from aldehydes amines and sulphurous acid are sulphites of aldehydoaminic bases. Such substances as the additive products from benzylideneaniline and sulphur dioxide or sulphurous acid do belong to that type but the other compounds described in the present paper and the aldehydo- and keto-sulphites of the alkaloids do not. The aldehydoaminic bases which are obtained when some of these decompose are not present in the compounds themselves but are formed by the interaction of the aldehyde and amine first formed in the decomposition. R. V.5. Electrolysis of Phenyldialkylhydroxyethylammonium Iodides and Some Derivatives of Choline. BRUNO EMMERT (Ber. 19 12 45 430-433).-The electrolysis of quaternary phenylammo- nium salts at lead cathodes leads to the formation of tertiary aliphatic amines (Abstr. 1909 i 376 602). An attempt has been made to extend this metfhod to those cases in which unsaturated aliphatic andORGANIC CHEMISTRY. i. 253 hydroxyalkyl groups are attached to the N-atom. By the electrolysis of phenyldimethylallylammonium iodide however propylene and dimethylaniline were obtained in good yield the ally1 instead of the phenyl group being eliminated. Electrolysis of phenyldimethyl- hydroxyethylammonium iodide and of phenylmethylethylhydroxy- ethylammonium iodide yielded dimethyl-P-hydroxyethylamine and methylethyl-P-hydroxyethylamiue whilst at the same time a certain amount of a tertiary aniline was formed one aliphatic group being split off.Dimethyl-P-hydroxyethylamine was dried over potassium hydroxide and barium oxide and whilst still somewhat moist had b. p. 129-133'. Ladenburg (Abstr. 1882 166) found 130-134" and Knorr (Abstr. 1889 905) 128-130". Methylethy 1-P-hydroxyethylamine isolated through its hydrochloride had b. p. 149-150'. The aurichloride was analysed. When treated with methyl iodide in ethereal solution it formed dimethylethyl- P-hydroxyethylamnaonium iodide which on treatment with moist silver oxide yielded the corresponding base. The latter was identified by conversion into its azwichloride m. p. 276-277" (decomp.). Methyl- ethyl-P-hydroxyethylamine and ethyl iodide reacted to form an iodide from which methyldiethyl-P-hydroxyethylammonium hydroxide was prepared.The aurichloride obtained from the latter had m. p. 246-247" (decomp.). A similar series of compounds was obtained from methylethyl- P-hydroxyethylamine and propyl iodide. In this case the corresponding awichloride could not be obtained in a crystalline state. The platini- chloride C,6€I,,0,N,CI,Pt was aaalysed. H. W. Diphenylhydroxylamine. HEINRICH WIELAND and ALEXANDER ROSEEU (Ber. 1912 45,494-499).-The interaction of nitrosobenzene and magnesium phenyl bromide in ether at -15O under carefully regulated conditions leads to the formation of PP-diphenylhydroxyl- amine NPh,*OH m. p. 60' (decomp.) colourless crystals. The substance when pure can be kept for eight days without decomposi- tion develops a deep blue coloration with concentrated sulphuric acid is neutral in character reduces ammoniacal silver solutions in the cold and yields diphenylamine by reduction. It reacts with diphenyl- hydrazine hydrochloride (0.5 mol.) in slightly acidified alcohol to form the hydrochloride of quinoneanildiphenylhydrazone (Abstr. 19 1 1 Action of Bromine in Presence of Aluminium Bromide on the Methylcyclohexanols. FERNAND BODROUX and FELIX TABOURY (Compt.rend. 1912 154 521. Compare Abstr. 1911 i 779).-The three rnethylcyclohexanols behave similarly to cylohexanol in their behaviour towards bromine in presence of aluminium bromide. In each case the solid pentabromotoluene is formed together with a yellow oil. The latter is a mixture of bromo-derivatives and is capable of undergoing further bromination giving gummy products in the case of methylcyclohexan-2- and -4-01.The third isomeride however gave a small quantity of he~brorrLomethylcyclohexane C7H,Br in the The gold salt was analysed. i 82) the constitution of which is thus definitely settled c. s. form of long colourless needles m. p. 2959 w. 0. w.i. 254 ABSTRACTS OF CHEMICAL PAPERS. Halogen Derivatives of Phenolic Ethers. ALPHONSE MAILHE and MARCEL MURAT (Compt. rend. 1912 154 601-604 *).-The catalytic method in which thorium oxide is employed is very advantageous for the preparation of diphenyl ether and its homologues which are obtained with difficulty by the ordinary processes. p-Chlorodiphenyl ether OPh*CqH401 prepared by the action of chlorine in presence of iodine on diphenyl ether in carbon tetrachloride solution has b.p. 284'/760 mm. D15 1.2026 n 1.599 ; di-p-chloro- diphenyl ether O(C6H,C1)2 formed a t the same time has b. p. 31 2-315'. p-Bromodipphenyl ether has b. p. 305O and the dibromo-derivative m. p. 54' b. p. 338-340°. Di-o-tolyl ether gave the following com- pounds a monochloro-derivative b. p. 308-310° a dichloro-derivative b. p. 338-340° a monobrorno-derivative b. p. 330°/670 mm. D1O 1.4162. Di-ptolyl ether gave a mowchloro-derivative b. p. 315'/760 mm. a dichloro-derivative b. p. 240-245O/20 mm. D1* 1.1800 a monobromo- derivative b. p. 330-333'/760 mm. DIO 1.417 and a dibrorno-deriv- Action of Bromine and Chlorine on Dehydrodicarvacrol.HENRI COUSIN (Compt. rend. 1912 154 441-443; J. Pharrn. Chim. 1912 [vii] 5 236-24O.T Compare Abstr. 1910 i 476).-Ddromo- dehydrodicarvacrol C,oH2402Br2 prepared by the action of bromine on dehydrodicarvacrol in chloroform solution occurs in pale yellow prisms m. p. 179-1 80' (cow.). The corresponding dichlord-derivative obtained by using the calculated amount of chlorine crystallises in pale yellow prisms. When excess of chlorine is employed dichloro- dehydrodicarvncropzi~one tetrachZoride C,,H,,O,Cl is formed as a yellow resin slowly changing to crystals m. p. 155-156' (decornp.). When treated with reducing agents this substance yields dichloro- dehydrodicarvacrol ; the corresponding quinone has not been isolated. ative m. p. 131'. w. 0. w. w. 0. w. Colour of Alkaline Solutions of Quinol and of Their Oxidation Products.ROBERT LUTHER and A. LEUBNER (J. pr. Chem. 191 2 [ii] 85 233-234).-0n treatment with aqueous alkalis quinone gives yellowish-green solutions which become brownish-black on exposure to air. Addition of sodium sulphite to solutions of quinone produces an intensely greenish-blue coloration which gradually changes to light yellow. When shaken with air the yellow solutions become green and then light yellow If the traces of oxidation- products formed by dissolving the quinone are destroyed by potassium hydrogen sulphite or quinol the addition of sodium sulphite produces a brown coloration. The blue coloration is probably due to the formation of an alkali salt of an oxidation product of quinone. According to Euler and Bolin (Abstr.1909 ii 374) quinol dissolves in alkalis yielding yellow solutions owing to the formation of quinonoid salts. The authors find however that solutions of potassium carbonate or potassium hydroxide and of quinol to which small quantities of sodium hydrogen sulphite have been added in * and Bull. SOC. chirn. 1912 [iv] 11 328-332. t and Bull. SOC. chim. 1912 [iv] 11 332-336.ORGANIC CHEMISTRY. i. 255 order t o destroy dissolved oxygen and traces of quinone do not yield yellow colorations when mixed but gradually acquire a dark brown colour on exposure to air. From these observations the conclusion is drawn that salts of quinol quinone hydroxyquinol and dihydroxyquinol are respectively colourless yellow bluish-green and reddish- brown.F. B. Isomerism Among the Ethers of Diisoeugenol. ERNESTO PUXEDDU (Atti R. Accad. Lincei 1912 [v] 21 i 124-129. Compare Abstr. 1909 i 225).-The author considers it probable that the polymerisation of eugenol ethyl ether observed by Wassermann is preceded by an isomerisation so that Wassermann's polyrneride is a diisoeugenol diethgl ether stereoisomeric with the diisoeugenol diethyl ether described by the author (loc. cit.). They differ not only in solubility and in m. p. but also give different bromine derivatives. Eugenol ethyl ether was prepared by the action of ethyl sulphate on eugenol dissolved in potassium hydroxide (lo%) and also by Wasser- mann's method. When it was distilled the residue which did not distil at 260" consisted of Wassermann's polymeride but had m.p. 140" (Wassermann gave 125'). It is obtained in better yield by heating eugenol ethyl ether for fifteen hours in a bath at about 270". I n chloroform solution it absorbs bromine but no individual substance could be isolated from the product. The diisoeugenol diethyl ether previously described by the author when treated with bromine in ethereal solution cooled with ice and salt yields rnorzobromodiiso- eugenol diethyl ether C,,H,,O,Br which forms yellowish-green rhombohedra1 crystals rn. p. 118". Iodothio-ethers Iodosulphones Iodosulphonic Esters and their Derivatives with Multivalent Iodine. CONRAD WILL- OERODT and MAX KLINGER (J. pr. Chenz. 1912 [ii] 85 189-198).- p- Iodot hiophenc t o Ze ( p-iod ophen y Z et h y I sulphid e) C6H4 I* S E t prepared by reducing p-nitrothiophenetole (p-nitrophenyl ethyl sulphide) with tin and hydrochloric acid and replacing the amino-group of the result- ing p-arninothiophmetole (p-aminophenyl ethyl sulphide) by iodine by means of the diazo-reaction is a yellow oil b.p. 146-147°/11 mm. When treated with chlorine in chloroform solution it yields an unstable iododichloride which rapidly decomposes into p-iodothiophenetole and p-iodobenxenesulphonyl chloride. The formation of the latter compound is considered to be due to the decomposition of the iododichloride into ethyl chloride and the compound (I) which then reacts with the iodoso-compound (11) produced by the action of moisture on the iododichloride (I) c6w,Iosc1 + (11) 2SEt*CGH4*I0 = 2C,H,I*SEt + C,H,I*SO,Cl. Methyl p-iodobennxenesulphonate prepared from the sulphonyl chloride and methyl alcohol crystallises in rhombohedra m.p. 74O. It yields a yellow crystalline iododichloride IC1,*C6H4*S0,Me which is converted by aqueous sodium carbonate into methy2 p-iodosobenxene- sulphonate IO*C,H,*SO,Me (decomp. 176-1 78') ; the iodosoacetate I(oAc),*C,H,*SO,Me forms rhombic prisms m. p. 174O. Methyl p-iodoxybenxenesdphonate is prepared by the action of sodium hypochlorite and acetic acid on the iododichloride. R. V. 5.i. 256 ABSTRACTS OF CHEMICAL PAPERS. p-lodophernylethylsuZphone C,H,I*SO,Et obtained as a white powder m. p. 83' by oxidising p-iodothiophenetole .with chromium trioxide in glacial acetic acid solution yields an iododichloride ICl$C,H,*SO,Et (decomp. lls') which is converted by the usual methods into p-iodoso- phenylethylsulphone (decomp. 235O) the iodosoacetate I(OAc),*C,H,*SO,Et monoclinic needles m.p. 167-1 70° and p-iodoxyphenyZet7~yZsuZphone I02=C,€€:,*S02Et which crystallises in small octahedra exploding at 220'. p-lododiphenyl sulphide C,H,I*SPh prepared from p-aminodiphenyl sulphide (Kehrmann and Bauer Abstr. 1897 i 27) by means of the diazo-reaction crystallises in lustrous white leaflets m. p. 35' b. p. 230°/1 1 mm. Attempts to prepare the iododichloride by the action of chlorine in chloroform solution yielded a yellow oil which on exposure t o air is transformed into p-iododiphenyl suZphoxide C,H,I*SOPh and p-iododiphenylsui'phone C6H,I*S0,Ph. The last-mentimed com- pound has also been prepared (1) by oxidation of p-iododiphenyl sulphide with chromium trioxide in glacial acetic acid solution and (2) by the interaction of p-iodobenzenesulphonyl chloride and benzene in the presence of aluminium chloride.It crystallises in white needles m. p. 141' and forms an iododichloride ICl,*C,H+-SO,Ph rhombic crystals (decornp. 130'). p-lodosodiphenylsulphone is a pale yellow powder (decornp. 210") ; the iodosoacetate I(Ohc),*C,H,*SO,Ph forms white needles (decornp. 195') ; p-iodoxydiphenylsulphone IO2*C,H4*SO2Ph crystallises in white leaflets which explode a t 220-223'. p-Iododiphenylsulphoxide prepared by oxidising a cold glacial acetic acid solution of p-iododiphenyl sulphide with aqueous chromic acid forms large white rhombic crystals m. p. 106'. F. B. Iodosulphones and Their Derivatives with Multivalent Iodine.CONRAD WILLGERODT and MAX PLOCKSTIES (J. pr. Chem. 1 9 1 2 [ ii] 85 1 9 8 -2 0 7). -p- Zodopherz yl- p-t ol y Zsdphone (4 -iodo- 4'- methyldiphenylsulphone) C,H,Me*SO,*C,H,I is prepared by the interaction of p-iodobenxenesulphon yl chloride and toluene in carbon disulphide solution in presence of aluminium chloride ; it crystallises in rhombs m. p. 162" and yields a n iododichloride which crystallises in slender sulphur-yellow needles (decornp. 1 ZOO) and forms with pyridine a n additive compound Cs H,Me*SO,* C,H,*ICl 2C,H,N decomposing at 11 8- 1 20'. 4-Iodosophenyl-ptolylsulphone is a pale yellow powder (decomp. 197") ; the iodosoacetate C,H,Me*SO,*C,H,'I(OBc) crystallises in lustrous needles decomposing a t 180'. 4-Zodoxyphenyl-p-tolylsu2phorne C,H,Me*S0,*C6H,~I0 forms a white powder (decomp.320°) and reacts with 4-iodosophenyl-p-tolylsulphone and silver oxide in the presence of water yielding di-p-4-toluenesulphonylphernyliodinium hydroxide OH~~(c,H4~S0,4C,H,Me)2,~ which was obtained only in aqueous solution and forms a yellow iodide.ORGANIC CHEMISTRY. i. 251 p-4 - To luenusul~honyldiphenyl~odi~i~~ chloride C,H,Me*SO,= C,H,-IPhCl is obtained in aqueous solution by heating phenyl-p-tolylsulphone- 4'-iododichloride with mercury diphenyl and water at 50' ; the iodide (decomp. 132') and pbtinichloride slender yellow needles (decomp. 178') are described. 4-Iododiphe~zylsulpJ~0ne-4~-carboxyZic acid C,H,I*S0,*C,H4*C0,H prepared by the oxidation of 4-iodophenyl-p-tolylsulphone with chromium trioxide in glacial acetic acid solution crystallises i n colourless slender needles m.p. 293" and yields crystalline sodium and silver salts; the iodoclkhloride could not be obtained in a pure condition. Ethyl 4-iododiphenyZsulpJ~o~ze-4'-carboxylate prepared by esterifyini the preceding acid crystallises in slender needles m. p. 140' ; it yields a yellow crystalline iododichloride IC1,*C,H,~S0,*C6H,*C02Et (decomp. 1 lo') which is converted by aqueous sodium carbonate into ethyl 4-iodosodiphenylsul~iione-4'-carboxyZn;te IQ*C,H,-SO,*C,H,*CO,Et a pale yellow powder decomposing at 235'. 4-lodop?tenyZ-2-p-xylyZs~lphone C6H,I*S0,*C,H,Me is obtained in quadrilateral prisms m. p. 115' by the interaction of p-iodobenzene- siilphonyl chloride and p-xylene in the presence of aluminium chloride. The iododichloride ICl,*C,FI,-SO,*C,H,Me forms short yellow needles (decomp. 138') ; 4-zodosop?~enyl-2-p-xyl~lsulphone is a pale yellow powder (decomp.134'). 2-p-XyZenesu~l~on~ldip~enyliodin~u~ (2 5 - dimeth?/MipJierzyZsulp~~one- 4'-phenyliodinium) chlo&Zc C,I3[,~~e;SO2~C6H~*IPh*~~ is obtained by the action of mercury diphenyl on the preceding iododichloride in chloroform solution ; the platinichloride (decomp. 182') and iodide (decomp. 135') are also described F. B. 4-Amino-1-naphthyl Mercaptan. THEODOR ZINCKE and FRANZ SCHUTZ (Ber. 1912 45 471-483).-4-Amirno-l-naphthyl mereaptan NH,*C,,H,*SH' m. p. 91-93' yellow needles is obtained by reducing 4-acetylamino-1 -naphthalenesulphonyl chloride by alcohol concentrated hydrochloric acid and zinc and hydroly sing the resulting acetylamino- naphthyl mercaptan by alcohol and hydrochloric acid. The hydro- chloride sulphate acetyl derivative m.p. 173" and diacetpl derivative m. p. 152" are described. With alcoholic benzsldehyde it forms the benxylidene derivative CHPh(S*C,,H,*N:CHPh) m. p. 68O yellow powder in which the benzylidene group attached to the sulphur atoms is hydrolysed by alkalis and those attached t o nitrogen by acids. The disdphide S,[C,oH6*NH2]2 m. p. 168' is obtained by oxidising the amino-mercaptan with 30% hydrogen peroxide in alcoholic or alkaline solution. It forms a diacetyl derivative m. p. 265O yellow needles which is also obtained by the oxidation of the acetylaminonsphthyl mercap tan. When a suspension of 4-acetylamino-1-naphthyl mercaptan in chloro- form or carbon disulphide is treated in a freezing mixture with chlorine (1 mol.) the preceding disulphide is first formed and then changes to 4-cceetylamiao- 1 -ch~orothio~~a~hth~b~ene NHAc.CIOH6* SCL a yellowi. 258 ABSTRACTS OF CHEMICAL PAPERS. powder which forms intensely yellow solutions and is very reactive (compare Abstr. 1911 i 368) yielding the disulpbide with alcohol or formic or acetic acid and 4-acetylarnino- 1 -acetonylthiolnaphti~alene NHAc*C,,H,-S*CH,~COMe m p. 155-160° white crystals with acetone ; the last compound is also obtained from chloroacetone and acetylaminonnphthyl mercaptan in dilute sodium hydroxide. 4-AcetyZ- amino-1-bromothiolnaphthalene NHAc*CloH,*SBr is obtained in a similar manner ; it can only be isolated in the form of the hydrobromide a yellow powder.An excess of bromine converts 4-acetylamino- 1 -napht h yl mercapt an in chloroform into 1 -bromo- 4-acetykaminonaphtha- lene hydrobromide CIoH,Br*NHAc,HBr m. p. 205' (decomp.) straw-yellow needles. 4-Aceiylarnino-l-nccphthyl methyl sulphide NHAc*C,,H,*SMe m. p. 193' yellow needles is obtained by shaking methyl sulphate and 4-acetylamino-1-naphthyl mercaptan in a slight excess of 10% sodium hydroxide. By hydrolysis with alcohol and concentrated hydrochloric acid it yields 4-amino-1 -naphthyZ methyl sulphide hydrochloride NH,*CloH6*sMe HC1 white needles from which the free base C1,Hl1NS m. p. 54" is obtained. The base is sensitive to oxidising agents forms solutions with blue fluorescence reacts with benzaldehyde in alcohol to give 4-3enzylideneamino-a-naphthyl methyl sulphide SMe*C,,H,-N:CHPh m.p. 66' yellow needles (which forms an intensely red salt with hydrogen chloride in ether) and yields by methylation 4-dimethyl- amino-l-naphthyl mthyl sulphide NMe,*C,,H,*SMe b. p. 1%'/ 16-17 mm. (hydviodide decornp. 171-173"). 4-Acetylamino-1-naphthyl methyl sulphide reacts with bromine in acetic acid to form a dibrornide (impure) C13Hl~ONSBr m. p. 157' (decomp.) a dark red crystalline powder which is converted by boiling glacial acetic acid into the acetyl derivative m. p. 232' white needles of 3-bromo-4-amino-l-naphihyl methyl sulphide NH,°CloH,Br*SMe rn p. 1 3 8 O colourless needles. By oxidation in glacial acetic acid with 30% hydrogen peroxide and hydrolysis of the product by alcoholic potassium hydroxide at 1004 4-acetylamino- 1-napht hyl methyl sulphide yields the sulphoxide NH,*C,,H6=S~~CH3 m. p.17 1-1 72' colourless crystals (acetyl derivative m. p. 183-184O ; a hydrate m. p. 109-lll' has also been obtained) the salts of which unlike those of the parent sulphide are only slightly hydrolyticall y dis- sociated. The sulphoxide reacts with hydrogen bromide in chloroform t o form the preceding red dibromide and its acetyl derivative is oxidised by an excess of hydrogen peroxide t o the corresponding aulphone NHAc-C,,H,*SO,Me m. p. 2364 the hydrolysis of which yields 4-amino- 1 -naphthylmeth ylsulplrone NH,*C,,H,*SO,Me m. p. 1 75' (hydrochloride decomp. about 247'). By warming its solution in acetic acid with a little concentrated hydrochloric acid 4-amino-1- naphthylmethylsulphoxide is converted into the hydrochloride of 3-chloro-4-amino-l -naphthyl methyl subhide NH,*C,,H,CI*SMe m.p. 719 c. s. C13H1302NS7&H,0?ORGANIC CHEMISTRY. i. 259 Trimethylene rcycloPropane1 Derivatives of the Type H2F>CHX. LOUIS MICHIELS (BUZZ. Acad. roy. Belg. 1912 10-34. H,C C&.npnreAbstr.,1901 i 581; 1902 i 525; 19111i,62,459).-A number of ketones containing the cyclopropyl group have been prepared and from these the corresponding secondary alcohols have been obtained. Methylisopropylcarbinol has in particular been studied with regard to its behaviour towards hydrogen bromide. I n the second half of the paper the author considers the physical properties of the cyclopropane derivatives as compared with those of the corresponding aliphatic compounds.cycloPropylmethylcarbinol H2?>CH*C€€M~*OH is obtained by the reduction of cyclopropyl'methyl kotone with sodium and dry alcohol as a viscous colourless liquid b. p. 119-120° D;'' 0.88045 1.42461. With hydrogen chloride it readily yields the corresponding chloride b. p. 105-106°/750 mm. and with hydrogen bromide in the cold the bromide a colourless mobile liquid b. p. 1 18-l2O0/75L mm. Di0 1.1552. From the bromide by the further action of hydrogen bromide or from the original carbinol by the action of concentrated hydrobromic acid a dibromide is obtained the trimethylene ring being opened which is probably y-pentylene dibromide (compare Lipp Abstr. 1890 20). cycloPropy2 isoamyl ketone CHMe,*[CH,],*CO* CH<vH2 a colourless liquid with an odour of mint is obtained by the action of magnesium isoamyl bromide on cyclopropanecarboxylonitrile the additive product being decomposed by water and acid.It has b. p. 183-185O/755 mm. DY 0.87408 ng 1.44064 ; and yields a semicarbaxone m. p. 140-141°. On reduction with sodium and alcohol cyclo~ropyEisoamylcarb~noZ is formed as a colourless viscous liquid with a citron-like odour b. p. 188-189'/766 mm. DY 0.8631 n2 1,44405. cy clo Prop y l isohexy I ketone CHMo [ CH,] C 0 C H<vH2 results from the interaction of magnesium isohexyl bromide and ethylene- acetonitrile. It is a colourless mobile liquid with an odour of mint b. p. 200-202°/739 mni. D;O 0.8631 n2 1.44325 ; on reduction it yields the caybinol a colourless viscous liqnid with a citron-like odour b.p. 306-207"/747 mm. D;'' 0.5603 n$' 1.44345. cycloinropylcccet?/icyc1o;u~woiuane H + ? > ~ ~ o ~ ~ * ~ ~ 2 0 ~ ~ < F H 2 is pre- pared by the interaction of magnesium cyclopsopylcarbinyl bromide and cyclopropanecarboxylonitrile as a colourless mobile liquid b. p. 175-177'/759 mm. D"," 0.9149 nZ,O 1.45'787 which yields a semi- carbazone m. p. 82-83O. On reduction i t gives the corresponding dicyclopropylethanol C3H,*CH(OH)*CH,*C',H~ b. p. 179-lSO0/ 770 mm. DY 0.9054 7ig 1.46036. This with hydrogen bromide gives a bromide D$ 1.535 in which only one of the cyclopropane groups has been opened. H2C CH CH2 H2C CH2i. 260 ABSTRACTS OF CHEMICAL PAPERS. The following secondary alcohols were prepared for comparison as regard their physical properties.is0 PropyZisobutyZcarbinoZ CHMe,. CH( OH)*CH,* CHMe is formed by the interaction of magnesium isobutyl bromide and iso- butaldehyde and subsequent treatment with water and acid. It is a colourless viscous liquid smelling of thyme b. p. 167-158O DY 0.8212 rn 1.42461. isoProp?/ZisoamyZcccs.binoZ CHMe,*CH(OH)*[CH,],*CHMe is simi- larly prepared and is a colourless viscous liquid with an odour of balm b. p. 175" Di0 0.8212 n2,0 1.42461. isoPro~yZisohexyZcarb~noZ is a similar substance b. p. 193-1 94 / 756 mm. Di0 0.8152 ng 1.43021. A comparison of the boiling points of the ketones indicates that the loss of two hydrogen .atoms accompanying the conversion of CH3>C into yH2>C produces in the case of the methyl- ethyl- and n-propyl- an increase of 19-20' and for the isopropyl- iso- butyl- and igoamyl- an increase of 13-15O.The replacement of a second CH'>CH- by YH2>CH- brings about a further rise of 14'. Similar differences are shown by the alcohols. A study of the densities of the alcohols of the two series shows that on an average the density of an alcohol of the cyclopropyl series is higher than that of the corresponding aliphatic alcohol by 0.043 and that this value is doubled by the introduction of another cyclopropyl group. The molecular refractions of the numerous cyclopropane derivatives containing one cyclopropyl group shorn on an average that the value found is higher than that calculated by 05'4 (compare Demjanoff Abstr. 1907 i 1033 who gave 0.66). GUSTAVE VAVON Compt.rend. 1912 154 359-361).-The reduction of aldehydes to alcohols by the ordinary method employing sodium amalgam gives yields not exceeding 50%. A theoretical yield is secured however by dissolving the aldehyde in a suitable solvent adding a few grams of platinum black (prepared by the action of formaldehyde in alkaline solution on platinic chloride) and submitting it to the action of hydrogen under a pressure of about one atmosphere. Successful application to a number of aromatic aldehydes of varied types shows I. K. TRAUBENBERG (J. Russ. Phys. Chem. Soc. 1912 44 132-1 38).-The author's investigations on betulin (compare Hausmann Abstr. 1877 i 94 ; Franchimont and Wigman Abstr. 1879 468) which include the determination of the molecular weight in boiling chloroform by Landsberger's method and in freezing benzene and also the preparation and analysis of the diacetyl and dibenzoyl derivat,ives indicate that betulin has the formula and that it belongs together with onocol arnidiol and faradiol to a group of dextrorotatory dihydric phytosterols GH3 C* CH3 CH W.G. Method for Preparing Aromatic Alcohols. that the reaction is a general one. w. 0. w. Betulin. C,,H3,(OH),,ORGANIC CREMlSTRY. i. 261 Betulin m. p. %lo [a] + 15-68' gives a number of colour reactions similar t.0 those for cholesterol Its diacetyl compound has [aID + 14*26O and its dibenzoyl derivative C24H,s0,Bz2 has m. p. 145-1 47'. When oxidised by means of alkaline permanganate betuliri yields acetic acid and a solid acid which was not investigated whilst with chromic acid it gives a ketone C24H3802 crystallising in prisms m.p. 177O and yielding a phenyZ/~ydraxone C,,H,,P*N,HPh m. p. 130'. r. H. P. Preparation and Estimation of Tyrosine and Glutamic Acid. EMIL ABDERHALDEN (Zeitsch. phyxiol. Chem. 19 12 '77 75-76).-Tyrosine can be prepared from silk by the simple method of hydrolysing with hydrochloric acid; the acid is removed by evaporation and then by the addition of sodium hydroxide ; tyrosine then crystallises out from the hot aqueous solution. The yield however is not quantitative and the mother liquor is not available for the separation of other amino-acids. These two disadvantages can be overcome in the following way. After hydrolysing with hydro- chloric acid the product is evaporated under reduced pressure to dryness ; the residue is dissolved in water and a stream of ammonia passed through the solution.It is then again evaporated to dryness and the residue treated with cold water ; tyrosine is left undissolved or the whole residue may be boiled with water and animal charcoal ; from the filtrate pure tyrosine crystallises out quantitatively. The mother liquor is again evaporated to dryness and the residue treated by the ester method for the other mono-amino-acids. The method serves for the estimation of tyrosine etc. in like products of hydrolysis. Glutamic acid may be prepared from its hydrochloride by passing ammonia through the solution and then evaporating to dryness. The deposit is dissolved in hot water and recrystallised; bhe main amount of glutamic acid can be separated by fractional crystallisation and the remainder can be obtained by precipitation with alcohol.W. D. H. [ Di-iodotyrosine.] A Correction. ADOLF OSWALD (Zeitsch. phyiol. Chem. 1912 76 499-500).-Yolemical (compare Abder- halden and Hirscb Abstr. 1911 ii 1119). E. F. A. Melting Point of 3 5-Di-iodotyrosine. EMIL ABDERHALDEN A reply to (Zeitsch. physiol. Chem. 19 12 '77 183-184).-Polemical. Oswald (preceding abstract). W. D. H. Action of Hydrogen Sulphide on Imino-ethers. 11. Formation of Thion Esters and Acids. MOTOOEI MATSUI (Mem. Koll. Sci. Eng. Kyijt6 1912 3 247-255. Compare Abstr. 1909 i 463).-When hydrogen sulphide is passed into an ethereal solution of an irnino-ether a thion ester is produced which ulti- mately reacts with the liberated ammonia with the formation of a thioamide.In alcoholic solution however ammonia decomposes thion esters with the formation of imino-ethers hydroxylamine having a similar action. VOL. CII. i. ti. 262 ABSTRACTS OF CHEMICAL PAPERS. By saponifying thion esters with cold alkali it has been found possible to prepare the corresponding acids. Thion-fatty acids are volatile pale yellow liquids having tf strong penetrating odour resembling t h a t of acetic acid and a very acidic reaction; thion- aromatic acids are yellow solid substances of characteristic odour. All are unstable decomposing even in ethereal salution in the course of a few days. They shorn a marked differeuce from ordinary mono- carboxylic acids in that their silver and lead salts remain in the ethereal layer when an ethereal solution of the acid is shaken with an aqueous solution of silver nitrate or lead acetate.Silver salts of thion-fatty acids are very unstable readily changing into silver sulphide whilst those of the aromatic acids are comparatively stable at the ordinary temperature. Ethyl thionbenaoate (Zoc. cit.) is a yellow liquid of b. p. 18l0/ 360 mm. When its alcoholic solution is treated with ammonia it yields ethyl iminobenzoate whilst in ethereal solution thiobenzamide is formed Hydroxylamine reacts with an alcoholic solution of the ester yielding a mixture of a- and P-ethylbenzhydroxamic acids. Methyl thionbenxoate resembles the ethyl ester. It has b. p. Methyl thionacetate has b. p. 85-90’; methyl thionpopionata has Ethyl thion-p-toluate is a yellow oil b.p. 205-20’7°/260 mm. m. p. about lo. Thionbenaoic acid was prepared by hydrolysing ethyl thion- benzoate with cold sodium hydroxide. Its silver lead and barium salts were examined. Thion-p-toluic acid was similarly prepared but in quantity insuficient for complete characterisation. l’hionacetic acid could not be obtained free from ether but has b. p. about 37O. The similar thionpropionic acid was also prepared and its lead salt was investigated. H. W. Terpenes and Ethereal Oils. CVIII. OTTO WALLACE (Annalern 1912 388 49-62).-Semmler’s method of preparing tanacetophorone by the dibtillation of salts of tanacetonedicarboxylic acid is unsatisfactory with regard to yield and purity of product. A very convenient process is the following Methyl a-tanacetonedi- b.p. 244-24’iO or 126-127O/ 13 mm. D2O 1.0535 n2,0 1.4506 [a]= 142-5O obtained from the acid methyl alcahol and hydrogen chloride forms with sodium in methyl alcohol a yellow crystalline compound C,,H~,O,Na,H,O which develops a violet coloration with ferric chloride yields impure tanacetophoronesemicarbazone with aqueous semicarbazide hydro- chloride and is converted into tanacetophorone by the successive operations of boiling its aqueous solution acidifying with sulphuric acid and distillation with steam. The transformations in the preparation of the ketone are probably as follows. Methyl a-tan- acetonedicarboxylate -+ methyl P-tanacetonedicarboxylate CB2<CPrKCIZ C0,Me’ -3 195-197°/320 IIJUI b. p. 110-1 15’. CH*CO,Me CPrP* CH,* C0,Me’ CarbOXyk6& CH,< I CH,*CO,MeORQANIC CHEMISTRY.i. 263 methyl sodium 1-hopropy 1- A'-cycZopenten-3-one- 2-carboxylate CH,-FO CH,'(Cpra:C*cO,Me' -+ The preceding constitution of the sodium compound is supported by the fact Chat the substance dissolved in water saturated with carbon dioxide is converted into dihydrotanacetophorone ( 1 -iso- propylcyclopentan-3-one) by treatment with hydrogen and colloidal palladium and subsequent acidification and distillation with steam. [ With FfiEDERSK CHALLENGER]. -1 -isoPropglcyclopentan - ;hne b. p. 188-189° D21 0*90(tO 9% 1.4428 (cdmpare Abstr. 1911 i 472) forms a dibenxylidene derivative m. p. 134-135' yellow needles and reacts with magnesium methyl iodide to yield ultimately i-1 -rnethyL3-isopwp~Zcycloplntccn-l-ol C,H,,O b. p. 185-lS6' ITI.p. 43-44' which apparently is the inactive modification of the tertiary alcohol obtained by the action of hitrous acid on fenchylamine (Abstr. 1911 i 311); by dehydration with oxalic acid it yields a hydro- carbon CSHIG b. p. 142-144' D2O 0.7970 ?a? 1.4418 which is almost identical in chemical and physical properties with that described WILRELM WISLICENUS and OTTO PENNDORF (Bey. 1912 45 410-41 1).-Naphthalic acid cannot be esterified directly The diethyl ester described recently by Errera (Abstr. 191 1 i 465) had already been prepared by the authors by the action of ethyl iodide on silver naphthalate; it has m. p. 59-60' and b. p. 238-239'/19 mm. ; the solution in strong sulphuricacid shows a blue fluorescence. previously (Zoc. cit.). c. s. The Ethyl Ester of Naphthalic Acid.D. F. T. Methylamino- and Other Derivatives of Terephthalic Acid. RUDOLF WEGSCHEIDER FRANZ FALTIS SIEGMUND BLACK and OSKAB HUPPEBT (Monatsh. 1912,93 141-168).-The object of the investiga- tion was a convenient method for the preparation of methyl- and dime t h p 1 -am1 not erep h t halic acids. Aminoterephthalic acid was obtained by successive nitration and reduction of terephthalic acid ; the corresponding methyl ester was obtained by esterification of the acid and algo by the reduction of the methyl ester of nitroterephthalic acid ; the last-named substance can be prepared by careful nitration of tho methyl terephthalate as well as by esterification of nitroterephthalic acid. The methyl ester of acetylaminoterephthalic acid (compare Cahn- Speyer Abstr.1907 i 849) is obtained by simple acetylatioo with acetic anhydride ; the alcoholic mother liquors from the recrystallisation of this substance contain methyl diacetyk~rninotereht~~aZa~~ which is also obtainable by the further acetylation of the monoacetyl compound ; the crystals of the substance m. p. 74-76O belong to the triclinic Bystem [ ~ ~ b c = 0 . 5 2 4 0 1 :0*7912; u=9lo12 @-85'22' y=96'19']; water hydrolyees the substance into the monoacatyl compound. t 2i. 264 ABSTRACTS OF CHEMICAL PAPERS. Methylaminoterephthalic acid is best prepared by the action of methyl sulphate on aminoterephthalic acid in the presence of barium carbonate ; it has m. p. 27 3-5-274*tio (corr.) (compare Cahn-Speyer Zoc. cit.) ; the solutions show a blue fluorescence.When the methyl- alcoholic solution is treated with hydrogen chloride at room tempera- ture 4-methyl 1 -hydrogen 2-methylaminoterep~t~ala~e separates m. p. 186.5-1 87" (corr.). The corresponding dimethyl ester was also obtained by esterification as an impure dark yellow solid m. p. 86.5-90O Acetylmethylaminoterephthalic acid was not obtainable by methyl- ating the acetylamino-acid with methyl sulphate but was successfully prepared by acetylating the methylamino-acid ; it crystallises in crusts the m. p. of which 216-216*5' is much below that given by Cahn- Speyer ; it is colourless and does not give fluorescent solutions. The acetyl group is removed by the action of dilute potassium hydroxide solution. Methyl acetylmethylarninoterepl~thalate obtained by the action of potassium and methyl iodide on a benzene solution of the methyl acetylaminoterephthalate has m.p. 78-80" ; the acetgl group is hydrolyhed off by heating with water. Dimethylarninoterepht~al~c acid is best prepared by energetic methyl- ation of aminoterephthalic acid with methyl sulphate in the presence of barium carbonate ; it is a white crystalline solid rn. p. 281" (corr. ; decomp.). The dimethyl ester obtained from the acid by esterification in the usual way crystdlises in needles belonging to the triclinic system [ a b c= 0.7920 1 0.8327 ; a = 82"21' p = 94'14' y = 104"50'] m p. 68-69'. D. F. T. Reduction of Acids with Several Double Bonds by Paal's Method. WALTHER BORSCHE (Rev. 1913,45,620-625).-Unsaturated acids when shaken with hydrogen and colloidal platinum are readily converted into the saturated substances.Cinnamylideneacetic acid CHPh:CH*CH:CH*CO,H yields phenyl- valeric acid. Cinnamylidenemalonic acid CHPh:C:H*CH:C(CO,H) gives w-phenyl-n-prop?/EmaZonic acid crystallising in colourless platelets m. p. 98". When heated carbon dioxide is eliminated and 8-phenyl- valeric acid obtained; this is the most convenient method for its preparation. .Methyl w-phenylloropylmalonate formed by reduction of methyl cinnamylidenemalonate is a colourless oil b. p. 183 -1 8 4 y O mm. a-Cyano-8-p7~nylvaleric acid prepared b y reduction of a-cyano- cinnamylideneaeetic acid is obtained as an oil which on distillation is converted into 6-phenylvaleronitrile. The ethyl ester of a-cyano-8-phenylvaleric acid is a colourless oil b.p. 192-193°/11 mm. a8 - Diphenylvaleric acid CH,Ph* CH,*CH,*CHPh*CO,H from a-phenylcinnam ylidenescetic acid crystallises in bunches of colourless needles m. p. 80-81" (compare Rupe and Liechtenhao Abstr. 1909 i 927). u~-Di~henylwales.onitr~l~ from cinnamylidenephenylacetonitrile forms large transparent crystals with lustrous faces m. p. 79"; it distils without decomposition. E F. A.ORGANIC CHEMISTRY i. 265 Syntheses in the Fatty Aromatic Series. 111. [Amino- acids Nitro-compounds Aldehydes.] JULIUS VON BRAWN and 0. KRUBER (Ber. 1912 45 384-402. Compare Abstr. 1911 i 968 ; 1910 i 843).-The authors have attempted in several ways to prepare the series of aldehydes corresponding with the series of alcohols already described in the earlier papers ; the most satisfactory sourae for the aldehydes proves to be the primary nitro-compounds.Various phenyl substituted amino-acids were obtained by applying the malonic ester synthesis as described by the series of changes CH2Ph*[CH2],*Br -+ CH,Ph*[CH,],*CH*(CO,H) -+ CH,Ph* [ OH,],* CHBr CO,H -+ CH,Ph* [CH,],*CH( NH,)*CO,H. 6-PhenyZpropylmaZonic acid CH,Ph*[ CH,],*CH(C0,H)2 m. p. 94' is obtained by hydrolysis of the ethyl ester a colourless oil b. p. 189-194O/13 mm. On distillation under reduced pressure it loses carbon dioxide with the formation of 8-phenylvaleric acid. Bromina- tion in ethereal solution yields a-bromo-6-phenylpropylmalonic acid m. p. 135-136O; this when heated above its m. p. loses carbon dioxide and forms a-bromo-6-phenylvaleric acid CH,Ph [ CH,],*CHBr CO,H m.p. 8 5 O b. p. 195-210°/16 mm. ; the same substance is obtained in a less pure condition by brominating 8-phenylvsleric acid. If the bromo-mid is heated with a concentrated aqueous solution of ammonia there is obtained a-amino-6-phenylvulevic acid m. p. 203-206' ; the copper salt was prepared also the P-naphtitulenesdpl~onyl derivative m. p. 83'. ePhenyl6utylmaZonic acid CH2Ph*[CH,],*CH(C0,H) needles m. p. ill' is obtained by hydrolysis of the ethyl ester b. p . 2 15-2 1 So/ll mm.; bromination gives a-bromo-c-phenylbutylmalonic aczd m. p. 123-124' (decomp.) which on heating yields a-bromo-e-phenyl- hexoic acid a yellow oil b. p. 210-230°/12 mm. which would not crystallise ; the preparation of this last substance by bromination of r-phenylhexoic acid is again unsatisfactory.When heated with aqueous solution of ammonia the bromo-acid is converted into a-amino-r-phenylhexoic acid white leafy crystals m. p. 237-242' (decomp.) ; the copper salt and the P-naphfhalenesui'phonyl derivative m. p. 112-113' were prepared. The above amino-acids failed to supply the desired easy passage to the required aldehydes. Phenylbutyronitrile CH,Ph*[CH,],*CN when treated in alcoholic solution with dry hydrogen chloride yields the hydrochloride of phenylbutyrimido-ether CH,Ph*[CH2],*C(:NH)*0Et,HCl which by the action of aniline in alcoholic solution is converted into the correspond- ing diphenylamidine compound CH,Ph*[CH,],*C( :NPh)*NHPh a white crystalline solid m. p. 81-82'. Reduction of tbis compound by sodium and alcohol yields a non-volatile viscous oil probably di-6-anilino-a-phenylbutane CH,Ph*[OH,],*CH(NHPh) which on hydrolysis yields only a few drops of 6-phenylbutaldehyde (compare Merling Abstr.1908 i 653). If phenylpropyl bromide is allowed to react with magnesium and then with ethyl orthoformate the expected phenylbutaldehyde diethyl metal CH,Ph-[CH,],*CH(OEt) is obtained ; it is however,i. 266 ABSTRACTS OF CHEMICAL PAPERS. much decomposed during distillation (b. p. about 200°/20 mm.) ; hydrolysis gives a very poor yield of the aldehyde. Phenylbutyl bromide magnesium and ethyl orthoformate yield no better result (compare Tschitschibabin Abstr. 1904 i 221 ; Bodroux Abstr. 1904 i 421). The reaction of magnesium phenylpropyl bromide and formomethyl- anilide gives no trace of phenylbutaldehyde (compare Houben and Doscher Abstr.1908 i 27) whilst the action of sodium hypochlorite on a hot aqueous solution of a-amino-8-phenplvaleric acid or a-amino-i- phenylhexoic acid yields small quantities of 6-phenylbutddehyde and 6-phenylvaleraldehyde respectively (compare Langheld Abstr. 1909 i 138). The desired aldehydes mere satisfactorily obtained by starting with the primary nitro-compounds which by reduction are convertible into the aIdoximes (Konowaloff Abstr. 1899 i '733). The interaction of y-phenylpropy 1 iodide and silver nitrite produced y-phenylpropyl nitrite b. p. 1 15-185'/14 mm. and y-natro-a-phenyl- propane a colourless inodorous oil b. p. 147-148'/1 1 mm. ; the latter on treatment with bromine in aqueous solution gives oily di-y-brorno- y-nit.ro-a-phenyZpopane CH,Ph*CH2:SBr,*NOp whilst with a diazonium salt it yields a-nitro-y phen ylpropaldeh ydephen ylh ydrazone small red needle crystals m.p. 153-134' ; the a-p~~enylproiDccne~~trolic acid has m. p. 75". If the sodium compound of nitrophenylpropane is reduced in aqueous solution by stannous chloride there is obtained y-phenyl- propaldoxime m. p. 93-94' ; this on hydrolysis yields yphenylprop- aldehyde Ph*[CH,],*CHO b. p. 110-1 13'/16 mm. (compare Fischerand Hoffa Abstr. 1898 i 659) ; the diphenylmethanedimethyldihydruzone CH,[C,H,*NMe*N:CH-CH,*CH,Ph] has m. p. 99-100'. 6-Nitm-a-phenylbutane (together with 8-phenylbutyl nitrite b. p. 125-130°/1 5 mm.) is obtained similarly to the corresponding propane derivative as a colourless oil of feeble odour b.p. 160-165"/15 mm. ; reduction of the sodium salt in aqueous solution and suhsequent hydrolysis yields 6yhenylbutaldel. yde CH,Ph*[ CH,],. CH 0 b. p. 129-131"/17 urn.; the semicarbaxone has m. p. 104-105'; the phenylhydraxome is an oil ; the diphenylmethanedimsthyldih ydraxone crystallises very slowly ; the methyl metal has b. p. 121-124']9 mm. ~-Nitro-a-phenyl~entans is a colourless inodorous liquid b. p. 16 1-166'/9 mm. whilst the isomeric ephenylamyl nitrite has b. p. 130-1 35"/10 mm. The dibromo-derivative of the phenylnitropentane is a yellow oil ; the nitrolic acid derivative and the product of coupling with a diazonium salt also show little tendency to crystallise. Reduction and subsequent hydrolysis of the nitro-compound yield r-phennyl-n-valeraldehyde CH,Ph*[CH,],*CHO as an oil b.p. 129-131°/10 mm. strongly resemblitig citral in odour ; the methyl a c e d b. p. 136-139"/11 mm. hits only a faint ethereal odour. The oxinze semicarbaxone phenylhydrazone and diphenylmethanedimt~~yl- dihydraxone are oily ; the p-nit~iophenyZhydazone slowly gives a solid m. p. 82-84O. r-Niti.o-a-plienylhexccne has b. p. 174-1 7S0/1 1 mm. whilst the isomeric [-phenylhexyl nitrite has b. p. 143-148O/11 mm. The nitro-ORGANIC CHEMlSTRY. i. 267 compound is easily converted into Y-phenylhexaldehyde b. p. 141-144'/9 mm. of feeble and not unpleasant odour; the substance offers considerable resistance to eatisfactory analysis by com bustion. q-Nitro-a-plhenylheptane has b. p. 182-186'/10 mm. and the isomeric 7-phenylheptyl nityite b.p. 164-166'/13 mm. The nitro-compound is convertible by the general process in to rl-13hen2/lhept"Zd~~~~~e CH2Ph*[CH,],* CHO b. p. 155-159'/9 mm. which like the lower aldehyde offers resistance to satisfactory combustion ; it has a feeble odour. The p-nitrophenyl- hydrazone is a brown powder m. p. 68-70'. The above series of aldehydes with the striking exception of 6-phenylvaleraldehyde show a gradual weakening of the odour with increase in the length of the carbon chain ; this is in marked contrast t o the oscillatory effect observed with the corresponding series of alcoh 01s. D. F. T. CH,Ph* [ CH,];CHO Combination of Phenolcarboxylic Acids. FERDINAND MAUTHNER (J. pr. Chem. 1912 [ii] 85 308-314).-An isomeride of the previously-described 3 4 5 2' 6'-pentamethyl ether of methyl digallate (A bstr.1 9 11 i 725) has been synthesised by condensing 3 4 5-trimethoxybenzoyl chloride with methyl 5-hydroxy-3 4- dimethoxp benzoate. The condensation was effected by shaking the ester in aqueous sodium hydroxide solution with an ethereal solution of the acid chloride. 5 - (3' 4' 5') - trimethoxybenzoyloxy-3 4-dimethoxybenzoate C,H,( O~~e),.CO,*C,H,(O~~e),.CO,~~~ thus obtained crystallises in coloiirless needles m. p. 127-128' and is the completely methylated derivative of the digaltic acid isolated by Nierenstein (Abstr. 1910 i 265) from tannin. Methy2 The following compounds were prepared in a similar manner Methyl p-3 4 5-trimethoxybenzoyloxybenzoccte C,,H,,07 obtained from 3 4 5-trimethoxybenzoyl chloride and methyl p-hydroxy- benzoate has m.p. 109-1 10'. Methyl 443' 4' 5')-trirr~ethoxybenzoyloxy-3 -methoxybenzoate C,,H,,O prepared from 3 4 5-trimethoxybenxoyl chloride and methyl vanillate forms colourless needles m. p. 131-132'. Methyl p- 4-methoxy benxo yloxybenzoate C 6H1405 obtained from anisoyl chloride and methyl p-hydroxybenzoate crystallises in colourless needles m. p. 146-1 47O. Methyl 4-ve~atroy2oxy-3-rnethox~benxoate C17H1,06 from veratroyl chloride and methyl vanillstley has m. p. 12s-129'. Methyl p-vsratroylox~benxoate C1,H,,07 forms colourless needles m p. 148-149". F. B. Mechanism of Cannizzaro's Reaction. VETCHESLAV E. TISTSHENKO I. F. VELTSA and I. L. RABTSEVITSCH-ZUBKOVSKY (J. Russ. Phys. Chem. Soc. 1912,44 138-151).-According to Claisen (Abstr.1887 574) when a sodium alkyloxide is heated in alcoholic solutioni. 268 ABSTRACTS OF CHEMICAL PAPERS with benzaldehyde a voluminous white precipitate is formed which is decomposed by water into benzyl alcohol and sodium benzoate or by acetic acid into benzyl benzoate and alkyl benzoate; he regarded this precipitate as an intermediate compound formed according to the equation /O*CH,Ph \ONa ZPh-CHO + R*ONa = CPh-OR The authors have investigated this reaction under various con- ditions and in all cases find the precipitate formed to consist simply of sodium benzoate. As has been previously asserted (Abstr. 1907 i 282) Claisen's explanation must be abandoned. T. H. P. The Action of Solutions of Etboxides on m-Nitrobenzylidene Chloride. ALFRED KLIEGL (J'e~h.Ges. deut. Nctturforsch. Aerzte 19 12 ii [l] 226-228. Compare Kliegl and Haan Abstr 1911 i 433).- m-Nitrobenzylidene chloride yields with solutions of ethoxides the acetal of m-nitrobenzaldehyde but this is accompanied into two compounds of the same composition and molecular weight but higher boiling point. They are unchanged by boiling with dilute sulphuric acid. Heating with hydrogen bromide in acetic acid forms bromo- derivatives from which the alcohols may be obtained. Oxidation with permanganate then yields cornpounds which are identified as ethers of 5-nitrosalicylic acid and 3-nitro-4-hydroxy benzoic acid respectively. The original compounds are therefore derived from m-nitrobenzy lidene chloride by the wandering of a chlorine atom into the nucleus followed by the replacement of chlorine by alkyloxy-groups.C. H. D. Action of Benzaldehyde on Polyhydric Alcoholrs Derived from Sugare. JEAN MEUNIER (Ann. Chim. Phys. 1912 [viii] 25 286-288).-The author points out t h a t the condensation of polyhydric alcohols with benzaldehyde to form acetals was first noticed by him in 1888 (Abstr. 1888 950 1265; 1889 233 479; 1890 730) and is wrongly attributed to E. Fischer in a recent paper (Ann. Chim. Phys. 1911 [viii] 24 398). The sorbitol derivative described already (Abstr. 1889 479) may be prepared by mixing the components at Oo concentrating to a syrup of 33OB6. and adding 60% sulphuric acid. The crystalline product which deposits is separated and washed and can be used for the production of pure sorbitol by hydrolysing with 0.002% sulphuric acid at 100' and distilling under reduced pressure when the benzaldehyde passes over in the steam leaving pure sorbitol.T. A. H. Aromatic Amino-ketones. FRANZ KUNCKELL (Ber. deut. pharm. Ges. 1912 22 103-114. Compare Abstr. 1900 i 663; 1911 i 990)-The methods described in the preceding paper of this series (Zoc. cit.) have been applied to p-acetotoluidide and the products obtained are described. [With CARL BLUMENREUTER. ] -w-Chl or0 -2 -acetylamino-5 -m ethylacetoORGANIC CHEMISTRY. i. 269 phenone CH,Cl*CO*C6H3RIe*NHAc already describd (Abstr. 1900 i 663) reacts wit,h potassium acetate to form an acetate OAc*CH,*CO*C,H,Me*NH Ac m. p. 94" and with bromine to give ~-chloro-~-bromo-2-acet~larn~no- 5-rethyZacetophenone m. p. 138O and this on hydrolysis with 20% hydrochloric acid loses 1 mol.of acetic acid and forms the correspond- ing umine m. p. 123O bright yellow needles. On treatment with warm dilute sodium hydroxide solution the chlorobromo-ketone yields dimethylindigotin. On iitraticn of o-chloro-2-;zcetylamino-5-methylucetop~enone one nitro-group enters probably in the unoccupied o-position to the acetyl- amino-group ; the nitro-derivative m. p. 167' forms glancing yellow needles and on treatment with alkalis does not yield a substituted indigotin. With aniline the chlorine atom in the parent substance is replaced and the substance NHPh*CH,*CO*C,H,Me*NHAc m. p. 1 4 6 O formed crystallising in yellow needles. o-Chloro-3-acetylamino-6-methylacetophenone formed along with its isorueride (see above) yields (1) on bromination ~chZo~ow-bromo~3-ucetyl- arni.no-6-methylacetophenone m.p. 1 12O colourless leaflets from which the corresponding amine m. p. 88" yellow needles is produced on hydrolysis ; (2) by nitration indefinlte products ; (8) by treatment with aniline the corresponding aniline derivative NHPh*CH,*CO*C,H,Me*NHAc rn. p. 184O colourless needles; (4) with potassium acetate in dilute alcohol the corresponding acetate OAc*CH,*CO*C,H,Me*NHAc m. p. 9 4 O hard colourless needles. m-Bromo-p-acetotoluidide reacts with chloroacetyl chloride to form ~-chlo~o-2(or 4)-bromo-3-acetgZumino-6-methyZc~cetophenone m. p. 134" glancing colourless leaflets which on hydrolysis yields the correspond- ing amine m. p. 11 6 O glancing yellow needles giving a hydrochlode m.p. 206' (decomp.) colourless needles. T. A. H.. Interesting Decomposition of Some Oximes. ANGELO ANUELI ( A t t i R. Accad. Lincei 1912 [v] 21 i 83-84).-Bei~zophenone- oxime decomposes at about 180° according to the equation 3CPh,:N*OH = SCOPh + N + NH,. I f it is supposed t h a t the nitrogen and ammonia are produced accord- ing to tbe equation 3NH = N + NH the Eeckrnann rearrangement becomes explicable on the hypothesis that a similar decomposition of the oxime first occnrs but the NH group takes up another position in the molecule instead of giving rise to nitrogen and ammonia. Analogous decompositions are those of some nitronic acids (Nef) and of ph t haly 1 p h en y 1 h y drazi de (compare CNO%away Cummin g and Wilsdon Trans. 1911 99 1950).K. v. s. Preparation of ae-Diphenyl-/3@38-tetramethylpentan-y-one and of a-Pbenyl-/3P66-tetramethylpentan-y-one Derivatives of Dibenzylacetone (ac-Diphenylpentan-y-one) and of a-Phenyl- pentan-7-one. ALB~N HALLER (Compt. rend. 191 2 154 555-559). -aeDiphenylpentaoone was repeatedly methylated by means of sodamids and methyl iodide. The final product was ae-diphenyl-i. 270 ABSTRACTS OF CHEMICAL PAPERS. ,B,B88-tetrarnethyZpentcm-y-one C H2Ph * CMe,* GO CMe2*CH2Pb an oily liquid b. p. 203-208°/10 mm. ; when heated with sodamide i t under- goes scission in the normal way. The same method of methylation applied to a-phenylpentan-y-one leads to the formation of a-phenyl- ,BP~~-tetrametliyZiPentan- y-one CH2Ph CMe,* CO - CMe b. p. I 3 9-1 4 4 O / 16 mm. Tho new tetra-dkyl ketones do not react with hydroxylamine senlicarbazide or pbenylhydrazine.w. 0. w. Dihalogenoindones. HUGO SIMONIY and CURT KIRSCHTEN (Bey. 1912 45 567-579).-From his investigations on the condensation of 2 3-dibromo-1-indone and dibromo-derivatives of quinones with ethyl rnalonrite and other substances containing a reactive methyleno group Liebermann (Abstr. 1899 i 219 373 522 ; 1900 i 310 666) has drawn the conclusivn that the mobility of the halogen atoms in these compounds is due t o the group CBr:CEr*CO being contained in a closed ring. It is now shown that the mobility is connected with the presence of the carbonyl group for compounds in which this group is lacking have their halogen atoms firmly attached ; thus 2 3-dibromo- I-methyl-l -indenol C6H,<CMe~~~;>CBr does not condense with substances containing a reactive methylene group and undergoes no change on treatment with potassium iodide or benzylamine.The reaction between magnesium methyl bromide and 2 3-dibromo- 1-indone yields 3-bromo-2-iodo-1-indone which crystalkes in brown prisms subliming above 80" with partial decomposition m. p. 158" (compare Roser and Haselhoff Abstr. 1888 1317) and 2 3-dibromo- 1-methyl-1-irdenoE. The latter compound crystallises in white platelets m. D. 126*5-127°. combines with bromine t o form 2 2 3 3-dibromo- - L 1-methyl-1-hydrindenol C 6 H 4 < ~ ~ ~ ~ ~ > C B r 2 and is converted by . I hydrogen bromide in glacia.1 acetic acid solution into 1 2 3-tribromo- 1 -rnethyZindene CsH4<FieBr C B r > ~ ~ r pale yellow prisms xu.p. 78"; the acetyl derivative crystallises in lustrous white needles m. p. 82". 2-lodo-3-benzylanaino- 1 - indone CO<5tf>C.NH*C7H7 prepared either by heating 3-bxomo-2-iodo-1-iudone with benzylamine in alcoholic solution or from potassium iodide and 2-broxno-3-benzylamino- 1-indone (Schlossberg Abstr. 1900 i 665) crystallises in long red needles m. p. 138O (decomp.). The action of ethylamine and aniline on 3-bromo-2-iodo- 1-indone yields orange-red compounds of a similar constitution. Attempts t o prepare 2-bromo-3-benzylaulino-1-indone by brominating 3-benzylamino- 1 -indone (Schlossberg Zoc. cit.) resulted in the removal of the benzylaulino-group and the formation of a dibromo- 1 -indone C,H3Br<E;!%3H which crystallises in reddish-brown needles m.p. 1 7 7 O and contains one of the bromine atoms in the benzene nucleus. 3- Bron~o-2-iodo-l-indoneoxime C,H,ONBrI exists in two stereo- itiomeric forms one crystallising in yellow needles m. p. 2 0 6 O theORGANIC CHEMISTRY. i. 271 other in yellow quadratic plates m. p. 195-197' ; the p-nitropheuyl- hydrazone forms brownish-red microscopic needles m. p. 2 1 2-2 14". On treatment with bromine 3-bromo-2-iodo-1 -indone is converted into 2 2 3 3-tetrabromohydrindene (Roser and Hnselhoff Zoc. cit.) ; with magnesium. methyl iodide i t forms 3-brorno-2-iodo-l-meth~Z- I-indenol C6H4<cMe(oH)>CI which crystallises in almost white leaflets m. p. 137O. 2 3-Dibromo-1 -ethyl- 1 -indenid C11HloOBr2 prepared from mag- nesium ethyl bromide and 2 3-dibromo-l-indone crystallises in colour- less prisms belonging to the rhombic system m.p. 77-78' and yields an acetyl derivative m. p. 91O. 2 3-Dibromo-1-phenyZ-1-indenol could not be obtained in a pure con- dition and was therefore characterised by means of its acetyl derivative CI7Hl2O2Br2 which forms pale grey prismatic needles m. p. 138-140O. CBr - F. B. CataIytic Elimination of Hydrogen f r o m Aromatic Nuclei and the Synthesis of Condensed Systems by means of Aluminium Chloride. ROLAND SCHOLL and CHMSTIAN SEER (Monatgh. 1912 33 1-8).-When aromatic compounds are heated with anhydrous aluminium chloride at from 80' t o 140° hydrogen is eliminated and a new ring formed. Previous examples of %his are the conversion of naphthalene and a-dinsphthyl into peryl- .Of\ ene (Scholl Seer and Weitzenboch Abstr.1910 i 616) and the conversion of meso-benzdianthrone into meso- N v N naphthadianthrone (Scholl and Manbfeld Abstr. 1910 1 I i 494). The method has been extended to the following cases. \/\/ Phenyl a-naphthyl ketone is converted a t 140' into I ICO benzanthrone. Similarly 6 7-ph thaloylbenzanthrone is (Io)\/ obtained from 2-anthraquinonyl a-naphthyl ketone. Dibenxoylpyrene is converted into pyranthrone a synthesis which proves the benzoyl groups t o occupy positions 3 and 8 in pyrene. Presumably oxidising agents act a t these positions so that pyrene- quinone is 3 8-diketopyrene (formula I) and not 3 10-diketopyrene as supposed by Bsmherger and Philip (Abstr. 1887 496) and by Goldschmiedt (Abstr. /\/\/\ 1907 i 310). I l l 1 Dibenzpyranthrones are obtained on beat- -\/\/\ ing di-a- or di-/I-naphthoylpyrenes. These dyes give in blue vats much redder shades 1 I I I 4 :4'-l)ibenzogl-l 1'-dinaphthyl when heated \/\/\/ at 95-1 OOo with aluminium chloride yields Heterocyclic rings are condensed in similar manner; thus from 3 8-di-a-thenoylpyrene a thiophen analogue of pyranthrone (formulaI1) is obtained; this is 3 brownish-red product which behaves like the vat dyes of the anthraquinone series.Benzil is converted into phenanthraquinone below looo. s co I l l \/v\- than pyranthrone. violanthrone. (114 co E. F. A.i. 272 ABSTRACTS OF CHEMICAL PAPERS. Syntheeis of a Ketone Derived from Cineole. GUIDO CUSMANO and ARRIQO LINARI (Gcczxetta; 1912 42 i 1-lo).-The action of hydroxylamine on a-terpineol nitrosochloride yields the hydroxylamine- oxime (I).From this by means of nitrous acid the o-ieonitroamine- oxime (11) is obtained. The o-isonitroamineoxime when heated with water yields an oxime CloH170,N which when oxidised or treated with ethyl nitrite and subsequently with ammonia gives a ketone CloH,,02 of the constitution indicated in formula (111). CMe*NH*OH CMe*NO( :NOOH) CMe--0 CH,/)C:N*OH CH2 CH2 CH*CMe,*OH CE*CMe,*OH (1.) (11.) (111.) a- Terp~neol-o-~y~roxy~ami~teox~~6 C10H2003N2 is prepared in the same way as the other hydroxylamineoximes previously described (compare Cusmano Abstr. 1910 i 685 863). It forms tufts of colourless acicular crystals m. p. 183' (decomp.). It condenses with p-nitrobenzaldehyde yielding a yellow crystalline compound m.p. 1 8 3 O . When treated with dilute hydrochloric acid and sodium nitrite in the cold i t yields the o-isonitroumineoxime C10H1904N3 which forms colousless prismatic crystals which decompose at 156-157'. The substance yields a blood-red coloration with ferric chloride and gives Liebermann's reaction. It dissolves in alkali carbonates and forms crystalline brucine salts When i t is treated with an aqueous solution of an alkali hydroxide nitrous oxide is evolved and hydroxydihydro- carvoneoxim e is formed quantitatively. When the isonitroamine- oxime is heated with water alone however two other oximes are produced. One has the composition CloHl,03N,H20 and m. p. 9 5 O the other has the composition ClOHl7O2N and m. p. 139-140'. In the presence of small quantities of mineral acids the isonitroamine- oxime decomposes yielding the oxime of m.p. 139-140' hydroxy- dihydrocarvone and the methyl ketone of homoterpenylic acid. The oxime Cl,H1702N when treated with hydrobromic acid at the ordinary temperature yields the methyl ketone of homoterpmy lic acid. Hydrochloric acid gives the hydrochloride C,oH,70,N,HC1 and a product which is decomposed by water with the formation of ammonium chloride and the methyl kekone of homoterpenylic acid. When the oxime C10H170,N is dissolved in ethyl nitrite a pernitrosyl derivative Cl0HI6O3N2 is obtained ; it forms large crystals m. p. 68-70'. The ketone CloH1602 is produced in small quantity by oxidising the oxime C,,H 1702N with acid permanganate but is best prepared by decomposing the pernitrosyl derivative with concentrated ammonia.It crystallises in shining colourless leaflets and has a slight odour reminiscent of cineol. Its semicarbazone C10H1902N3 has m. p. about 220'. When oxidised with acid permanganate (1%) the ketone yields the methyl ketone of homoterpenylic acid almost quantitatively. Alkaline permanganate attacks it much less readily the products being the above methyl ketone and cineolic acid. R. V. S.ORGANIC CHEMISTRY. i. 273 Hydroxyketoperinaphthindene (peri - Naphthindandione). GIORGIO ERRERA aud A. CUFFARO (Gazzetta 1911 41 ii 807-814. Compare Errera Abstr. 191 1 i 465).-Since the substance previously described under the name of peri-nnphthindandione always behaves as a keto-enol containing the grouping -CO*CH:C(OH)- and since no derivative of the corresponding diketonic form is known and moreover the free substance contains a n hydroxyl group the authors propose to substitute for their original name that of hydroxyketoperinaphthindene.When the substance is oxidised with potassium dichromate and acetic acid (allowing one atom of oxygen per molecule) anhydrobishpdroxy- ketoperinaphthindene (annexed formula) is obtained ; it crystallises in yellowish-brown needles which on heatirrg GO co blacken at 360' and melt with clecom- /\C-c/\C,oH position a t a higher temperature. The oxidation of hydroxyketopeyinapht hindene by means of alkaline permanganatle pro- ceeds quite differently. Even when less than the theoretical quantity of per- manganate is taken a vigorous reaction occurs and the following substances are obtained (I) unaltered hydroxyketoperinaphthindene ; (2) naphthalic acid and (3) a substance C13HS05 which crystallises in tufts of very small colourless needles m.p. about 225' (decomp.). To this substance is assigned the constitution CO,H*C,,H,-CO-CO,H and it is termed naphthalonic acid. It is decomposed by heat in the same manner as is phthalonic acid (compare Graebe and Trumpy Abstr. 1898 i 318) naphthalic anhydride being formed and also a substance C,4H!,0 which is to be regarded as the anhydride of naphthalccltielydzc acid; it has m. p. 310-313' (rapid heating) and is identical with a product obtained by Graebe and Gfeller (Abstr. 1893 i 656). When hgdroxy ketopurinaphthindene is boiled with benzaldehyde in alcoholic solution in presence of a trace of pyridine dihydroxy- Letoperinccphthind~n~~hen ylnaethane lo 6\/ \/ C C \ / \/ 0 co- co- 'C-CHPh-d \C H c10H6<c (OH) \q*q/ lo 6' is obtained ; it is a golden-yellow crystalline powder (from alcohol) or forms red crystals (from xylene) m. p.295-297" (decomp.). The substance can give metallic derivatives but both the sodium and potassium salts are very sparingly soluble in water. The mono-sodium salt C33H1904Na is a yellow crystalline When dihydroxyketopesinaphthindenil- /\/\/\/\/\ phenylmethane is boiled with an alcoholic I I 11 11 I 1 solution of sulphuric acid a substance is \/\/\/\/\/ precipitated to which the constitution of co I co ylbenyl diketo perinaphthindemxanthene (an - nexed formula) is ascribed ; it crystallises in yellow needles melts with decomposition a t /\ substance./\ I I O I I CHPhi. 274 ABSTRACTS OF CHEMICAL PAPERS. some temperature above 365* and does not contain ethoxy-groups or form salts. R. V. S. Transformation of a Phloroglucinol Derivative into One of cycZoEexantrione. 11. GUSTAV HELLER (Ber. 191 2 45 41 8-427. Compare Abstr. 1909 i 656).-The author gives a summary of reactions in which the ester of a phenol has been observed to suffer rearrangement into a hydroxy-ketone and indicates that in the pre- paration of hydroxy-ketones by the condensation of acyl chlorides with phenols the phenolic esters must be intermediate products. In extension of the previous investigation (Zoc. cit.) it is observed that tribromophloroglucinyl triacetate trichlorophloroglucinyl tri- acetate and 1 3 5-triacetyltriarninobenzene when heated with zinc chloride shorn no sign of molecular rearrangement. [With GEOKG KRETZSCHMAR.] -Phlorogzucinol diacetate m.p. 104O is obtainable by the action of phloroglucinol with sodium acetate and the theoretical quantity of acetic anhydride. Triacetylcyclohexantrione is so resistant to complete hydrolysis that this does not occur without rearrangement. If it is dissolved in dilute sodium hydroxide solution slow hydrolysis occurs ; the p~ ecipitate obtained on acidifying is treated with boiliug water when the undissolved residue consihts of d~c~cety~cyclohexantrwne ; this crystal- libes from benzene in needles m. p. 1684 This substance is also obtained as a by-product in the transformation of phloroglucinyl triacetate into the triacetylcyclobexantrione.Tribenxoyldzacetylcyclo- >CO obtained by benzoylation crys- Iiexantrione C A C B ~ < ~ ~ ~ ~ ~ ~ ~ CO-CHBz tallises in needles m. p. 137-138O; it dissolves slowly in sodium hydroxide solution but gives no coloration with ferric chloride. The action of a diazolrium solution yields benxenecczodiacetylcyclohexam trione C H A C < ~ ~ . - ~ . co- (N,ph)>CO CHAc orange-coloured needle crystals m. p. 209'. hexantriori- MU A - The action 'ofY nitrous acid gives oximinodiacetdcyclo- v - - ./co-cHAc\nn --,lden leaflets m. p. 1 4 9 O \ which by reduction gives a colouhess substance decomposing at 200'. The hot aqueous filtrate from the diacetylcyclohexantrione (above) on cooling deposits monoacetylcyclohexantr~one ; tbis gives pale rose- coloured crystals of a monohydrate but when anhydrous it is colour- less m.p. 209-210'. Its tribenzowl derivative forms colourless needles m. p. 116-11'7'; it reacts with a diazonium sol i i tion forming a bis-aso -compound N,Ph*CH<CO. CO-CHAc cH(N,ph)>CO purple needles m. p. 241-242' (decornp.). With nitrous acid a bis- oeinzino-compound is obtained which decomposes a t 115-120'. Di- and mono-acetylcyclohexat] trione resemble the triacetyl com- pound in dissolving in sodium hydroxide solution giving a colorationORGANIC CHEMISTRY. i. 275 with ferric chloride and in forming copper salts ; the acid character is more marked the fewer the acetyl groups present. All three sub- stances react with benznldehyde in alkaline alcoholic solution pro- ducing yellow amorphous substances.TotvarJs phenylhydrazine and hydroxplamine they are inert whilst bromine attacks them all the monoacetyl compound most readily. D. F. T. Certain Derivatives of Tetrachloro-o-benzoquinone. C. LORING JACKSON and GEORGE LESLIE KELLEY (Arner. Chem. J. 1912 47 197-221).-A continuation has been made of the study of three substances prepared f rom tetrachloro-o-benzoquinone (Jackson and MacLaurin Abstr. 1907 i 856). The compound m. p. 215' obtained by the action of benzyl alcohol on tetrachloro-o-benzoquinone has proved to be the heptachloro-o- quinocatechol hemiether described by Jackson and Carleton (Abstr. 19OS i 428). This was confirmed by analyses of its acetgl derivative m. p. 195" its reduction product (heptachlorodihydroxycatechol hemiether) m.p. about 188-19O0 and the tyiacetyl derivative OAC*C,CI,*O*C,C~,( OAC) m. p. 144" which forms white hexagonal prisms. The other two compounds investigated were those m. p. 198' and 210° which were respectively obtained by the action of methyl and ethyl alcohol on tetrachloro-o- benzoquinone. They can also be pro- pared by the action of the alcohols on heptachloro- or hexachloro-o- quinocatechol hemiether. The methyl cornpound was originally regarded as hexnchloro-o- benzoquinomethylhemiscetalcatechol ether C6CI,O,:C,C1,O(OH)(OMe) on account of its being produced by the action of methyl alcohol on the ether C,Cl,O,:C,CI,O but has now been found to be hexachloro- methoxy-o-quinoccctechol hemiether OH*C,Cl,*O*C,Cl,O,(OMe).On re- ducing the compound with zinc dust and sulphurous acid it was cou- ver ted into hexachloromethoxy-o-dihydroxycatechol hemiethey OH*C,C1,*O*CGCl,(OH),(OMe) 111. p. 191' which crystallises i n long colourless needles and yields a triacetyl derivative m. p. 128-1294 and a monoucetyl derivnt'ive m. p. 186-188'. In the course of preparing these acetyl compounds another compound was obtained m. p. 122'. The compound m. p. ZlO' obtained by the action of ethyl alcohol on tetrachloro-o-benzoquinone has been found to be hezachloroethoxy-o- quinocatechol hemiether OH~C,Cl,*O~C,Cl,O,(OEt) ; its acetyl derivative has m. p. 195O. On reducing the compound with sulphurous acid it is converted into ~~exacl~loroethoxy-o-dihydroxycatechol hemielhey m. p. 173' which forms white needles and yields a triacetyl derivative m.p. 165'. If however the reduction is effected by zinc and acetic acid a compound m. p. 249' is produced and readily undergoes decomposition with formation of hexachloro-o-dihydroxycatechol ether which furnishes an acetyl derivative ~,Cl,O,:C,C~,(OAC)~oH) m. p. 251° as well as the diacetyl derivative described previously. OH* c6c1,*0* C6C1,(OH),(OEt) E. G.i. 276 ABSTRACTS OF CHEMICAL PAPERS. Method of Formation of Alkylated Anthraquinones from Alkylated Benzoyl Chlorides and Aluminium Chloride. 11. 33-34. Compare Abstr. 191 1 i 386).-Mesitylenyl chloride C',H,Me,*COCl reacts when heated with aluminium chloride at 115-120° t o give 1 3 5 7-tetramethylanthrayuinone. The com- pound so obtained differs from all other anthraqninone derivatives in that it is not reduced by alkaline sodium hyposulphite or by CH CO /\/\/\CH3 zinc dust and sodinm hydroxide.It is not I I I 1 attacked by acetyl or benzoyl chloride or by cH3\/\b<)4$3 phosphorus pentachloride and when dihtilled with zinc dust tetramethylanthracene is obtained. The structure is confirmed by the synthesis from m-xylyl mesityl ketone which was heated for some days the tetramethylanthrncene formed separated by distillation and oxidised with acetic and chromic acids to the quinone. 1 3 . 5 7-Tet~arnethylanthraquinoneis not identical with the substance obtained by Dewar and Jones (Trans. 1904 85 212) by the action of nickel carbonyl on m-xylene to which they ascribe the same COJL- stitution. It is however the same as the oxidation product of the tetra- methylxnthracene obtained by Friedel and Crafts (Abstr.1887 1102) from the reaction of methylecs chloride and m-xylene in presence of aluminium chloride. It is now fonnd that a little of the isomeride described by Dewar and Jones is produced at the same t i m e ; the constitution of I 3 6 8-tetramethylanthraquinone is ascribed to this. 1 3 5 7-Tetramethylanthraquinoue forms yellow needles m. p. 235"; it dissolves in concentrated sulphuric acid with a dark red coloration. The corresponding 1 3 5 7-tetramethylanthracene forms yellowish-white platelets m. p. 155-157' or when purified by regeneration from the picrate m. p. ,163-164'. The picrate has m. p. 189-190°. Anthraquinonel 3 5 7-tetracstrboxylic acid and its salts were obtained amorphous m.p. above 300'. 4 8-Diuitro-1 3 5 7-tetramelhylccnthra~ui~one prepared by the action of potassium nitrate and concentrated sulphuric acid on the quinone separates in greyish-brown needles m. p. 296". 2 4 6 8- Tetranitro-l 3 5 7-tetramet~ylccnthrup~inone crystallises in yellow microscopic plates. E. F. A. CHRISTIAN SEER [ W1 t h &ON EHBENZWEIG) (h?oma;tsh. 1 9 12 33 Action of Ammonia on Chrysophanic Acid Methyl Ether. OTTO A. OESTERLE (J. pr. Chem. 1912 "11 85 250-232. Compare Abstr. 1910 i 860).-It is pointed out that Fischer and Gross (Abstr. 1911 i 886) have erroneously attributed t o the author the view that the actiou of ammonia on chrysophanic acid mouomethyl ether leads to t h e replacemeut of the hydroxyl by an amino-group.The product of the action crystallises in long glistening brownish-red needles m. p. 237-23g0 and has the constitution of a l-hydroxy-8- methoxy met hylan thraquinoneimide. F. B.ORGANIC CHEMISTRY. i. 277 Commercial Chryaarobin. OSWALD HESSE (Annalen 19 12 388 65-96. Compare Tutin and Clewer Tram. 1912 101 290).-Com- mercial chrysarobin is demethylated by hydriodic acid D 1.7 at 120-1 2 5 O or by equal volumes of hydrochloric acid D 1.19 and glacial acetic acid a t 130-140' and the dried product is boiled with petro- leum (which extracts a portion of the chrysophanol) and then with chloroform in which chrysophanol in much more soluble than emodinol. Chrysophunol C,,H,,O (previously called chrysarobin by the author and by Jowett and Potter Trans.1902 81 1575) has m. p. 204' (not 205-210° as stated previously) The presence of a small amount of the methyl ether lowers the m. p. by 6-44' and of emodinol raises i t by about the same amount (compare Fischer Falco and Gross Abstr. 1911 i 886). It is insoluble in alkali hydroxides or carbon- ates in the absence of air. By the admission of air chrysophanol dissolves with the formation of chrysophanic acid; the latter is also formed by oxidising the anthranol with chromic and acetic acids a t 60-70°. When heated with acetic anhydride at 90-100' for four hours with occasional boiling for periods of ten minutes chrysophanol yields a triacetate m. p. 238-240' (Jowett and Potter's diacetate Zoc. cit.) which is converted into diacetylchrysophxnic acid m.p. 208" (Liebermann and Seidler'e "acetylchrysarobin") by acetic and chromic acids at 60-7'0'. Triacetylchryaophanol like diacetylchrysophanic acid yields diacetylrhein by oxidation with chromic acid in a hot solution of equal volumes of acetic acid and acetic anhydride (compare Fischer Falco and Gross Zoc. cit.). Hexa-acetyldichrysophanol m. p. 125' is a by-prod rict of the acety1ation"bf chrysophanol Emodinol C1,HI2O4 isolated as described above has m. p. 230-240" (decomp.) and yields acetplemodinol C,,H,,O,Ac m. p. 159' yellow leaflets by heating with acetic anhydride at 90-100' for two hours. Emodinol and acetylernodinol yield emodin and acetylemodin respec- tively by oxidation with chromic and acetic acids. The acetylntion of emodinol by acetic anhydride and sodium acetate at 90-100' for two houts yields teera-acetlyZemodinoZ C,,H,O,Ac m.p. 19 7O yellow prisms octa-acetyldiemodinol C,oH,~OsAcs m. p 125" yellow powder being formed as a by-product l'he tetra-acetate is oxidised by chromic (calculated quantity) and acetic acids at 50-60' to triacetylemodin which is converted into triacetylemodic acid by chromic acid acetic acid and acetic anhydride a t 60-70'. Octa-acetyldiemodinol is converted into triacetylemodin by chromic and acetic acids a t 60-'70°. Chrysmobol Cl5HI2O4 m . p. 250-252' almost colourless needles is obtained from the portion of commercial chrysarabin which is insoluble in ethyl acetate at 55". It is unattacked by boiling concentrated nitric acid does not yield methyl iodide with hydriodic acid dissolves in aqueous potassium hydroxide with a yellow colour and in concentrated sulphuric acid with a purple-red colour changing t o reddish-brown.It is insoluble in alcohol and therefore does not develop a coloration with alcoholic ferric chloride. It yields p- methylanthracene by reduction with zinc dust It is converted into acstylchrysarobol Cl5Hl1O4Ac m. p. about 245" yellow needles by hot acetic anhydride and into te~.a-c6cety~chrys~robo~ C,,~,0,Ac4 m. p. about 190° greenish-yellow flocks by acetic anhydride and VOL. CII. 1. ?I.i. 278 ABSTRACTS OF CHEMICAL PAPERS. sodium acetate at 90-100°. The tetra-acetate is oxidised by chromic and acetic acids at 50’ to a red amorphous substance which does not yield emodin by hydrolysis. The substance which crystallises from the ethyl acetate extracts of commercial chrysarobin (obtained in the isolation of chrysarobol) consists essentially of emodinol methyl ether.It is seen from the preceding that commercial chrysarobin contains chrysophanol and its methyl ether emodinol and its methyl ether and chrysarobol. Of these only the first and the last can be isolated directly and pure. These results are confirmed by the direct oxidation of chrysarobin with and without previous acetylation or demethylation. By direct oxidation by oxygen in alkaline solution or by chromic and acetic acids chrysarobin yields chrysophanic acid and emodiu and their methyl ethers. When acetylated and sub- sequently oxidised by chromic acid chrysarobin yields diacetyl- chrysophanic acid diacetylemodin methyl ether acetylchrysophanic acid methyl ether and a small quantity of a substance m.p. 202O orange-yellow needles which /\/ \/\Me is probably chry8arobic acid. 1 1 1 I 1 The paper closes with a discussion of the \/\I/\/ constitutions of some of the preceding anthranols. Chrysophanol has probably the annexed formula not that previously OH OH given (compare Oesterle Abstr. 1911 i 887). c. s. Derivatives of Menthone. EYVIND BODTKER (Compt. rend 19 12 154 437-439. Compare Abstr. 1907 i 857).-The constitution previously ascribed to the compounds obtained by acting on benzyl- idenementhone with magnesium alkyl bromides is confirmed by an examination of their oxidation products. When benzylidenementhone is treated with magnesium methyl iodide and benzoyl chloride added before the addition of water is formed phenylmenth~l~~~~thyl~~thane benzoate C8H16<I I C-CHMePh OOBz having m.p. 152-153’ 145’40’; on hydrolysis it yields phenylmenthylrnethyl~~~e~~ane c8H16< I m. p. 111-112° CH* CHPhMe co [a] + 95O16’. Phenylmenthylisoamylmethane C,,H,,O is a viscous liquid b. p. 21fio/15 rum. [a]:” + 13’45’ m F 2 1,50568 ; the benzoate bas m. p. 93-94O [a]ag’5 + 186’29’. Be.lzxoyZrnenthone C1,H2,02 was obtained as a yellow liquid by treating a toluene solution of menthone successively with sodamide and benzoyl chloride; it has b. p. 1SSo/ 12 mm. [a]!’5 +32’11’ n 1.51745. The rotations given are for benzene solutions. w. 0. w. The Camphenilone Group. 11. isoCamphenilone and Con- stitution of Camphenilene and of apoBornylene. s. V.HINTIHKA and GUSTAV EOMPPA (Annalen 1912 38’7 293-316. Com- pare Abstr. 1909 i 5OO).-The generally accepted view that cam- phenilone and fenchooe are horndogous is further strengthened by the conversion of the former into isocamphenilone through the followingORGANIC CHEMISTRY. i. 279 series of compounds the change being quite analogous to that whereby fenchone has been converted into isofenchone. Camphenilone the preparation of which from camphene by a very simple process is described is reduced to camphenilol a camphenilone pinacone m. p. 146O being obtained as a by-product. Camphenilol which forms a benzoate C,H,,*OBz b. p. 172'/15 mm. is converted into camphenilene by phosphoric oxide at 140-1 50'. Cam- phenilene has also been prepared by converting camphenilol into camphenilyl chloride and hoating this with aniline a t 175 -1 SO' with diethylaniline at 180-1 85' with alcoholic potassium hydroxide or most frequently by direct distillation with aniline after the mixture has been boiled under reflux for five hours.The hydrocarbon obtained by these processes has b. p. 140-141° Di0 0.8693 n'$ 1.46848 T.$" 1.47850 n; 1.47425 and nEo 1.46507. Camphenilene forms a hydi*ochloride C,H,,Cl m. p. 60-61° needles or plates (which is probably identical with camphenilyl chloride since mixtures of the two substances show no depression of the m. p.) and a nitrosite C,H,,O,N2 m. p. 122' (decomp.) bluish-green prisms and is converted by the Bertram-Walbaum mixture of acetic and sulphuric acids at 50-55' into an acetate C,H,,*OAc b.p. 195O the hydrolysis of which by alcoholic potassium hydroxide yields isocamphenilol CgH,,*OH b. p. 196' m. p. 7s'. This alcohol forms a benzoate m. p. 79" phenyl- carbamate m. p. 65O and hydvogun phthalate m. p. 118-1 19O and is oxidised by potassium dichromate and dilute sulphuric acid to isocamphenilone CgHl40 m. p. 55-57' large white plates (semi- carbazone m. p. 225-2264 clusters of short monoclinic prisms). Camphenilene in glacial acetic acid yields with 17% ozone an ozonide by the distillation of which in a vacuum is obtained n keto-aldehyde C9H1402 b. p. 123-125"/15 mm. Dy 1,0325 n," 1.46571 cnz 1.46867 n 1,47969 which reduces Fehling's and ammoniacal silver solutions forms a disemicaybazone m. p. 205-206' and by further oxida- tion with ozone yields a keto-c6cid C7H,,(CO)*C02H.These results prove that camphenilene must have the constitution (I) assuming that Wagner's camphenilone formula is correct. Moreover it follows that isocamphenilone probably has the constitution (11). C H2-$lH--CiMe2 CH,*? H--CMe CH,*?H-CH CH2*CH-CH CO-CH-CH CH2*C==CH (1.1 (11.) (111.) Finally since apobornylene which is also derived from campheni- lone yields by ozonisation an ozonide by the decomposition of which is obtained a di-aldehyde which oxidises to apocamphoric acid in the air it follows that apobornylene has the constitution (111); the formation of a substance of this constitution from camphenilone Rotatory Power of Camphor in Carbon Tetrachloride Solution. A. FAUCON (Compt. rend. 1912 154 652-655).-The specific rotatory power of camphor in solutions of carbon tetrachloride of different concentrations is given together with empirical formuh I YMe2 /I I QH2 I I Y"2 I (Wagner's formula) is readily explicable.c. s. 26 2I. 280 ABSTRACTS OF CHEMlCAL PAPERS. expressing the connexion between rotation and concentration. For solu- tions containing 25-55 grams per 100 C.C. of solvent [a] = 43.56Of 0.1 148'~. The variation in rotatory power with temperature depends on concentration especially when this is high. The increase for a The Principal Constituents of Labdanum Oil. Ketonic Compounds. HENRI MASSON (Compt. rend. 19 12 154 51 7-5 19). -Gum labditnum from Cistus creticus or C. t?adaniferzcs gave 0-7-0.9% of a yellow oil when distilled in steam. 'The oil had b. p. 50-1 S5'/ 15 mm.and contained alcohols phenols esters terpenes and ketones. The latter were removed and on fractionation yielded acetophenone and a fraction b. p. 70-'78'/15 mm. containing 1 1 :5- trimeth&yclohexanone C H,,O. When regenerated from the oxime (m. p. 106O b. p. 126-127"/17 mm.) this was obtained as R liquid b. p. 66-67'/10 rum. 178-179°/760 mm. D 0.922 ng 1.4494. It does not form a bisulphite compound but yields a semicarbaxone m. p. 220-221' and a nzonobromo-derivative m. p. 41'. Reduction with sodium and alcohol gives 1 1 5-trimethy2cyclohexano2 m. p. 51° b. p. 87"/28 mm. Oxidation with potassium permanganate lends t o the formation of eketo-aa-dimethylhexoic acid COMe*[CH&*CMe2*C0,H b. p. 190-191'/31 mm. (semicarbazone m. p. 164'). The constitution of the acid was established by converting it into aa-dimethyladipic acid KARL DEITERICH (Verh.Ges. deut. Natur- forsch. Aerzte 1912 ii [l] 315-318. Compare Kiistenmacher Abstr. 19 11 ii 127).-Extraction of propolis with light petroleum removes wax and balsam and these are separated by means of 70% alcohol. Resin m. p. 90-106' is extracted from the residue by absolute alcohol and tannin is then extracted from the resin by water. The resin is then extracted with cold absolute alcohol when an insoluble residue proporesen remains. Ether precipitates a-proporesen from the solution and the filtrate after evaporation is separated by chloro- form into a soluble part the "pure resin," and a n insoluble part P-proporesen. Propolis balsam is free from cinnamic acid but contains vanillin.Proporesen is chemically indifferent fluoresces in concentrated sulphuric acid sinters at 76' and has m. p. 8 3 O and is insoluble in chloral hydrate solution. a-Proporesin has m. p. 187' and is not fluorescent in sulphuric acid. P-Proporesin is completely soluble in chloral hydrate solution fluoresces in sulphuric acid and yields an alcohol on hydrolysis. The acid sublimes in needles sinters at 88-90° and melts a t 124-125O. The (( pure resin " fraction is also fluorescent and yields an acid and a resinotannol on hydrolysis. rise of 1' is greater a t 12' than at 40°. w. 0. w. by means of sodium hypobromite. w. 0. w. Bee Resin (Propolis). C. H. D. Structure of Polymerised Vinyl Bromide and Caoutchouc. IWAN I. OSTROMISSLENSKY (J. Buss. Phys. Chem. Soc.1912 44 204 -240).-The author shows that polymerised vinyl bromide (com- pare 'Hofmann AnnaZe?h 1860 115 271 ; Bsumann Annnalen 1872,ORGANIC CHEMISTRY. i. 281 183 315) to which he gives the name caouprene honzide exists in three modifications possessing identical chemical but different physical properties and readily convertible one into the others. Caouprene bromide is a simpler homologue of the bromide of natural Para caoutchouc which contains methyl groups ; further it is either identical with butadiene-caoutchouc bromide (comphre Harries Abstr. 1911 i 798) or isomeric with it the isomerism being due to a difference in the distribution of the halogen atoms in the molecule. The compounds obtained by the action of aniline or phenols on these bromides and the hydrocarbon resulting from the removal of hydrogen bromide from them are also discussed. a-Caouprene bromide is alone formed by the action of sunlight on vinyl bromide the velocity of the polymerisation being dependent in high degree on the presence of traces of contact substances which may either retard or accelerate the change ; hydrocarbons of low boiling point such as light petroleum retard or even arrest completely the reaction.The a-bromide dissolves readily in carbon disulphide and a number of other solvents from some of which i t may be precipitated in the form of asbestos-like threads from others in an amorphous state and from others as a milky emulsion It resists the action of energetic oxidising agents concentrated alcoholic potassium hydroxide and concentrated mineral acids.@- and y-Caouprene bromides are obtained by the action of the ultraviolet light of a quartz-mercury lamp on vinyl bromide best in the gaseous state. The P-compound is soluble i u carbon disulphide but the 7-bromide is quite insoluble and merely swells up in this solvent and forms two layers the upper one of pure carbon disulphide and the lower which shows intense violet fluorescence of the gelatinous bromide retaining a considerable proportion of the solvent. On prolonged heating at 50' of the a-bromide or boiling of its carbon disulphide solution isomeric change into the p-form takes place. The change a- -+ /3- -+ y-modification is readily brought about by ultraviolet light or by protracted boiling with anhydrous acetic acid. The y- may be changed completely into the @-bromide by dissolving in boiling chlorobenzene and precipitating- with light petroleum.The compound -described by Harries (Zoc. cit.) as butadiene- caoutchouc tetrabromide is also found to exist in three modifications one of which does not dissolve but swells in carbon disulphide form- ing a fluorescent jelly. The other two forms are soluble in carbon disulphide in which one gives a fluorescent and the other a non- fl uorescent solution. The tetra bromide of neutral Para caoutchouc which is homologous with caouprene bromide also exists in certain analogous modifications (compare Weber Abstr. 1900 i 353). Free Para caoutchouc is like- wise obtainable in three forms (Harries Zoc. cit.) which are probably due to the same cause as the three caouprene bromides and the three butadiene-caoutchouc bromides since in all three cases the inter- conversions take place under similar conditious.The differences between the three modifications of any one of these compounds are probably due to differences in the physical structures of their mole-i. 282 ABSTRACTS OF CHEMICAL PAPERS. cules for example such differences as exist between sodium chloride in the ordinary and colloidal states. I n some instances however the variation in properties seems to depend on the absence or presence in the surface layers of oxidation products. p- and y-Caouprene bromides give exclusively colloidal solutions as is shown by the boiling and freezing points of their solutions. Cryo- scopic measurements in ethylene dibromide indicate for a-caonprene bromide the molecular weight 1809 corresponding with (*CH,*CHBr*),6.Each of the three caouprene bromides and also butadiene caoutchouc bromide react with phenol at 150' (compare Weber Zoc. cit.) giving a reddish-violet elastic amorphous compound (CH,*CH-OPh),. When an aniline solution of caouprene bromide is heated it assumes a cherry-red colour the quaternary ammonium salt being formed. Rapid cooling of the solution results in the depoaition of a spongy mass to which the name meta-aaouprene bromide is given (CH,*CH),(NH2Ph),,,Brn,2 = meta-(CH,*CH),Br,, + m/2NH2Ph. The meta-bromide dissolves readily in carbon disulphide a t the ordinary temperature giving an intensely fluorescent violet solution and unlike the normal bromide dissolves readily in fused phenol with formation of a pale brown solution from which benzene precipitates a brown powder ; normal caouprene bromide gives an intense violet solution with phenol the compound (CH,*CH),(OPh) being formed.The rearrangement of halogen atoms to which the formation of the meta- bromide is due is not effected by quinoline caouprene bromide precipitated from this solvent retaining its original chemical and physical characters. When a 10% solution of caouprene bromide in aniline is heated for thirty minutes at 120-130' out of contact with air subsequent precipitation with alcohol or ether yields a new bromo-compound which does not give Weber'a reaction with phenol. This compound which has not yet been obtained pure and is apparently non-homogeneous dissolves in fused phenol to a pale reddish-yellow solution not pre- cipitated by benzene; when heated in nitrobenzene it gives up hydrogen bromide.The removal of hydrogen bromide from caouprene bromide its meta- modification butadiene-caoutchouc bromide and the bromide of natural caoutchouc leads to the formation of a hydrocarbon (CH) and may be effected in various ways (1) by prolonged heating with water in sealed tubes a t 150'; (2) by heating solutions of the bromides in various solvents such as aniline quinoline dichloroacetic acid aromatic nitro-derivatives etc. best in absence of air ; the influence of these organic compounds on the removal of hydrogen bromide from the molecule of the complex bromide depends not entirely on their power of dissolving the latter or the hydrocarbon formed but also on their ability to absorb the hydrogen bromide.From a consideration of the above results of the possible compounds obtainable by the polymerieation of vinyl bromide and of the fact that Weber's colour reaction with phenol is given by bromides of the terpene series in which the number of halogen atoms is a multiple of ~ Q W the (CH,*CH),( NH,Ph)n,,BJkj2,ORGANIC CHEMISTRY. i. 283 conclusion is drawn that the formation of caouprene bromide takes place according to the scheme n(CH,:CHBr) = (*CH,=CHBr*) -+ ~H,*CHBr*CH,*CHBr*CH,*CHBr*CH,*~HBr CHBr.CH ,............................. CHBroCH (the dotted line representing an unknown number of *C H2*CHBr* groups) the value of n being not less than 12. The alternate dis- tribution of the bromine atoms is rendered probable by the fact that the autopolymerisation of halogen derivatives of ethylene or acetylene yields exclusively symmetrical trihalogen compounds of benzene ; bromoacetylene for example gives 1 3 5-tribromobenzene.The hydrocarbon dehydrocaouprene obtained by the removal of hydrogen bromide from caouprene bromide and its isomerides is regarded as a higher homologue of benzene of the formula FH CH*C H CH* CH CH*CH YH CH :CH’ The action of aniline on caouprene bromide and the subsequent decomposition or” the quaternary ammonium compound thus obtained into aniline and meta-caouprene bromide are represented as follows QH2* C H Bra CH,. H Br ................................ ............ + NH2Ph -+ ( 3 3 2 CHBr.. $!H2* CH(NH,PhBr)-CH,*QH*NH,Ph Br -+- CH2*CHBr*CHBr 51H2 CH2 CH(NH,PhBr)..........-... ...............NH2Ph + &HBr.. C H,‘ I n view of the results of Kinrichsen and Kindscher (Abstr. 1911 ii 445) and of Pickles (Trans. 1910 97 1085) the statement made by Harries that caoutchouc must be regarded as an associated dimethylcyclooctadiene of the form ~Me*CH,*CH*FH-FMe*CH,*CH,*~H**.,...= QMe*CH,*CH,*EH CH*CH,.CH,-CMe*CH-CH,-CH,-CMe**....*CH*CH,-CH,-CMe is admissible only on the assumption that when caoutchouc is brominated it undergoes preliminary splitting with formation of dimothylcyclooctadiene. The author hence regards this formula as discordant with the facts. The most probable structure for caoutchouc bromide is QH,*CHBr*CMeBr*CH,*CH,*CHBr*CMeBr*QH CH,.CHBr.CMeEr. ...............CH,*CMeBr*CH2’ which is similar to the formula given by Pickles n(CH,:CMe*CH:CH,) = (*CH2*CMe:CH*CH2*)n = The polymerisation of isoprene to caoutchouc is best represented thus ~H2*CMe:CH*CH,*CH,*CH:CMe*CH2*CH2*CH2*#H CH,*CH:CMe*CH,*CH,*CH:CMe* ......... *CH,-CMe The positions of the double linkings are here fixed and isomerism is possible only in so far as the positions of the methyl groups are concerned. The name caoutchouc tetrabromide is irrational this compoundi. 284 ABSTRACTS OF CHEMICAL PAPERS. being a t the least a hexabromide of the formula C15H24Br6; for the present it is best termed simply caoutchouc bromide. The various properties of caouprene bromide synthetic butadiene- caoutchouc bromide and natural Para caoutchouc bromide are collected in tabular form.Willstatter and Waser's results (this vol. i 17) published after the author's paper was in the press compel the assumption that dehydro- caouprene is not a higher homologue of benzene but that i t has the following structure or one similar t o it ~HOQH*QH*QH*~H*..=.....* fiH CH.CH.CH.CH.CH.......... CH' T. H. P. Regeneration of Caoutchouc from its Bromide. Synthesis of Butadiene-caoutchouc. IWAN I. OSTROMISSLENSKY (J. BUSS. Phys. Chem. Xoc. 1 9 12 44 240-244. Compare preceding abstract). -The action of zinc dust on caouprene bromide or butadiene-caoutchouc bromide dissolved in either naphthalene or chlorobenzene yields free caoutchouc possessing identical chemical and physical properties in the two cases. The action of sodium on these bromides especially in presence of ether proceeds t o some extent in the same direction but is complicated by secondary processes such as the formation of dehydro- caouprene (CH)n.The action of sodium on a 2.3% solution of caouprene bromide in chlorobenzene containing a little ether is accom- panied by sudden heating the solvent boiling vigorously and the chlorobenzene (which alone is quite inactive towards sodium) as well as the caouprene bromide being acted on by the sodium. The solution of caouprene bromide or butadiene caoutchouc bromide in naphthalene or chlorobenzene shows a violet-red fluorescence. As caouprene bromide is readily obtainable from alcohol the above reaction leads to a new synthesis of butadiene caoutchouc CH,*CH,*OH + Al,O -+ CH,:CH -+ CH,Br*CH,Br + KOH + Sphingosine.PHCEBUS A. LEVENE and WALTER G. JACOBS (Proc. Arner. Soc. Biol. Chern. 191 1 xxix; J. Biol. Chem. ll).-Sphingosine obtained originally from phrenosin by Thudichum appears to be an unsaturated amino-alcohol of the olefine series. The substance obtained later by Thierfelder in the filtrate from sphingosine sulphate and described by him as a nameless base isdimethylsphingosine. Full data will be published later. W. D. H. Physcion. OSWALD HESSE (Annalen 1912 388 97-1 02). - Physcion (parietin) yields emodin by demethylation by concentrated sulphuric acid a t 160'. It is demethylated and also reduced by hydriodic acid D 1.7 yielding a substance (protophyscihydron) m. p. 230-240° which is shown to be emodinol by its conversion by acetylation into tetra-acetylemodinol m.p. 19So which yieldsORGANIC CIIEMISTRY. i. 285 triacetylemodin by oxidation by chromic and acetic acids. The further proof that physcion is emodin methyl ether (compare Oesterle and Johann Abstr. 1910 i 860) is given by its methylation whereby ernodiu trimethyl ether m. p. 226O is obtained. Physcihydron the product of the reduction of physcion by zinc and acetic acid is proved to be emodinol methyl ether by its conversion into triacetylemodinol Duality of Chlorophyll. C. A. JACOBSON and LEON MARCHLEWSKI (Bull. Acad. Sci. Cracow .1912 A 28-40 ; Arner. Chem. J. 1912 47 221-231).-Evidence is given to support the contention t h a t the ratio of chlorophyll to allochloroyhyll varies with different species of plants and also with changing cooditions of growth of the same species.Tbe actual amount of allochlorophyllan the nearest acid derivative of allochlorophyll isolated From a given weight of chloro- phyllan from Acer platanoides of different years is very different. The absorption bands in the visible spectrum of the chlorophyllans obtained by identical methods from different species differ consider- ably. The same applies to the chlorophyllan bands in the ultra-violet part of the spectrum. The extinction coefficientp in monochromatic light of equally concentrated solutions of chlorophyllans from different species vary considerably. The variable ratio between the two constituents of chlorophyll ranges from almost pure a2lochlorophyll in Acer negundo to a product very rich in neochlorophyll in the nettle.E. F. A. methyl ether. c. s. Chlorophyll. XIX. Chlorophyllid es. RICRAR D W ILLSTATTEB and ARTHUR STOLL (Annalen 1912 38'7 317-386).-The isolation of pure chloropbyll is difficult on account of its solubility decom- posibility and chemical indifference. So far .as the degradation of chlorophyll is concerned the phytyl group is without signi ticance Hence for working out the early steps of the degradation of chlorophyll it is convenient to use the substance in the form of the sparingly soluble crystalline alkylchlorophyllides. Hitherto no description and analyses of an individual chlorophyll derivative have been given the crystallised ethylchlorophyllide previously described (Abstr. 1911 i 659) being a mixture of the a and 6 compounds.The authors have now succeeded in separating methylchlorophyllides a and b from one another and also in the separation of the chlorophyllides a and b the methylphaeophorbidee a and 6 and the phaeophorbides a and b. The mixture of methylchloro- phyllides a and b has been obtained by the metharlolysis of the fresh leaves of the acanthus (IZeracleum spondykium) hy Willstatter and Isler's process (Abstr. 1911 i 392). The separation of the two components has been effected by the partition method the b compound being much leas soluble in ether than the a compound. For practical purposes the two partition liquids consist of 66% aqueous methyl alcohol 'and a mixture of ether and petroleum b. p. 30-50'. The method of procedure varies somewhat according as the methylchlorophpllide mixture is rich or not in the b compound but in principle the process consists in shaking the ether-petroleum solution of the methylchlorophyllides with successive quantities of 6 6% methyli.286 ABSTRAC'I'S OF CHEMICAL PAPERS. alcohol until the b compound together with some of the a compound has passed into the aqueous alcoholic layer. The ether-petroleum layer is then frequently shaken with water to remove the bulk of the ether whereby methylchlorophyllide-a which is insoluble in petroleum is precipitated. The methylchlorophyllide-b is isolated from the aqueous alcoholic extracts by a somewhat complicated process and is finally purified by the fractional precipitation of its ethereal solution by petroleum and talc. MethyEchEoro~hyElide - a C,,H,,ON,Mg(CO,Me),,~~H,O crystallises from ether in bluish-green rhombic leaflets yields bluish-green solutions with red fluorescence exhibits the '' brown phase " reaction and is converted when quite pure only into phytochlorin-e by treat- ment with methyl-alcoholic potassium hydroxide under definite conditions. MethyEchEorophyZZide - b C,,?,,O,N,Mg( CO,Me),,$H,O crystallises in olive-green or brown rhombic plates and forms in abso- lute alcohol a greenish-yellow solution with brownish-red fluorescence is more stable than the a compound towards dilute hydrochloric acid develops in the phase tests initially a red coloration which changes to brownish-red and finally to yellowish-green and yields phytorhodin-g by proper treatment with methyl-alcoholic potassium hydroxide. The enzymatic hydrolysis of chlorophyll by chlorophyllase yields a mixture of the free chlorophyllides a and b ; the hydrolysis is effected best by extracting fresh leaves (of Heracleum or Xtachys) with 60-80% aqueous acetone (also the enzymatic hydrolysis of the preceding methylchlorophyllides a and b in aqueous acetone yields the corre- sponding free chlorophyllides ; the process however is more difficult than is the case with crude chlorophyll).The separation of the chlorophyllides a and b is effected as in the case of the methyl esters by the partition method with aqueous methyl alcohol and ether-petroleum. ChZorophyEZide-a C0,H*C32H300N,Mg*C02Me,~H20 crystallises from aqueous ether or acetone kin six-sided plates which are bluish- black by reflected and green to bluish-green by transmitted light.Its solutions are bluish-green with red fluorescence. By treatment with dry ammonia the substance absorbs 2NH3 one of which is easily lost the other only with difficulty. In consequence of its acid nature chlorophyllide-a is extracted from its ethereal solution by N/lOOO- potassium hydroxide. The separation of chlorophyllide from alkyl- chlorophyllides is conveniently effected by leading ammonia into the ethereal solution whereby the former is precipitated as the ammonium salt. By prolonged warming in a vacuum or by keeping in the solid state or in dilute solution the chlorophyllide changes to magnesium phseophorbide which is insoluble in ether. ChlorophyZEide-b C02H~C,,H2,0,N,Mg*C02Me crystallises from acetone in yellow to olive-green six-sided leaflets forms yellowish-green solutions with brownish-red fluorescence absorbs 2NH one of which is retained even in a vacuum and is more strongly acidic than the a compound being extracted from ethereal solution by ~V/2000-potassium hydroxide.Methylchlorophyllide-a is easily and quantitatively converted into ~~ethyZphaeophorbi&e-a by treating its ethereal solution with 10% hydrochloric acid for two minutes ; the pure crystalline methyl- phaeophorbide-a is then obtained by concentrating the etherealORGANIC CHEMISTRY. i. 287 solution. In a similar manner methylchlorophyllide-b is converted into methylphaeophorbids b by 15% hydrochloric acid. On account of their difference in basicity mixtures of methylphzeophorbides a and b are separated much more conveniently by hydrochloric acid than by the partition method.The a compound is extracted completely from its ethereal solution by 18% hydrochloric acid whilst the b compound requires the use of 23% acid. The ethylphaeophorbides a and b (Abstr. 1911 i 659) can be separated in a similar manner. Methylphaeophorbidc-a C3,H,,0N,(C0,Me) crystallises in rhombic leaflets or twinned prisms which have a violet-black lustre appear brownish-yellow or brownish-red under the microscope and form a dark violet powder. The ester dissolves in formic or hydrochloric acid with a blue colour and in ether or other indifferent solvents with an olive-green colour similar to that of phytochlorin-e but differing by exhibiting a red fluorescence. Methy lphaeophorbidea has acid number 16. When heated slowly it softens at about 150' and has m.p. 210-220" (decomp.); at 220" i t still yields mainly phgtochlorin-e after hydrolysis. Nethylphaeophorbide-b C,2H,00,N,(O0,Me)2 forms large olive-green or brown rhombic crystals and yields a reddish-brown fluorescent solution in ether and a green solution in hydrochloric acid. The ester which has acid number 21 softens at 200' and begins to decompose at about 250'; after being heated at this temperature i t still yields nearly pure phytorhodin-g by hydrolysis with potassium hydroxide. Excluding phytochlorin-e and phytorhodin-g the free phaeophorbides u and b are the most easily obtainable chlorophyll derivatives. They can be prepared by three methods (1) By shaking an ethereal solution of the chlorophyllides a and 6 with 16% hydrochloric acid the magnesium compounds are decomposed and the phzeophorbide-a passes entirely into the acid solution the 6 compound remaining in the ethereal layer ; (3) an ethereal solution of the methylchlorophyllides a and b is treated for two hours with 25% hydrochloric acid whereby the magnesium compounds are decomposed and the carbomethoxy- group a is hydrolysed.The mixture of phaeophorbides a and b is then isolated and is separated as in method (1). The best process is (3) in which phaeophytin (phytylphaeophorbide a and b ) in ethereal solution is treated with 34-35% hydrochloric acid for three-quarters tc one hour. The solution is diluted with water the phytol removed by ether and the solution is further diluted with water; the phaeophorbides are extracted by an excess of ether and the ethereal solution is con- centrated and treated with 16% hydrochloric acid whereby phaeo- phorbide a is removed.Phaeophorbide-a C0,H*C,,H3,0N4*C3,Me crystallises in bluish- black rhombic plates which appear olive-green or olive-brown under the microscope. The colours of its solutions in different solvents are like those of methylphaeophorbide-a. The substance absorbs 2NH one of which is lost only in a vacuum. The acid number is 15. Phaeophorbide-a is extracted from its ethereal solution by N/lOO- ammonia or potassium hydroxide by 0.1% sodium carbonate and by 1% sodium hydrogen carbonate or phosphate. Phaeophorbide-b C02H*C,,H,0,N4*C02Me crystallises from ether in small rhombici.288 ABSTRACTS OF CHEMICAL PAPERS. plates and needles which appear olive-green or brown under the microscope. The substance absorbs approximately 2 NH which is almost entirely lost at the ordinary pressure. It forms a reddish- brown fluorescent solution in ether and a green solution in hydro- chloric acid. Phaeophorbide-b is more acidic than the a compound; its acid number is 19-20 and i t is extracted from ethereal solution by 0.2% sodium hydrogen carbonate or by 0.25% disodium hydrogen phosphate. By treatment with methyl-alcoholic potassium hydroxide it gives a “red phase.” The term ‘‘ allomerism ’’ is employed to denote the changes which the chlorophyllides and the alkylchlorophy llides undergo in alcoholic solution (Ahstr. 1911 i 660). Allomerism in alcoholic solution is catalytically accelerated by the presence of glass but not of platinum or silver; it is prevented by the presence of a trace of acid.Allomeric changes are to be explained probably by the rupture of the lactam group in the chlorophyll derivative and the formation of a new lactam group. The degradation of chlorophyll (for example chlorophyll-a annexed formula) can now be Y Y effected in three ways in each of NH-GO which the reagent attacks the P L 1 a chlorophyll molecule at a diff went CO,Me*LC,,H,,N,Mg]*CO,*C,,H Point- (1) BY the enzymatic action of chlorophyilase changes only occur at the a-group; in methyl or ethyl alcohol the phytyl group is replaced by methyl or ethyl whilst in aqueous acetone i t is replaced by hydrogen this being the only method by which t h e free chlorophyllides can be obtained.(2) By gentle treat- ment with acids the magnesium is replaced by hydrogen and phsophytin is obtained. By more energetic treatment hydrolysis occurs at the a-group and the free phaeophorides are produced ; since these still exhibit the ‘(brown phase,” the y-lactam group is still intact. (3) Alkalis first attack the y-lactam group in the “brown phase ” ; subsequently a new lactam qroup is Formed. Then follows hydrolysis at the a-group and finally with difficulty at the P-group. At higher temperatures alkalis cause an elimination of carbon dioxide and degradation to di- and mono-basic pbyllins and porphyrins ensues. A diagrammatic representation of these changes is given. Tho formulae of the compounds in this paper are t o replace those previously recorded (Abstr.1911 i 659). c. s. Phylloporphyrins. LEON MARCHLEWSRI (Amnalen 191 2 388 63-65).-Willstiit4ter and Fritzsche (Abstr. 1910 i 136) state t h a t Schunck and Marchlewski’s phylloporphyrin is a mixture of two substances of different basicity. The author therefore has heated allophyllotaonin (A bstr. 1907 i 866) with 10% alcoholic potassium hydroxide at ZOOo whereby only Schunck and Marchlewski’s phyllo- porphyrin together with feebly basic by-products is obtained. Chlorophyllanic acid however by the same treatment yields two markedly basic products which are separated by 0.25% hydrochloric acid One of these products called phylloporphyrin-a is identicalORGANIC CHEMISTRY. i. 289 with Schunck and Marchlewski’s phylloporphyrin ; the other more basic product is called phylloporphyrin-P. By treatment with alcoholic potassium hydroxide at 200° phyllocyanin and allochloro- phyllanic acid each yield mainly phylloporphyrin-P very little of the a-compound being produced (compare following abstracts).The Chlorophyll Group. XII. P-Phylloporphyrin. LEON MARCHLEWSKI and J. ROBEL (Biochem. Zeitsch. 1912 39 6-11 ; Bull. Acccd. Sci. Cracow 1912 A 41-46).-The authors believe that the so-called pyrroporphyrin of W illstatter and Fritzsche is essentially the phylloporphyrin of Schunck and Marchlewski which had not‘ been sufficiently purified in that the former investigators had under- estimated the basicity of the less basic product in the mixture. When these porphyrins are prepared from made chlorophyllanic acid (from maple chlorophyll) by the method described in detail by the authors two products are formed simultaneously namely a strongly basic p - phylloporphyrin which can be dissolved out from its solution i n ether by 2% hydrochloric acid and the phylloporphyrin of Schunck and Marchlewski. If & acid be used instead appreciable quantities of the last-named porphyrin are also dissolved.A comparison of the spectra of the two substances is given. The Chlorophyll Group. XIII. Porphyrias from Phyllocyanin and Phylloxanthin. LEON MARCHLEWSKI and B. ZURKOWSKI (Bzochern. Zeitsch. 19 12 39 59 -63).-In view of the possibility of separating a- and P-phylloporphyrius (see Marchlewski and Robel preceding abstract) investigations were made with the object of finding the parent substance of these two derivatives.The /?-derivative is not obtained at all from the phyllotaonin of Schunck and Marctilevski or from the pure allophyllotaonin of Marchlewski and Robel. These yield the a-substance. On the other hand phyllocyanin and phyllo- xanthin which stand in near relationship t o neochlorophyll and alZo- chlorophyll yield chiefly the P-derivative. The previously-expressed views on the subject are not correct owing at the time to the want of a satisfactory method for separating the two porphyrins. The experi- mental details of the method of preparing the p-substance from phyllocyanin and phylloxan thin are given in full. S. B. S. The Red and Blue Pigment8 of the Algze. RARALD KYLIN (Zeitsch. yhgsiol. Chem. 1912 ’76 396-425. Compare Abstr.1910 i 866).-The occiirrence of phycoerythrin and phycocyanin in a number of varieties of Floridem and C’ymzophycee has been investigated. I n addition to the properties previouely given (loc. cit.). phycoerythrin crystallises in hexagonal prisms usually without pyramidal faces ; these are optically negative. The same modification has been isolated from twenty species of B’Zoridem ; from three species Polpiphonia Brodicei P. nigreacens and Rhodomela subfusca a modification was cbtained which lacked the fluorescent properties. So far phycoerythrin has only been obtained from the FZoridece. C. S. S. B. S. Three modifications of phycocyanin have been identified. Bluish-green phycocyanin shows a remarkable dark carmine-red fluorescence and has an absorption band in the orange between C and D290 ABSTRACTS OF CHEMICAL PAPERS.with a maximum at X=624-618. It crystallises in hexagonal rhombohedra. Blue phycocyanin also gives a splendid dark carmine-red fluorescence and has two absorption bands one in the orange between C and D with a maximum at X=615-610 and the other in the yellow-green between D and E but nearer to D with a maximum at X=577-573 ; i t was not obtained crystalline This modification is widely distributed amongst the Cyanophyceae. Bluish-violet phycocyanin has the same fluorescence and shows absorption bands in the orange between C and D with a maximum a t X = 618-613 and in the green between D and E but nearer E with the maximum a t X = 553-549. It crystallises in rhombic plates which are blue across the shorter diagonal violet across the longer.This modification occurs in Cevamium rubrum. Phycocyanin is characteristic of the Cyanophycece but occurs in a few Floridem. E. F. A. Melanin. Ross AIKEN GORTNER (Biochern. Bulletin 19 1 1 1 207-215. Compare Abstr. 191 1 ii 908).-Melanins are probably formed by th'e interaction of an oxydase and an oxydisable chromogen. They differ in solubility in dilute acids; those which are soluble contain a protein complex; those which are insoluble are the granules seen in hairs and tissues. Tyrosine lysine and arginirie are obtained as hydrolytic products from the former class (melano-proteins). W. D. H. Formation of Gallamide from Acetyltannin. MAXIMILIAN NIERENSTEIN (Ber. 1912 45 533-534. Compare Abstr.1910 i 487).-The formation of gallamide from acetyltannin by heating with alcoholic ammonia is regarded as doubtful ; the former analytical values were calculated incorrectly. E. F. A. Hydroxyhydrofurans. GEORGES DUPONT (Compt. rend. 19 12 154 599-601. Compare Abstr. 191 1 i 554 804).-Ketohydro- furans are not reduced by zinc and alkalis by sodium amalgam or by hydrogen in presence of platinum. Sodium ethoxide at 1 20° however gives red compounds which on treatment with water yield the corresponding hydroxyhydrofurans together with viscous high-boiling liauids. 1 >o OH*$!H*CMe,- C Ha* CMe 3-fiydvoxy-2 2 5 5-tetramethyZtetrahydrofuran has b. p. SPo/15 mm. D17 0.9483 H~ 1-4435; the &etat/ has b. p. lSl-ISZo D15 0.9587 nD 1,4256 and the acid phthulate m.p. 139-141O. 3 - Hydroxy - 2 5-dimethyl-2 5 - diethyztetrcchydrofuran has b. p. 107O/19 mm. D15 0-9539 n 1.4547; the acetate has b. p. 97-98"/15 mm. D15 0.9589 nD 1.4382. Ketodimethylhydrof uran reacts with organo-magnesium halides giving derivatives of hydroxyhydrofurans whereas the ketotetra- alkylhydrofurans react in the enolic form yielding hydrocarbons. The following compounds have been obtained 3-H?/droxy-S 3 5 - t r i m e t h y Z t e t r ~ ~ ~ d r o f ~ ~ ~ n b. p. 71-73'/16 mm.,ORGANIC CHEMISTRY. i. 291 171-173"/755 mm. D21 0.9719 n 1.4420 ; 3-hydroxy-2 5-dimethyl- 3-ethyltetrahydrofuran b. p. 79-Sl0/16 mm. IF1 0.9693 nD 1.4485 ; 3-hydroxy-3-phenyl-2 5-dimethyltetrc~hydrofura?a b. p. 138-140°/ 16 mm. D20 1.0827 n 1.5310 ; 3-hydroxy-3-benzyl-2 5-dimethyltetra- hydrofurun b.p. 146-147'115 mm. D15 1.0598 n 1.5251 ; 3-hydroxy- 3-p-tolyl-2 5-dimethyltetrahydrof2lralz b. p. 149-150"/ 15 mm. D15 1.0456 n 1.5380 ; 3-hydroxy-3-bennyl-2 2 5 5-tet?.amethyltetra- hydrofuran m. p. 89". w. 0. w. Action of Sodium Hydroxide on 5-Methylfurfuraldehyde. JAN J. BLANESMA (Chem. Weekblad 19 12 9 186-187).-Sodium hydroxide converts 5-methylfurf uraldehyde into the corresponding alcohol 5-methyl-2-hydroxymethylfurc~n and acid 5-methylpyromucic acid. The alcohol is a colourless mobile liquid of fruit-like odour. It has b. p. 100°/ll mm. Exposure to light and air converts it into a yellow syrup which gradually becomes brown and viscous and ultimately changes t o a dark-coloured resin. A. J. W. Synthesis of Pyrorneconic Acid.ALBERTO PERATONER (Qccxxetta 1911 41 ii 686-697).-The author has effected the synthesis of pyromeconic acid by direct oxidation of 4-pyrone after unsuccessful attempts to obtain derivatives of rneconic acid from the substance CO,Et*CO*CH,*CO*CH(OEt)*~O*CO,Et by dehydration. When ethyl acetol ether is condensed with one molecule of ethyl oxalate in the presence of sodium ethoxide the vessel being cooled externally with ice and the solvent subsequently evaporated in a vacuum below 40° a sodium salt is produced which on treatment with concentrated acetic acid and distillation in a vacuum yields ethyl a-ethoxt&tane-/36-dione-6-cnrboxylc~te OEt*CH,*CO* CH,* CO* CO,Et which is a slightly yellow oil b. p. 135-140°/20 mm. I t s aqueous solution gives a cherry-red coloration with ferric chloride and with copper acetate it yields a green salt C,,H,,O,oCu.By the action of a second molecule of ethyl oxalate 0x1 the sodium salt above described and proceeding as suggested by Willstatter and Pummerer in the case of xanthochelidonic acid (Abstr. 1904 i l043) diethyl P-ethoxypentane- aye-trione-ac-dicarboxylate C0,Et CO*CH(OEt)-CO* CH,*CO* CO,Et is obtained. The triketone is purified by sublimation at 20 mm. treatment with water and resublimation and then forms colourless acicular crystals or scales m. p. 124-125". With alkalis it yields yellow amorphous xantho-salts but with ferric chloride it gives a dirty green coloration which becomes reddish-brown whilst copper acetate yields a green copper salt. It was not found possible t o eliminate the elements of water from the triketone in any way but when it is boiled for half an hour with hydriodic acid (D 1.7) n-pimelic acid is produced.Pyromeconic acid is formed when one molecule of hydrogen peroxide (3% solution) is added slowly to a solution of one molecule of .Q-pyrone one molecule of ferrous sulphate and sulphuric acid the mixture being cooled in ice. The isolation of the acid may be effected either by treating the liquid at its boiling point with ammonia and air until the1. 292 ABSTRACTS OF CHEMICAL PAPERS. pyrone is converted into pyridone and the iron is precipitated or by prolonged extraction of the liquid with chloroform the product in either case being purified by sublimation in a vacuum below 100' and by recry stallisation. R.v. s. Anthocyanins. 11. An Anthocyanin-like Oxidation Product of Chrysin. &~AXIMILIAN NIERENSTEIN (Ber. 19 12 45 499-501. Compare this vol. i 42).-By oxidation with chromic and acetic acids in the cold chrysin yields chrysone (annexed formula) m. p. above 360° dark red needles. I t exhibits the blue and the red colour reactions HO/\/\Ph of anthocyanin with alkalis and concentrated I I 11 sulphuric acid respectively. It forms an acetyl \/\/ derivative C1'7H1006 m. p. 324-326' (decornp.) 0 Go red needles and when heated with acetic anhydride and zinc dust yields an actrtglated hydroxychrysin by the hydrolysis of which 1 3 4-tri~~ydroxy~c~vone m. p. 304-305' is obtained (triacetyl derivative m. p. 214-21 7O colourless needles). C. s. 2 0 Fisetin is not oxidised by chromic and acetic acids.Some Derivatives of Eydroxyquinol. VII. GUJDO BARGEL- LINI and ERMANNO MARTEGIANI (Gaxxetta 1911 41 ii 612 -618),- The paper deals with two coumarins obtained by condensation of hydroxyquinol with ethyl acetoacetate and ethyl benzoylacetate respectively. When hydroxyquinol triacetate and ethyl acetoacetate are heated together for half an hour on the water-bath with 73% sulphuric acid P-methylssculetin is obtained identical with that prepared by von Yechmann and von Krafft (Abstr. 1901 i 285). Its diacetyl derivative C14H1206 has m. p. 149-151O; i t dissolves in concentrated sulphuric acid giving a yellowish-green coloration. The dibenxoyl derivative C24H1606 crystallises in colourless needles m. p. 152'; it dissolves in concentrated sulphuric acid giving a slight yellow coloration.The dimethyl ether crystallises in colourless needles m. p. 130-134'. The monomethyll ether CllHlo04 formed in its preparation crystallises in slightly yellow needles m. p. 173-1 75'. P-Phenylaescutetin C,,H,,O is a yellow crystalline powder obtained by condensation of hydroxy quinol triacetate with ethyl benzoylacetate in the presence of 73% sulphuric acid. It dissolves in concentrated siilphuric acid giving n yellow coloration and with ferric chloride in alcoholic solution it gives a green coloration. The diacetyl derivative Cl9Hl4O6 crystallises in colourless needles m. p. 156'. The benxoyl derivative crystallises in colourless needles m. p. 162-164'. The dimethyl ether was not obtained in crystalline form but crystals of a substance m.p. 122-124° were obtained which was probably the monomethyl ether. R. V. S. New Method for the Preparation of Thiophen. WILHELM STEINKOPF (Verh. Ges. deut. Natudorsch. Aerxte 1912 ii [l] 220-281).-Acetylene is passed through an iron tube containing pyrites at a temperature of 300O. The tube is provided with a transporting screw for the removd of spent pyrites The liquidORC; AN IC CHEMISTRY. i. 293 product obtained in the condensing vessel contains 40% of thiophen. In seven or eight hours 800 grams of distillate may be obtained using 8 kilograms of pyrites. The thiophen is easily obtained with a purity of 95-96% the impurities being sulphur compounds with traces of benzene. Larger quantities of benzene are not obtained in the process.The remainder of the distillate is a complex mixture from which only a single compound C,H6S b. p. 36-38O with a very penetrating odour of garlic has been isolated. C. H. D. s-Dioxythionaphthen. MAURICE LANFRY (Cornpt. rend. 19 12 154 519-521. Compare Abstr. 1911 i 555 740 1009).- s- Dioxythionaphthen C,H,O,S is prepared by the action of hydrogen peroxide on thionaphthen (Gattermann Abstr. 1894 i 92) employing 0.5-0.8 gram of active oxygen per gram of thionaphthen. The compound crystallises in cdourless needles m. p. 142-143' ; it does not give the Laubenheimer reaction and does not show the properties of a phenol a ketone or a quinone. It follows therefore that the oxygen is attachcd directly to sulphur as indicated by the name the author suggests for the compound.Dioxythionaphthen unites with bromine to form a dibromide C8H,02SBr occurring in slender needles m. p. 168-1 70". When treated with fuming nitric acid it yields a mononit?-o-derivative C,H,O,S*NO crystallising in yellow rhombohedra m. p. 187-1 88'. w. 0. w. ( ( Thio-indigo " Dyes of the Naphthalene Series. PAUL FRrEDLXNDER and N. \~OROSHZOW (Annalen 19 12 388 1-23). -The series of reactions whereby anthranilic acid has been converted into " thio-indigo " (Abstr. 1906 i 378 ; 1907 i 334) is applicable in the naphthalene series to the preparation of " bis-2 S-napht?~athiophen- indigo " [bis- 2 3-~uphtT~ccthiophen] and bis-1 ; 8 -naphth apenthiophen- indigo '' [bis- 1 8-nuphthathiophen] (formula I and 11 respectively). (1.1 (11.) [With E. ECKSTEIN.]-T~~ sodium salt which is precipitated by the addition of sodium chloride to the not too dilute diazotised solution of 2-amino-3-naphthoic acid is added to a hot solution of potassium xanthate. When the oil which separates has become solid i t is dissolved in sodium hydroxide and warmed with chloroacetic acid.By acidification p-3-carboxynaphthylthiolucetic acid CO,H*CloH,*S*C~,*CO,H m. p. 224' (decornp.) white needles is obtained. I t s sodium salt is boiled with acetic anhydride and sodium acetate the resulting acetoxynaphthathiophen is hy drolysed by dilute sodium hydroxide VOL. CII. i. 12:i. 294 ABSTRACTS OF CHEMICAL PAPEHS. and the hydroxynaphthathiophen is oxidised by a1 kaline potassium ferricyanide whereby bis-2 3-naphthathiophen is obtained.The dye crystallises in almost black needles sublimes without decomposition yields an orange-red vat with alkaline hgposulphite and develops an olive-green coloration with fuming sulphuric or chlorosulphonic acid. Naphthastyril (Abstr. 1910 i 201) is converted by boiling 10% sodium hydroxide into sodium 8-amino-1 -naphthoate the diazotised solution of which is converted by reactions similar to the preceding into bis-1 8-naphthapenthiophm which crystallises in long needles with a copper lustre and sublimes with decomposition. The inter- mediate products isolated in its preparation are the anhyds.ide of 8-thiol-1-naphthoic acid c10H6<(!,0 m. p. 144-5-145*5O yellow needles a-8-carboxynaphthyZthioZacetic acid C02H*GloH6*S*CH2aC02H m. p. 177" and hydroxy-1 8-naphthape~thiop~~n cloH6<~(oH)>CH m.p. 84.5-85*5" .yellow prisms (acetyl derivative m. p. 130*5O yellow leaflets) which is oxidised to the dye best by atmospheric oxygen. (( Bis-1 2-naphthathiophenindigo " [big-l 2-naphthathiophen] and his-2 1-naphthathiophen [bis-2 ; 1 -naphthathiophen] (formula? I and 11 respectively) cannot be prepared by the preceding method S > co GO because the necessary aminonaphthoic acids are unknown. The latter dye has been prepared in three ways (1) a-Naphthylamine-2- sulphonic acid is converted in the usual way into 1-cyanonaphthalene- 2-sulphonic acid the potassium salt of which yields the chloride CN*C,,H6*S02C1 m. p. 141-142" by heating with phosphorus penta- chloride. The chloride is reduced by zinc and hydrochloric acid to the mercaptan which reacts with sodium chloroacetate in alkaline solution to form after acidification - 1 - carboxynaphthylthiolacetic acid C0,H-C,oH,*S-CH2*C0,H,H20 m.p. 6 9 O (1 34.5' when anhydrous) colourless needles. By prolonged boiling with concentrated sodium hydroxide and acidification of the hot solution this acid yields hydroxy- 2 1 -nap/ithnt/uiopjben c,,H~<~ER)>cH m. p. 12 10 colourless needles which reacts with benzaldehyde and p-nitrobenzaldehyde to form the thioindogenides C,,H6<s->C:CHPh m. p. 159O yellow GO needles and C10H,<_5->C:CH*CBH,.N0 co m. p. 287'. yellow needles respectively and with /3-naphthisatin chloride in hot xylene to formORGANIC CHEMISTRY. 295 naphthifidole-2 1-naphthathwphen (annexed formula) dark violet crystals which develops a bluish-violet /\ coloration in concentrated sulphuric acid.(2) 2-Thiol-a-naphthylamine and potassium \/\/\ ?;)\) chloroacetate are beated with concentrated 1 1 C:C I 1 potassium hydroxide whereby after acidi- \/\/ \/\/ fication the Eactam of p-1 -aminonaphthyl- thiolacetic acid Cl,,H6<s-LH- m. p. /\ I I co NH*CO S NH 203O is obtained. CN *C,oH6*S*UH2*C02H m. p. 173' which is prepared from the preceding compound is con- verted by hot potassium hydroxide into potassium 3-arninonaphtha- tl~iophen-Z-cccr~oxyZate an acidified solution of which yields hydroxy- 2 1-naphthathiophen by boiling. (3) ,5-Naphthylthiolacetic acid CloH7*S*CH2-C0 H m. p. 91' obtained by heating p-naphthyl mercaptan and chloroacetic acid in alkaline solution is converted directly into hy droxy-2 1-naphthathiophen by 10% chlorosulphuric acid in chloroform at the ordinary temperature.Bis-2 l-naphthathiophcn which is obtained by the oxidation of hydroxy-2 I-naphthathiophen best by alkaline potassium ferricyanide crystallises in reddish-brown needles with a bronze lustre develops a dark blue coloration with concentrated sulphuric acid and yields a yellow vat with alkaline hyposulphite. Bis-1 2-naphthathiophen which can be obtained by methods analogous to the preceding forms dark red needles develops a brownish-red coloration with concentrated and an intense blue with fuming sulphuric acid and yields a yellow vat. The Zactam of a-2-amino- naphthylthiolacetic acid c&fit6<&-8 m. p. 210° a-2-cyano- naphthylthiokacetic acid CN~CloH6*S*C132*C0,H m.p. 137-138° and p- 1-Cyanonaphthylthiolacetic acid hydroxy-1 2-naphthathiophen CloH,<X C W ) >CH m. p. 142' (benxyl- i d e m derivative m. p. 181° yellow leaflets) are also described. c. s. Organic Syntheses by meana of Sunlight. VII. Photo- synthesis of a New Alkaloid from A etophenone and Ammonia EMANUELE PAT ERN^ and CONCETTOCMASELLI (Gaazetta 1912 42 i 65-75 ; Atti R. Accad. Lincci 1912 [v] 21 i 235-243).-When acetophenone dissolved in saturated alcoholic ammonia is exposed to sunlight for several months a substance is produced which from its properties is to be regarded as an alkaloid. The yield does not exceed 20%. The new alkaloid C18H18N2 forms large transparent crystals [ZAMBONINI the crystals belong to the triclinic system a;b:c==1.5017 1 :1.5993; a 91' 21.5' /3 106' 14 y 7g3 60'1 which have m. p.2 2 7 O and dissolve in alcohol giving a strongly alkaline solution. The substance has about the normal molecular weight in freezing acetic acid. The nitrate is a white crystalline powder m. p. 958O. The hydrochloride C,sH1sN2,HCl x 2i. 296 ABSTRACTS OF CHEMICAL PAPERS. crystallises in tufts of long colourless needles and does not change when heated in a current of dry hydrogen chloride in a bath a t 350'. The plntinichloride (C,,H,,N,),,H,PtCI forms silky flesh-colouretf lamin% which begin to blacken at 260'. The silver salt is a white amorphous powder. when warmed with potassium nitrite in solution in glacial acetic acid and alcohol ; the substance crystallises in lustrous laminse m.p. 218' (decom p .). Negative results mere obtained in attempts to oxidise the alkaloid with permanganate and to determine its alkyloxy-groups. When the substance is heated in a sealed tube for three hours at 370' a portion of i t is converted into a reddish-brown oil but the greater part remains unchanged When the alkaloid was heated with hydriodic acid and phosphorus for six days the product consisted of the hydriodide of the base together with a small quantity of a yellow oil. The base yields a mononitroso-derivative C&#2 NO R. V. S. Rearrangement of Cinchonine and Quinine into Their Poisonous Isomeridea Cinchotoxine and Quinotoxine. HENRY C. BIDDLE (Ber. 1912 45 526-528. Cornpare Rnbe 1911 ii 33).- Salts of cinchonine and quinine wheii heated at 95-98' in aqueous solution with or without excess of acid undergo rearrangement into their poisonous isomerides cinchotoxine and quinotoxine.The velocity of the reaction is illcreased when the dissociation constant of the acid used is lessened; this applies to the action of acids both on salts and on free alkaloid. With acetic or propionic acid the change is practically complete after forty-eight hours' beating ; under the same conditions wing an excess of hydrochloric acid practically no rearrangement takes place. The same change also takes place slowly when the salts are heated a t 36c or when the salt solutions are exposed to direct sunlight at the ordinary temperature; in this case much resinous matter is also formed which colours the solution brown.It is possible that cinchotoxine and quinotoxine are formed similarly in the human organism. E. P. A. The Symmetry of Sparteine. CHARLES MOUREU and AMAND VALEUR (Corrryt. rend. 1912 154 309-312. Compare this vol. i 2lO).-The action of methyl iodide on isosparteine hydriodide at 135' leads t o the formation of isosparteine a-methiodide. The action of methyl iodide on sparteine has already been described ; since it leads t o analogous results it follows that both bases are symmetrical. As this is impossible owing to the mode of formation of isosparteine i t follows that the action of methyl iodide on the hydriodides is not purely one of simple addition but involves displacement of the halogen hydride by the alkyl iodide and direct addition of the displaced hydrogen iodide.There is therefore no absolute proof of the sSmmetry of the bparteine molecule. Reasons are adduced in support of the view that stereoisomerism of the groups about the nitrogen atom is sufficient to explain the existence of two isomeric methylsparteine methiodides. W. 0. W.ORGANIC CHEMISTRY. i. 297 Methylation of Brucine. GUSTAV MOSSLER (Monatsh. 19 12 33 1 9-32).-MethyZbrucine acetate C2,B3,0,N2,C,H,0,,5H20 prepared by the cautious addition in portions of silver acetate to a finely divided suspension of brucine methiodide iu water crgstallises in rhombic plates m. p. (anhydrous) 208-209O (decomp.) - 9.97". The same substance was obtained by the action of acetic acid on methylbrucine. When warmed with hydrochloric acid brucine methochloride is obtained.On treatinent with methyl iodide in methyl-alcoholic solution dimethybbrucine iodide C,5H,305N2T,2~-H,0 is obtained in flat right- angled plates m. p. 268' (decomp.). L)imethyZbrucins acetate C,7H,,07N,,5H20 is very similar t o the monomethyl compound m. p. 205-206' [a] - 7.14". With hydro- chloric acid the salt C,5€S3,0,N,C1 is obtained m. p. 261'. Crystalline products could not be obtained by the oxidation of methyl hrucine. Methyl- and dimethyl-brucine are considered to have t h e structure of betaines whereas dimethglbrucine iodide is a quaternary iodide. E. F. A. Hzemopyrrole. ' J. GRABOWSKI and LEON ~Y~ARCHLEWSKI (Ber. 191 2 45 453-456).-The authors have subjected 2 4-dimethyl- 3-ethylpyrrole (Knorr snd Hess Abstr. 1911 i 1019) to the action of benzenediazonium chloride and find that i t s behaviour differs from that of hsmopyrrole obtained from hsmin since it yields orange needles of benxeneazo-2 :-4-dimetl~yl-3-ethyIplc/l'roEe hydrochloride C8H12N *N,C6H5,HC1.This substance has no definite m. p. but begins to decompose at 120° and evolves gas at about 155'. Attempts to convert i t into a disazo- derivative were unsuccessful. The authors draw the conclusion that trisubstituted derivatives of pyrrole are incapahle of reacting with more than one molecule of a diazonium salt and doubt the view that one -N,C6 H group of the hsmopyrrole derivative C8Hl,N( N2C6H5)2 is attached to the nitrogen atom. The stability of the hsmopyrrole dyes towards hydrochloric acid and the so-called H-acid is a further argument against an azo-diazoamino-constitution.The reduction of methyl-n-propylmaleinirnide (Msrchlewski and Buraczewski Abstr. 1905 i 399; 1906 i 779) has been repeated with larger quantities of material. From the product of the reduction two crystalline dyes were isolated in the form of hydrochlorides but in quantity insufficient for analysis. I n hydrochloric acid and in neutral solution however their spectra are identical with those of the dyes prepared from haemopyrrole. H. W. Syntheses of Phyllopyrrole. Chemistry of Hamopyrrole. HANS FISCHER and E. BARTHOLOM~US (Bey. 19 12 45 466-471).- When s u b d t u t e d pyrroles are heated with alcoholic solutions of sodium met'hoxide or ethoxide alkglation occurs at a carbon atom. In this manner the authors have syu thesised phyllopyrrole C M e ( p NW<cMe:CEti.298 ABSTRACTS OF CHEMICAL PAPERS. (compare Willstiitter and Asahina Abstr. 1912 i 42) from 2 4-di- methyl-3-ethylpyrrole and sodium methoxide from 2 4 5-trimethyl- pyrrole and sodium ethoxide and from hzemopyrrole and sodium methoxide. The highest m. p. observed for phyllopyrrole was 69". Phyllopyrrole picrate has m. p. 104-105'. Similarly 2 4-dimethyl-3-ethylpyrrole was converted by means of sodium ethoxide into 2 4-dimethyl-3 5-diethylpyrrole. When hsrnopyrrole is heated with sodium ethoxide it yields a dimethyldiethylpyrrole (isolated in the form of its picrate m. p. 102-103') differing from that described above. Since the relative positions of the methyl and ethyl groups in hfemopyrrole have been determined by its oxidation to methylethylmaleinimide the authors cMe'FMe for hsmopyrrole and OH-CEt are led to propose the formula NH< regard its product of its ethylation as 2 3-dimethyl-4 li-diethyl- pyrrole.By coupling 2 4 5-trimethylpyrrole with diazobenzenesulphonic acid a red dye C,,H,,O,N,S was obtained. The preparation of phyllopyrrole from hzemin is fully described. Mirror Image Isomerism with Iron Compounds. ALFRED WERNER (Ber. 1912 45 433-436).-1n order to ehow that ethylene- diamine is not a necessary cause of optical activity in complex metal ammonias the author has investigated the tri-a-dipyridylferrous com- pounds [ (Dipyr),Fe]X2 and has succeeded in obtaining the optically active lzevo-isomerides by means of d-ammonium tartrate. The observed specific rotations are very great ( > 500') but racemisation takes place very quickly in aqueous solution the rotation falling to half its original value in half-an-hour.The compounds obtained belong to the class of molecular asymmetry I1 (this vol. i 166); they prove that optical activity does not depend on the presence of ethylenediamine and also that it can occur with co-ordination compounds of a divalent element. Tri-a-dipyridylferrous bromide was prepared in a manner described previously (Blau Abstr. 1889 1212; 1899 i 387) and resolved as follows 2.5 grams were dissolved in 112 C.C. of water and 60 grams of d-ammonium tartrate added to the filtered solution which was then cooled to -4'. After some time intense red crystals of l-tri-a-dipyridy(fmrous-d-tartrate separate which cannot be recrys- tallised without loss of activity A 0.125% solution gave a - 0.35O in a decimetre tube at 15O; after three and a-half hours the rotation had fallen to zero.l-~~i-a-dipyridylferrous bromide [Fe( Dipyr),]Br,,6H20 was obtained from the tartrate by double decomposition with potassium bromide ; it could not be recrystallised owing to rapid racemisation. It forms dark red flat crystals and bas [a]-520' and [M]-4117*8° although these values are probably too low because of racemisation. The iodide [Fe( Dipyr)$,,5H20 was similarly prepared from the tartrate and sodium iodide and forms glistening dark red flat leaflets; it has [a] - 440' and [MI - 3818.7O. H. w. T. S. P.ORGANIC CHEMISTRY i. 299 The Preparation of Nitropyridine. FRANZ FRIEDL (Ber. 191 2 45 428-430).-The direct nitration of pyridine has been accomplished by gradually adding potassium nitrate t o a solution of pyridine in 18% fuming sulphuric acid heated at 330'.P-Nitropyridine crystallises in long colourless needles m. p. 41° b. p. 216'. P-Nitropyridine nitrate has m. p. 150-151'. The position of the nitro-group in the molecule was determined by reducing nitropyridine by means of stannous chloride to /3-amino- pyridine (Pollak Abstr. 1895 i 391) and further by the trans- formation of this compound into P-hydroxypyridine (Fischer and Renouf Abstr. 1884 1370). Nitropyridine is also formed in small quantity by the action of concentrated nitric acid on a solution of pyridine in fuming sulphuric acid a t 330' and atmospheric pressure.H. W. 4-Oxgpyrone and Some of its Derivatives. ALBERTO PERATONER (Occxxetta 1911 41 ii 619-685. Compare Ost Abstr. lS79 708 ; 1582 601 ; 1883 '791 ; 1884 1302 ; 1885 48 ; Peratoner Abstr. 1902 i 421 493 ; Peratoner and others Abstr. 1905 i 806 SO7 ; Palazzo Abstr. 1905 i 458; Palazzo and Onorato Abstr. 1905 i 459).-The paper deals with Ost's nitrosopyromeconic acid and with some of its transformation products and their derivatives. The author discusses fully the constitution of the substances concerned in the light of the previous work of himself and others and of the new experimental data now obtained. Further details are given as to the preparation of Ost's nitrosodipyro- meconic acid by the action of ethyl nitrite on pyromeconic acid. The author also finds that phenol catechol resorcinol! pyrogallol a-naphthol and thymol yield traces of the corresponding nitroso-derivatives when they are treated with alkyl nitrites at a low temperature. Benzoyl- acetone and ethyl benzoylacetate yield nitroso-derivatives in this way a t the ordinary temperature.When nitrosodipyromeconic acid C5HsO,N,C5HpO is treated with rather more than two molecules of phenylhydrazine in glacial acetic acid two products are obtained (1) a substance crystallising in yellow needles m. p. 165' ; (2) a greyish-white crystalline su6stalzce which by treatment with hot benzene is converted into a substance crystal- lisiog in yellow needles m. p. 199-200'. composition required by the formula Both compounds have the ? C (N 0 H) Q N *N HP h and CH:CH--C:N*NHPh' are t o be regarded as stereoisomerides.Both yield the same oso- tetrazone CI7Hl3O2N5 when treated with warm alcoholic ferric chloride solution. The osotetrazone crystallises in red needles m. p. 137-138' which appear black with a metallic lustre when viewed by reflected light. Both hydrazo-oximes when kept at 210' lose one molecule of water yielding a substance C17H,,0 N which forms white needles m. p. 242O. Ost's nitrosodipyromeconic acid also yields a quinoxaline Cll'BC702N3 when treated with o-phenylenediamine hydrochloride in glacial acetic acid in the presence of sodium acetate. The substance forms lemon-i. 300 ABSTRACTS OF CEEMICAL PAPERS. yellow crystals gives a green coloration with sulphuric acid and dissolves in alkali hydroxides forming yellow solutions from which the original substance is precipitated by carbon dioxide.[With A. TAMBURELLO.]-In proof of the constitution previously given for Ost's pyromecazonic acid (2 3-dihydroxy-4-pyridone) i t is found that the product of the reaction of its diacetgl derivative with diazomethane yields about the same figures for -0Me and :NMe groups when analysed by the methods of Zeisel and of Herzig and Meyer respectively. The pyromecazonic acid does not react with ethyl nitrate and therefore does not contain a ketomethylenic grouping. Ost's pyromecazone (obtained by oxidation of pyromecazonic acid) bebaves in the same way when treated with diazomethane for the yellow oil which is obtained co6tains only half the calculated amount of -0Me group. The action of diazoet'hane is different the product both from the free quinone and from i t s additive product with ethyl alcohol contains almost the amount of -0Et group corresponding with the formula C,H,B,N*OEt. To the quinone the constitution CH:N-YO &H.C( OH)*CO is assigned. It gives the reddish-violet coloration with potassium hydroxide described by Bamberger as characteristic of o-quinones and with o-phenylenediamine it forms a quinoxaline C,,H70N which crystnllises in canary-yellow needles and for which the formula The acetyl derivative of the quin- EH*NH*F:N CH-CO-CZN oxaline ClsHQO2Ns forms greenish-yellow needles.I n support of the conclusion that Ost's oxypyromecazonic acid is 1 2 3-trihydroxy-4-pyridone the author finds that when a saturated aqueous solution of the substance is treated with ferric chloride a red iron salt is precipitated having the composition Fe(C,H,01N),,3H20. The acid also forms a trincetyl derivative C,H,O,NAc which crystal- lises in aggregates of minute needles m.p. 123-124' and a tribenxoyl derivative C5H204NBz8 crystallising in colourless needles m. p. 162-163'. The position of the third hydroxyl group (attached to nitrogen) follows from the fact. that it is readily reduced by tin and hydrochloric acid or by hydriodic acid and from the production of the iron salt above mentioned. [With A. TAMBURELLO.]-B~ the action of hydroxylamine on the ethers of comenie acid derivatives of 1-hydroxypyridone can be obtained When ethylcomenic acid is treated with hydroxylamine an acid C,H,O,N is obtained m.p. 174-175' (with evolution of carbon dioxide). The substance gives a red coloration with ferric chloride. Its eth3l ester OEt*C,H,O(CO,Et):N*OH forms colourless needles m. p. 156'. The cmetyl derivative OEt*C,H,O(CO,Et):N*OAc forms rosettes of colourless needles m. p. 81-82'. The action of hydroxylamine on ethyl ethylcomenate yields the above ethyl ester of m. p. 156O. To the acid of m. p. 174-175O the structure of 1-hgdroxy- 2-ethoxy-4-pyrior~~-6-cclrboxylic acid is ascribed. When it is reduced with tin and hydrochloric acid it yields a substance C,H,O,N which crystallises with 1H,O in rosettes of colourless needles m. p. 224-225' >C,H is suggested.3RGANIC CHEMISTRY. i. 301 but when dehydrated (at 150') it melts at 235' (decomp.). It gives an orange-yellow coloration with ferric chloride and to it is assigned the constitution of 3-ethozy-4-pyridone-G-carboxylic mid.It is identical with the product of the action of ammonia on ethylcomenic acid and is also obtained by reduction of the ethyl e$ter above mentioned (m. p. 156') since the ester is saponified a t the same time. 3-Ethoxy-4-pyridone-6-carboxylic acid is hydrolysed when boiled for two hours with hydriodic acid (I3 1 *74) yielding 3-lqdroxy-4-pyi-idone- 6-carbox~Zic acid (Ost's comenamic acid). When l-hydroxy-3-ethoxy-4- pyridone-6-carboxylic acid is kept a t 190' for some time l-hydroxy-3- etho:q-4-pyridone is obtained ; it crystallises in colourless needles m. p. 156' and gives a brownish-red coloration with ferric chloride. [With E. &EtAPELLE.]-The phenylhydrazones of pyrorueconic acid and some of their derivatives have also been investigated.When a solution of phenyldiazonium acetate is treated with a solution of pyromeconic acid a t O' the monophenyhydracxone CllH803N2 is pro- duced ; it forms dark red or purple crystals which decompose a t 176". When it is treated with two molecules of phenylhydrazine it yields two triphe)zylhydraxones C5H,0(:N*NHPh) which are apparently stereo- isomeric. One of these has m. p. 161-162' the other has m. p. 212-214'. The former is converted into the latter if hydrogen chloride is passed through its alcoholic solution for half an hour. The monohydrazone reacts with o-phenylenediamine yielding a puinoxaline C17H120N,. The monohydrazone is also readily converted into an hydroxy pyridone derivative and this indicates the analogy bet ween its structure and that of oximinopyromeconic acid.When it is mixed with a little water and treated with sulphur dioxide at O' a substance C',,H,,0,N2. is obtained which forms crystalline scales rn. p. 220° and is assigned the constitution of l-anilino-2 3-dihydroxy-4-pyridom. Its hydrochloride C~lHlo03N2,HCl crystallises in colourless needles. Its dicccetyl derivative C H803N2Ac2 crystdlises in lustrous scales m. p. 155-156'. l-Anilino-2 3-dihydroxy-4-pyridone gives with ferric chloride a deep blue coloration which disappears when excess of ferric chloride has been added. The quinone thus produced reacts with o-phenylenediamine yielding a quinoxaline Cl7Hl20NI which forms golden-yellow scales m.p. 181-182'. The quinone is best obtained by oxidising the pyridone with silver oxide but i t has been isolated only in the form of its additive product with methyl alcohol Cl,H,O,N,,MeOH which dissociates and melts (forming a red liquid) at 87-48'. [With A. D'ANCEEO.]-T~~ authors have also prepared some derivatives of dibromocomenic acid. Dibromocomenic acid (compare Mennel Abstr. 1883 656) reacts with basic lead acetate losing both atoms of bromine and the corresponding quinone is formed but could not be isolated. Both dibromocornenic acid and this auinone react 1 with o-phenylenediauine yielding a quinoxaline t o which the formula Cu2H*f?o-?:N>C6H4 is ascribed. It dissolves in alkalis giving a CH*CO*C:N yellowish-red coloration and in concentrated sulphuric acid giving a red coloration.It yields a phenyZhydrazone which decomposes about 1 70° to which the formula When heated it decomposes abdve 200'.i. 302 ABSTRACTS OF CHEMICAL PAPERS. CO,H *C-O--- ?:N>C6H is assigned. The phenylhydrazone 8H-C(:N-NHPh)*C:N yields the corresponding xantho-salt when ' treated with potassium hydroxide. The constitution of these substances is an argument in favour of the ketomethylenic formula for comenic acid. R. V. S. 4 6-Dinitrophenyl-1 3 - dipyridinium Chloride and 4 6 - Dinitro-3-aminopyridinium Ohloride. THEODOR ZTNCKE and G. WEISSPFENNING (J. pr. Chem. 1912 [ii] 85 207-210. Compare Abstr. 1910 i 585).-When 4 6-dinitro-1 3-dipyridinium chloride is heated for five minutes with aniline in alcoholic solution it is converted into 4 6-dinitro-3-aminophenylpyridinium chloride and the previously-described dianilide NPh:CH*CEL:CR*CH:CH*NHPh only one of the pyridine groups being removed. The further action of aniline on 4 6-dinitro-3-aminophenylpyridinium chloride results in the removal of the second pyridine group with the formation of the dianilide together with 4 6 - dinitro - m -phnylenediamine which separates from glacial acetic acid in brownish-yellow crystals m.p. 300O. I f the action is continued for three to four hours the dianilide disappears and on the addition of hydrochloric acid 4 6-dinitro-1 3- diaminobenzene hydrochloride and p hen ylpyridinium chloride (A bstr. 1904 i 921) are obtained. The successive action of excess of 2N-sodium hydroxide and hydro- chloric acid on an aqueous solution of dinitroaminophenylpyridinium chloride yields a red crystalline substance C,,H,,O,N the constitu- tion of which is represented by one of the following formule.This substance decomposes when heated gives a reddish-violet coloration with alcoholic potassium hydroxide and is reconverted by warm concentrated hydrochloric acid into dinitroaminophenyl- pyridinium chloride. The interaction of dinitrophenyldipyridinium chloride and phenyl- hy drazine in alcoholic solution yields a deep black crystalline substance the composition of which is represented by one of the following formuls C6H,(N0,)2(N:CH*CH:CH*CH:CH*NH*NHPh)2. C6H,( NO,),(NH* CH CH*CH:CH*CH:N*NHPh),. The same compound is produced by the action of phenylhydrazine on the blackish-green substance C,,H,,O,N formed from dinitro- phenyldipyridinium chloride and alkalis (Abstr.1910 i 585). F. B. Action of Hydrogen Sulphide on Dinitrophenylpyridinium and Dinitrophenyldipyridinium Chlorides. THEODOR ZINCKE and G. WEISSPFENNING (J. pr. Chem. 1912 [ii] 85 211-21'7).- The action of hydrogen sulphide on 4 6-dinitrophenyl-1 3-dipyri-ORGANIC CHEMISTRY. i. 303 dinium chloride leads to the removal o€ one of the pyridine groups and the formation of a thiobetaine anhydride (I) similar in constitution to the anhydride previously described (Abstr. 1910 i 585). The thiobetaine anhydride exists in two forms an orange-red modification containing 1H20 obtained by passing hydrogen sulphide into an aqueous solution of the pyridinium chloride and a dark red form which crystallises in leaflets and explodes on heating.The latter modification is produced by (1) the action of hydrogen sulphide on (1.1 (11.1 a 90% alcoholic solution of the pyridi- nium chloride and (2) by dissolving the orange-red variety in concentrated hydrochloric acid and diluting the solution with water. The anhydride forms salts which are instantly decomposed by water ; the hydrochloride (11) prepared from the anhydride and hydrogen chloride in alcoholic solution crystallises in white needles ; the phtinichloride is also described. The anhydride is converted by successive treatment with aqueous alkalis and acetic acid into an orange crystalline substance probably SH*C6H,(N02),*N :CH*CH CH* CH :CH*OH. A similar removal of the pyridine group takes place by the action of hydrogen sulphide on 2 4-dinitrophenylpyridinium chloride in aqueous solution the product in this case consisting of 2 4-dinitro- phenylmercaptan accompanied by a small amount of 2 2' 4 4'(?)-tetra- nitrodiphenyl sulphide.The latter compound forms the main product when the hydrogen sulphide is replaced by sodium sulphide or the action carried out in alcoholic solution NO2 NO2 ')SH Cp5N- ' C~H,kC1 E. B. Trinitrophenylpyridinium Chloride THEODOR ZINCKE (J. pr. Chern. 1912 [ii]? 85 217-221. Compare Busch and Kiigel this vol. i 50)-2 4 6-Trinitrophenylpyridinium chloride is best prepared by the interaction of picryl chloride and pyridine in ethereal solution. It has m. p. 128-129O (decomp.) and is resolved by alcoholic hydrogen chloride at 100" into its components ; the yellow crystalline pkatinicldoride ( Cl,H70,N,C1),PtC16 has m.p. 265O (decomp.). On successive treatment with hydrogen sulphide and hydrochloric acid it yields a substance which crystallises in dark violet leaflets of a metallic lustre. It reacts with aniline forming the dianilide C17H16N2 previously described (Abstr. 1904 i 921). The $-base C11H807N4 obtained by the action of alkalis forms brown crystals m. p. 190-193O (decomp.) yields a sodium salt and is converted by acetic and hydrochloric acids into picramide and the original pyridinium salt F. B. Conversion of Oxindole into Coumaran-1-one. CHARLES MARSCHALH (Ber. 19 12 85 582-585).-Oxindole has been trans- formed into coumaran-1-one by heating it with barium hydroxide in aqueous solution at 1 50° converting the resulting barium o-amino- phenylacetate (Baeyer and Comstock Abstr.1883 1130) by means ofi. 304 ABSTRACTS OF CHEMICAL PAPERS. the diazo-reaction into o-hydroxyphenylacetic acid and removing water from the latter compound by distillation. The diiizotisation is accomplished by the addition of an aqueous solution of the barium salt and sodium nitrite to cold dilute sulphuric acid. Oxindole is readily prepared by the reduction of isatin with sodium hyposulphite t o dioxindole and subsequently reducing this by means of sodium amalgam in aqueous alcoholic solution. Dioxindole has m. p. 167-1683 and not 180' as given by Baeyer and Knop (Annulen 1866 140 11). When di.-solved in aqueous sodium hydroxide and the solution treated with alcohol i t yields a crystalline sodium salt.which however is two unstable t o be isolated is converted by dilute sulphuric acid into dioxindole but is apparently different from the sodium salt obtained by Baeyer and Knop by reducing isatin with sodium amaIgam. F. B. Some New Derivatives of Garbaaole. BRUNO LEVY (Monatsh. 1912,33 177-184).-1t has been discovered that the high temperature (170-190") used by Graebe and von Adlerskron (Abstr. 1880,660) in the preparation of methyl- and ethyl-carbazole was unnecessary and that potassium csrbazole reacts with methyl iodide almost quantita- tively at the ordinary temperature. I n extending the reaction t o other alkyl halides it is found that the velocity of the reaction decreases as the series is ascended and also that the normal alkyl halides give a greater reaction velocity than the branched ones.Although no exact measurements were made ally1 iodide and benzyl chloride were found t o react much more readily than ethyl iodide n-Propylcarbazole was obtained by the reaction of the iodide with potassium carbazole on the water-bath; i t forms needle crystals rn. p. 50° and gives a picrate m. p. 98". isoPropyZcarbaxoZe obtained similarly has m. p. 120° and gives a picrate m. p. 143". n-Butylcarbaxole forms needles m. p. 58O and gives a picrate m. p. 89". sec.-Butylcarbazole is an oil which gives a picrate m. p. 64". isoAmyZcarbazole is an oil; the picrate has m. p. 85O. sec.-Amyl- carbazole is also an oil ; m. p. of picrate 93". Allylcurbaxole obtained by reaction at room temperature crystallises in colourless rhombs in.p. 56'; the picrate has m. p. 86". Benxylcarbazole also prepared at the ordinary temperature forms colourless needles m. p. 11 4" ; m. p. of picrate 105". Triphenylmethylcarbasole obtained by reaction of triphenylmethyl chloride and potassium carbazole in boiling benzene forms rhombic crystals m. p. 2454 isoButyZcarbazoZe is also an oil ; the picrate has m. p. 177". D. J?. T. Thioamides. 1V. Action of Hydrogen Sulphide O n Ni trogen-mbstituted Aminoacetonitriles. TREAT B. JOHNSON and GERALD BURNHAM (Amer. Chem. J. 1912 47 232-242).-ln a n earlier paper (Abstr. 19 11 i 712) it has been shown that arninoaceto- nitrile reacts with hydrogen sulphide to form the corresponding thioamide which is unstable and undergoes condensation in alcoholicORGANIC CHEMISTRY.i. 305 solution with production of thioglycylglycinethioamide. This thio- polypeptide is also unstable and becomes converted into dithio- piperazine. The present investigation was undertaken in order to ascertain whether thioamides of N-substituted amino-acids of the type R*NH*CH,*CS*NH would undergo similar transformations. It has been found t h a t phenylaminoacetonitrile p-tolylaminoacetonitrile anisoylaminoacetonitrile hippuronitrile carbethoxyaminoacetonitrile and carbamidoacetonitrile all combine smoothly with hydrogen sulphide at the ordinary temperature to form the corresponding thioamides which are stable compounds and can be heated with alcohol without undergoing any change. When these thioamides are heated above their m.p.’s they sufler decomposition but without producing a thiopolypeptide derivative or dithiopiperazine. Hjppurothioamide C6H,*COoNH*CH20(Y,So~~~2 m. p. 150’ (decomp.) crystallises in transparent blocks and reacts with bromoacetophenone with production of 4-phenyl- 2-ber,xoyZaminonzethylthiaxole m. p. 148O which forms rosettes of needles. Carbsthoxyccmir~oacetothioamide CO,Et*NH*CH,* CS*NH m. p. 11 8 O crystallises i n rectangular blocks and condenses with bromoaceto- phenone to form 4-phenyl-2-ca~bethoxy~cminomsthyZthiaxole CPh-N fiH-S>C*CH2*NH*C0,Et m. p. 59-61’ which crystallises in prisms and yields an unstable hydrobromide. When this hydrobromide is heated with hydrobromic acid it is converted into 4-phen~l-2-aminomethyEtl~iacxole hydyobromide - . ~H-S>C*CH2*NH2,2HRr m.p. 253’ (decomp.). CPh*N Anisoylaminoucetonitl.ib OMe*C,H,.CO*NH*CH,*CN m. p. 153-154’ prepared by treating an aqueous solution of aminoaceto- nitrile sulphate with anisoyl chloride and potassium hydroxide forms thin transparent plates. Anisoylaminoacstothioamide O~e*C,H,.UO.NH*CH,.CS.NH m. p. 189O (decomp.) crystallises i n slender prisms. Anilinoacetothioamide NHPh*CH,*CS*NH m. p. 166’ (decomp.) forms stout blocks. p-Toluidinoacetothioamide C,H,Me*NH*CH,-CS-NE m. p. 152O crystallises in rhombic plates or tabular prisms and reacts with bromoacetophenone to form 4-phenyZ-2-p-toZuidinomethyZthia~oZe gH-S>C*CH2*NH*C,H,Me m. p. 110-1 1l0 which crystallises i n CPh*N prisms. When p-toluidinoacetonitrile is heated with phenylthio- carbimide 2-thio - 5 -phe.rzylthiocarbamido - 1 - phenyl - 3 - p-toZyZdihydro- NPh-CS glyoxaline NHPh*CS*NH.C~,,__rS.C.H,Me’ m.p. 2Olc isproduced which crystallises in bright yellow need&. Cccrbarniduacetothioamids NH,’CO*NH*CH2*CS*NH m. p. 190-191’ (dacomp.) forms colourless prisms and condenses with bromoacetophenone with formation of 4-i”henyZ-2-ccicrbamidornethyZ-i. 306 ABSTRACTS OF CHEMICAL PAPERS. CH-5 tkiaxole ePh. N>C*CH,*NH*CO*NH m. p. 190° which crystailises in slender needles and yields a hydrobromide m. p. 214' (decomp.). E. G. Formation of 1 3-Thiazines from Thiocerbamide. WILLIAM J. HALE and HARVEY 0. BRILL (J. Amer. Chem. Soc. 1912 34 295-300).-1n an earlier paper (this vol. i 216) it has been shown that carbamide condenses with nitromalonaldehyde with formation of 5-nitro-2-hydroxypyrimidine.It has now been found that the condensation of thiocarbamidelwith nitromalonaldehyde takes place in an entirely different manner When thiocarbamide and nitromalonaldehyde are allowed to react in aqueous solution in presence of a very small quantity of sodium hydroxide or diethylamine the monothioureide of the aldehyde is produced. If piperidine is used as the condensing agent however 5-nitro-2-imino-1 3-thiazine separates whilst a small amount of the thioureide remains in the mother liquor. Nitromaclonaldehyde monothioureide NH C(SH)*N CH CH( NO,) *CHO m. p. 206-207' (corr.) crystallises in lustrous yellow leaflets and is readily desulphurised by treatment with basic lead acetate solution or mercuric oxide ; its potassium salt forms reddish-brown crystals ; the lead salt was also prepared.The methyl ether m. p. 78-79' (corr.) obtained by the action of methyl sulphate on an aqueous solution of the potassium salt forms yellow plates. Phenylhydrazine acetate reacts with the thioureide with formation of the phenylhydraxone. When the thioureide is suspended in alcohol and piperidine added it is transformed into 5-nitro-3-imino- 1 3-thiazine. 151-152O (corr.) crystallises in long yellow needles and is not affected when boiled with an alkaline solution of lead acetate or with mercuric oxide. Phenglhydrazine and aniline do not have any effect on the compound but benzonesulphonyl chloride reacts with it to form a yellow mass thus establishing the presence of the imino-group.By the action of acetic anhydride it is converted into the acetyl derivative NO,°C<cH:N>C:NAc /CH*S m. p. 141' (corr.). E. G. A Peculiar Auxochrorne Action. WALTER KONIG (Ved. Ges. deut. Naturfordb. Aerxta 1912 ii [ 13 221-223).-The colour of the pyridine dyes obtained from pyridine and primary or secondary amines is not satisfactorily accounted for by the usual formula NRR*CH:CH*CH:CH*CH:NClRR. The yellow colour of the simplest representative obtained from methylaniline becomes more green when the side-chain is lengthened by saturated alkyl groups or when an ortho-substituent is introduced into the benzene ring. On the other hand cyclic secondary amines such as tetrahydroquinoline or dihydroindole change the colour to red. These changes areORGANIC CHEMISTRY.i. 307 accounted for if one Tor other of the following formuh is used involving subsidiary valencies C1 H C CH '77 / /\ /\ \ \,,.,:.' LLL /\ HC YH ('I.) R e CH.NRR' (I.) ;b 1 ZH' I CH*NRR' N N c1 /\ R R' X R In accordance with Kaufmann's hypothesis the subsidiary valency indicated by the dotted line should shift the colour more towards red the stronger it is. This is explained by a comparison with Kaufmann's views on benzene compounds. C. H. D. Optically Active Hgdrazino-acids. AUGUST DARAPSKY ( Verh. Ges. dezct. Naturforsch. Aerxte 1912 ii [l] 215-216).-Hydrazino- acids of the formula NH,*NH*CHR*CO,H have only been obtained in she racemic form by Traube (Abstr. 1896 i 340) and Thiele (ibid. 341) The author's simpler method of preparation (Chem.Zeit. 1910 84 1280) allows of the preparation of the active modifications. 1-Hydrccxi~o~heny Iacetic acid NH,*NH*CHPh* CO,H prepared from the d-chloro-acid and hydrazine hydrate ihas [ug - 157.8' in 2.7% solution in N/1-hydrochloric acid ; the d-acid prepared from the Z-chloro-acid has [a]? + 158*0°. The rotation is nearly the same as that of the analogous amino-acid ( & 157.9') and of the hydroxy-acid (mandelic acid + 157"). d- and I-Hydrazinophenylacetic acids crystallise from water in silvery leaflets m. p. 183-184" (racemic compound 188-189O). Condensation with benzaldehyde yields active benxylidene compounds crystallising from dilute alcohol in slender needles m. p. 136-13S0 whilst the racemic compound has m. .p. 150'. The rotatory power is [a]?+ 166.5' in acetone 2.5% solution.It has not been found possible to-resolve the racemic compounds. C. H. D. Reduction of Aromatic Aldazines. THEODOR CURTIUS ( J . pr. Chem. 1912 85 [ii] 137-188).-A continuation of previous work (this vol. i 137). [With FRITZ MAYER.]-~ 4-DirnethyIbe~~zyl~dra~~ne? C,H3Me,*CH,*NH*NH2 is obtained as a colourless viscid liquid b. p. 136-137"/13 mm. by distilling the monohydrochloride (Abstr. 1900 i 610) with calcium oxide under diminished pressure. It is very unstable giving off nitrogen when kept and is much less basic than the lower homologues previously described (Abstr. 1901 i 573) ; its dihydrochloride m. p. 164O loses hydrogen chloride very readily and is almost completely resolved into the monohydrochloride by crystallisation from alcohol.The suZphte microscopic crystals m. p. 1 6 3 O oxaZate m. p. 192q and pitwate lustrous yellow needles m. p. 148O are described.i. 308 ABSTRACTS OF CHEMICAL PAPERS. On exposure to air it is oxidised to 2 4-dimethylbenzaldehyde- 2 4-dimethylbenzylhydrazone m. p. 78O (Abstr. 1900 i 610) ; the oxidation may also be effected by heating the hydrochloride with mercuric oxide and alcoholic sodium hydroxide. When heated with dilute hydrochloric acid it yields 2 4-dimethylbenzyl chloride C,H,Me,*CH,Cl a colourless viscid liquid b. p. 103-104°/1 9 mm. having a pleasant aromatic odour. The dibemoyl derivative C,H,Me,*CH,*N,H Bz crystallises in short colourless columns m. p. 169-170' j the diacetyl derivative C,3H,80,Np forms colourless leaflets m.p. 129'. 2 4-Dimethylbenzylhydraxine hydrochloride reacts with potassium cyanate in aqueous solution yields 2 4-dinaetlzylbernz~le~icarbanide C,H,Me,*CH,*N(NH2)*CO*NH2 columnar crystals m. p. 1 6 2 O and with phenylthiocarbimide and alcoholic potassium hydroxide yielding phenyl-2 4-dimethyEbenzyZthiosernicnrbasi~e C,H,Me,*CH,*N(NH,)-CSoNHPh which crystallises in short colourless columns m. p. 1 3 8 ~ 5 ~ . a-2 4-0imethyZbenzyll~ydrasonopropionic acid is obtained as a yellow oil by the interaction of the hydrochloride sodium acetate and pyruvic acid in aqueous solution. a-NitTOSO-a-2 4-dimethylbensyZhydra/draczir2e C,H,Me,=CH,*N(NO)*NH prepared from the hydrochloride and sodium nitrite crystallises in colourless leaflets or needles m. p. 6 0 . 5 O ; it reacts with 2 4-dimethyl- benzaldehyde yielding 3 4-dimethylbenzaldehyde-2 4-dimethylbenzyl- nitrosohydrazone (Zoc.cit.) and when heated a t 80° with 10% sulphuric acid is converted into 2 4-dimethyZbens~Zasoirnide C,H3Me,*CH,*N,. This forms a colourless liquid b. p. 114'/15 mm. and is stable towards alkalis ; it is hydrolysed by 20% sulphuric acid to hydrazoic acid and 2 4-dimethylbenzyl alcohol small quantities of ammonia 2 4- dimethylbenzaldehyde 2 4-dimethylbenzylamine and m-4-xylidine being produced simultaneously. When heated with etbpl acetoacetate 2 4-dimothylbenzylhydrazine yields ethyl p-2 ~-dzmethy~ban~y~aminocrotonate C,H,Me,* CH,*NH *CMe:CH* CO,Et colourless leaflets m. p. 85O together with an oil consisting probably of ethyl Paminocrotonate.The formation of these two substances is considered to be due to the reduction of the hydraeine base by ethyl acetoacetate to ammonia and 2 4-dimethylbenzylamine which then react with the ester to form ethyl /3-amiuocrotonate and ethyl p-2 4-dimethylbenzylaminocrotonate respectively. . 3- Phenyl- 1 -&-dikuth ylbenx yl- 5-2 yraxoZ&e V"2 cPh=K * C o > ~ ~ ~ ~ 2 0 ~ ~ ~ e prepared by heating the hydrazine base with ethyl benzoylacetate crystallises in colourless needles 113. p. 1 6 2 O dissolves in both acids and alkalis and combines with p-toluenediazonium sulphate to form a scarlet-red aso-dye ; its solution in aqueous ammonia gives sparingly soluble crybtalline precipitates with nickel cobalt copper and silver salts. 4-Oxirnino-3-phenyZ-1 -op - dimethylbenxyl-5 - pyrazolone C,,H,,O,N obtained by the action of sodium nitrite on the prcceding compound inORGANIC CHENISTRY.i. 309 acetic aci i solution crystallises in slender red needles m. p. 128" (decomp.). On treatment with silver nitrate i t forms a brownish- yellow silver salt which becomes green when warmed with glacial acetic acid nd then has the composition Cl8Hl,O3N3Ag. The latter com- pound decomposes at 236" and is probably the szlver salt of 4-nitro- 3-phenyl- 1 -op-dimeth yl benzyl-5-pyraxo Zone. 3-Phenyl-I -op-dimeth y lbenxy I- 2-ntetlhyl-5 -pymcxolone prepared from methyl iodide and the above-mentioned phenyldimethylb enzyl- pyrazolone is a brown oil. 3- Phenyl- I -op-dimet?Ayl benxyl-%mst?byZ-6-p yriclaninone CH,<gz::>N* CH,*C,H,Me is obtained by the interaction of dimethylbenzylhydrazine hydro- chloride sodium acetate and hvulic acid in aqueous solution; it has m.p. 79.5". [With HARTWIG FRANZEN.1-aa-Di-2 4 5-trirnetl~ylbenzyLIydrazine NH2*N(CH2*C6H,Me3)?l prepared from the hydrochloride (Abstr. 1901 i 293) and sodium hydroxide in aqueous alcoholic solution crystallises in white needles m. p. 75" and forms a sdphate needles m. p 151'; nitrate leaflets or needles m. p. 118' (decornp.) and platznichloride m. p. 95" (decomp.). It reacts with acetone yielding acetonedi-2 4 ; 5- trimetlujlbenxy lhydraxone CMe,:N*N(CH,*C,H,Me,) crystallising in small needles m. p. 1 3 2 O and with isobutaldebyde t o form isobutalde?~ydedi-2 4 5-t~imethylbenzyZhydraxone CS4H34N2 m. p. 112". When heated with acetic anhydride it yields a diacetyl derivative C24H3,0,N m.p. 126" ; the monobenxoyl derivative CZ7H,,ON has m. p. 129". NH,*CO*NH*N(CH2*C6H~~3;\4e,) prepared from the hydrochloride and potassium cyttnate in aqueous solution crystallises in needles or leaflets m. p. 173". 02-2 4 5-trimethylbeiaxylsemicctr6axide aa-Di-2 4 5-trimethylbenzylhydrazine forms an ethiodide c22H33N21C white needles m. p. 160° and is oxidised by mercuric oxide in chloro- form solution to di-2 4 5-triniet?~yEbenzlyItetraxone N(CH,*C,K2Me,),*~:N*N~CH2*C6H2Me3) which forms white needles or leaflets. [With REINHOLD KORTE.1-p - Cuminaldazine prepared from cuminaldehyde and hydrazine sulphate has m. p. 111" (compare Gattermann Abstr. 1906 i 592). On reduction with sodium amalgam in alcoholic solution it yields p cumi72aZdehyde-p-cumilzyl- hydi*axone C,H,PrP*CH:N*NH*CH,*C,H4Prfi which crystallises in small lustrous strongly refractive yellowish-green columns of a rhombic habit m.p. 75" (decomp.). The hydrazone is unstable becoming oily when kept. It forms a benxoyl derivative C,TH,,ON m. p. 78" and a nitroso-compound C613[,PrP*CB N (NO)*CH C6H4Prfi crystallising in light yellow felted needles m. p. 59'. When heated in alcoholic solution the nitroso-compound is converted into cuminaldazine. VOL. CII. i. Yi 310 ABSTRACTS OF CHEMICAL PAPERS. S-Di-p-curni~~lhydraxi~ N,H,(C,H,Pr~) obtained by the pro- longed reduction of cuminaldazine with sodium amalgam and alcohol forms a white wax-like mass which rapidly decomposes ; the hydro- chZoride crystallises in hexagonal plate& m.p. 217' (decomp.) the diacetyl derivative C24H3202N2 in large rhombic columns m. p. 719 The diniotww-derivative N2(NO),(C6H,Pr9 forms small tufts of yellow needles m. p. 5 9 O and when heated in alcoholic solution yields the above-mentioned p-cuminaldehydenitroso-p-isopropylbenzyl- hydrazone together with cuminaldazine and di-pcumimylidene- di- p-cumi~yldihydrotetraxone. N,(CH,.C,H4PrSb2{N:CH.CsH,PrS) m. p 194". The formation of the latter compound is considered to be due to the intermediate formation of p-cuminaldehyde-p-cuminyb hydrazone which is then oxidised by the nitrous acid produced by the hydrolysis of the corresponding nitrosohydrazone but all attempts to prepare the tetrazone by oxidising p-ciiminyl- hydrazone with mercuric oxide in alcoholicor benzene solution proved un- successful the sole product of the oxidation consisting of cuminaldazine.p - CuuminyZhydraxine C,H,PrP:CH,*NH*NH 2 obtained in the form of its hydrochlode (slender needles m. p. 199O with previous sintering at 143') by hydrolysing p-cuminaldehyde - p - cuminyl- hydrazone with dilute hydrochloric acid has m. p. 46'; i t is very unstable and rapidly loses nitrogen a t the ordinary temperature. The nitroso-compound C6H4PrP*CH2*N(NO)*N H forms very slender felted needles m. p. 63O and when heated with 10% sulphuric acid is converted into p-cuminylnxoimide C6H,Prfi*CH2*N a pale yellow oil b. p. 11 8'/23 mm. which is stable towards alkalis but is decomposed by 40% sulphuric acid with the evolution of nitrogen ; hydrazoic acid is not produced.[With BERMANN W~w~a].-m-Chlorobenzaldazine m. p. 1 41°(compare Curtius and Melsbach Abstr. 1910 i 508) is reduced by zinc dust and glacial acetic acid in alcoholic solution to di-m-chlorobenzylamine. This crystallises from alcohol in small needles m. p. 112' and is identical with Berlin's '' P-gechlortes Bibenzylamin " (Annalen 1869 151 141). The following salts of the amine are described the hydro- chloride m. p. 227' ; nitrate m. p. 203' ; platinichloride brown needles m. p. 222O (decomp,) and nitrite lustrous white needles m. p. 133'. Di-m-ch~orobe.nxyl~t~t~o~oam~~e NOON( CH2*C6H,Cl) prepared by boiling an alcoholic solution of the nitrite forms clusters of yellowish- white needles m. p. 53O and is reduced by zinc and acetic acid in alcoholic solution to di-m-chlorobenzylamine and aa-di-m-chlorobenxyyl- hydrazine NH2-N(CH,*C6H4C1) which reacts with benzaldehyde yielding benzaldeh y de - d i- m-chloro benx y lh ydraxone CHPh:N*N( CH,*C,H4C1)2.This crystallises in small yellow needles m. p. 66' and is hydrolysed by hydrochloric acid to benzaldehyde and au-di-m-chZoroben~yZ~ydrazine hydrochloride white leaflets m. p. 200'. On treatment with sodium nitrite the preceding hydrochloride yields di-na-chlorobenzylamine nitrite. s-Di-m-chlorobenxylhydrazine N,H,(CH,*C,H4Cl)2 prepared by reducing m-chlorobenzaldazine with sodium amalgam and alcohol,ORGANIC CHEMISTRY. i. 311 crystallises in small white needles m. p. 43"; the hydrochloride yellowish-white needles m. p. 19l0 the dibenzoyl derivative m.p. 88O and the diacetyl derivative m. p. 73" are described. The yellow nitroso-derivative N,( NO),(CH,* C,H,Cl) m. p. 48O when heated in alcoholic solution is converted into m-chlorobenxaldehydenitroeo-m- chlorobenx y2h ydraxone C,H,Cl*CH N*N( NO) CK2*C,H,C1 which forms yellow needles m. p. 98" and is hydrolysed by hydrochloric acid to m-cl~2ol.obenxylhydrGGxirte hydrochloride C,H,Cl*NH*NH2,HCl colourless needles m. p. 134". F. B. iV-Aminonaphthalimide and its Derivatives. ADRIANO OSTROGOVICH and M. MIHAILESCU (Gaxxetta 19 11 41 ii 757-807). -Ey the action of hydrazine sulphate on naphthalic anhydride the authors have obtained N-aminonaphthalimide for which the annexed symmetrical formula is /-\-Go to be adopted in view of the reactions of the \-/ \N*NH substance described below.The same sub- / \-GO/ stance is obtained when naphthalimide or even \-/ naphthalic acid is taken instead of naphthalic anhydride. N-ArninonaphthaZimide is obtained by treating a boiling solution of naphthalic anhydride in glacial acetic acid with a boiling aqueous solution of hydrazine sulphate and sodium acetate. Ebullition is continued for a few minutes and on cooling the imide C,,H,O,N is deposited in long lemon-yellow needles m. p. 262' after recrystallisa- tion. The same substance is obtained by heating hydrazine sulphate and sodium acetate with a solution of naphthalimide in aqueous glacial acetic acid for some hours in a sealed tube at 200-220'. The imide can also be prepared by boiling hydrazine sulphate (or better hydro- chloride) with a solution of naphthalic acid in aqueous potassium hydroxide N-Aminonaphthalimide is a stable substance which sub- limes unchanged and is not attacked by boiling concentrated acids or alkalis.It dissolves in boiling concentrated alkalis however and is reprecipitated by carbon dioxide but the solution is not to be ascribed to the production of a metallic derivative. The subhate is obtained in tabular colourless crystals by adding concentrated sulphuric acid to a solution of the base in glacial acetic acid; it is stable only in the presence of sulphuric acid of sufficient concentration. The hydrochloride forms small colourless needles and is immediahely hydrolysed by traces of moisture. is an orauge-yellow crystalline powder. forms orange-yellow needles m.p. 1929 When treated with sodium nitrite in the presence of glacial acetic acid N-aminonaphthalimide yields naphthalimide identical with that of Jaubert (Abstr. 1895 i 239) and nitrous oxide is evolved. With sodium hypobromite N-aminonaphthalimide yields naphthalimide according to the equation 2C,,H,02N + NaOBr = NaBr + H,O + N + 2C,,H70,N. N-Aminonaphthalimide yields acgl derivatives for the convenient naming of which the author proposes the term naphthalimyl to denote The platinichloride (C,2H,O,N )2,H2PtC4-9 The picrute C12HS02N2*C6H307"3~ VOL. c11. i. 2i 312 ABSTRACTS OF CHEMICAL PAPERS. the group Cl,H,<CO>N-. CO For these derivatives the two tautomeric forms R*NH*COoR and R*N:C(OH)*R' are possible but the enolic formula is excluded because the substances give no coloration with ferric chloride.~ormyl-N-aminoizap~thalimide C12H602:N*NH*CH0 is obtained by heating N-aminonaphthalimide with formamide at 1 40' for about an hour; it forms almost colourless prismatic crystals m. p. 245-246". It is a very stable substance which dissolves unchanged in cold strong acids or alkalis and is hydrolysed only when these solutions are boiled. Acetyl-N-urninonaphthcdimide Cl,H,02N2H~Ac obtained by boiling N-aminonaphthalimide with an excess of acetic anhydride crystallises in colourless needles m. p. 260-261' ; in stability it resembles the formyl derivative. Benzoyl- N-aminonaphthalimide C12H,0,N,HBz (from benzoic anhydride) forms colourless needles which begin to soften at 280' and melt at 290-291" and is also very stable towards acids and alkalis. N- Aminonaphthalimide reacts with the anhydrides of dibasic acids giving in the case of phthalic and naphthalic anhydrides the corre- sponding imide one molecule of water being eliminated ; succinic maleic and citraconic anhydrides yield amic acids from which the imides may be obtained by dehydration.N - ~ a ~ ~ t ~ a Z i r n i ~ o s u c c i n c ~ ~ n i c acid (termed N-~ap~thalimylsuccinamic acid by the author) C,2H602:N*NH-CO*CH,*CH2-C0,K obtained by the interaction of N-aminonaphthalimide and succinic anhydride either in the warm or at the ordinary temperature forms acicular crystals m. p. 213" (with evolution of gas presumably steam). When it is boiled with glacial acetic acid or heated a t 180' in a current of dry air N-nap~thalimidosuccirLimide Cl,H,O2:N*N:C,H,O is produced; it is a white crystalline powder which begins to ball together towards ZSO' and melts at 272-273'.This imido may be reconverted into the acid by dissolving it in dilute potassium hydroxide and adding a slight excess of dilute acetic acid or hydrochloric acid. N-Naphthalimidonzuleinamicacid C,,H,O,:N*NH*CO *CH:CH*CO,H is a white microcrystalline powder m. p. 205" (decomp.). It is probably the cis-form because it does not absorb bromine and it does yield an imide. The ammorniunz salt and the silvev salt C,,H,?,N,Ag were prepared. N-L~aphthalimidomal~~~i~ide C,,H,O,:N*N .C,H202 is obtained with some difficulty; it is necessary to boil the acld for some minutes with a large excess of ncetyl chloride. It forms minute acicular colourless crystals m.p. 118-120°; if the heating is con- tinued it resolidifies at 150" and melts again at The authors suppose that the treatment CO with acetyl chloride yields the unsymmetrical imide (annexed formula) which when heated above its melting point is transformed into the symmetrical imide ; in one preparation this isomeride was obtained direct crystallising in small colourless needles m. p. 240'. N-Naphthalimidomaleinimide gives Piutti's reaction (with sodium methoxide or ethoxide) for substituted unsaturated imidea. vH=TH 215". C12H602:N*N :C \/ '0ORGANIC CHEMISTRY. i. 313 ~-~aphthc6~~m~doc~traconam~c acid C12H6O2 N.NH*C5HbO5 forms colourless prismatic crystals. Like the corresponding maleinamic acid it dissolves in alkalis and is reprecipitated by dilute hydrochloric acid or sulphuric acid but not by acetic acid.The ammonium and silver salts were prepared. N-I~a~htAalimidocit~~aconimide C,,H,O, N ON C5H402 is obtained by heating the acid f o r some time a t 140° or by boiling i t with glacial acetic acid. On heating it begins to soften at 250" and melts at 254-255'. Ths imide can also be obtained by boiling N-aminonaphthalimide with an excess of citzaconic anhydride. It gives Piutti's reaction. N-N~6phthalimidophthalimide Cl2HGO,:N*N3C8H4O2 is obtained by the interaction of N-aminonaphthalimide and phthalic anhydride in presence of glacial acetic acid or chloroform in the cold. It crgstal- lises in colourless scales m. p. about 320'. It dissolves readily in alkali hydroxides and is reprecipitated by carbon dioxide.N-Nccphthalimidonaphthcclimide C,,H,O, N*N:C,,F,O is prepared by heating together equimolecular quantities of N-aminonapht tialimide and naphthalic anhydride a t 240-260'. After cooling the reaction product is dissolved in concentrated sulphuric acid and the solution poured into an excess of water. It is a white crystalline powder m. p. about 330'. It dissolves in alkali hydroxides and is reprecipi- tated by casbon dioxide. Neither this nor the preceding irnide is attacked by hydrochloric acid ; concentrated sulphuric acid hy drol yses them in the warm yielding N-arninonaphthalimide. Aldehydes react with N-aminonaphthalimide giving in general the Schiff's bases resulting from the elimination of the elements of water. I n the case of the aromatic aldehydes containing a p-hydroxy-group (p-hydroxy benzaldehyde protocatechualdehy de and vanillin) an inter- mediate additive product is formed which can then be dehydrated.When the p-hydroxy-group is substituted however (as in ani-aldehyde veratrsldehyde and piperonaldehyde) the condensation product is obtained direct. It was not possible t o isolate a formaldehyde derivative. Ethy Zidene-N-clnzil-Lona~T~t~~aZ~m~d~ C12HS02 N* N C €€Rile is obtained on mixing acetaldehyde with N-aminonaphthalimide ; i t fornis sniall colourless needles m. p. 172' and is readily hydrolysed. Benxylidene-N-a~zilzoncc~hthosli~~~de C1,H,O, N*N :CHPh (o b tained in presence of acetic acid or on warming with an excess of benz- aldehyde) crystallises in colourless needles m.p. 206-207'. Cinnamyliclene-N-arninonaphthccZimide Cl,H,O, N-N CH. CHI CHPb prepared in the same manner as the preceding derivative forms small colourless needles m. p. 195-196'. O- Hydroxpbenx ylidene-N-ccmipzonaphthu Zirnide Cl,H,0,:N*N:CH*C6H4*~H crystallises in thin colourless needles m. p . 230-231O. When a mixture of N-aminonaphthalimide and p-hydroxybenz aldehyde is kept in the presence of glacial acetic acid t.he additive product C12H,G2N2*C7H60 is obtained in the form of thin colourless ueedles. If it is boiled with glacial acetic acid p-hydroxybenzylidem- N-aminonccphtlTlalimids Ci2H602:N~~:CH~C,H,~OH is obtained ; it s 2i. 314 ABSTRACTS OF CHEMICAL PAPERS. crystallises in slightly yellow prisms which begin to soften at 270° and melt at 283-281' (decornp.).C ,H602:N *N C,H,O crystallises in colourless needles which begin to ball together a t 21OC and melt at 216-2217'. When resorcilaldehyde reacts with ,!I-aminonaphthalimide a mixture of the additive product and the irnide is formed which on boiling with glacial acetic acid yields 2 4-dihyd~*oxybenxylidene-N-aminonaphthaZ- zmide C1,2H,0,:N*N:CH*C6H~(OH)2 which crystallises in slightly yellow prisms which become red about l8O0 and then almost black and melt a t 289-290' (with slow heating); when placed in a bath a t 2S5O the substance becomes reddish-purple balls together and melts a t 2SS-289' (decornp.). nT-Ami uonaphthalimide and protocatechualdehyde in presence of glacial acetic acid yield an additive product C121502 N-N :C7H603 a slightly yellow microcrystalline powder which on heating becomes brown at 260' and black at 280'.When it is boiled with glacial acetic acid 3 4-dihyd~~ox~benxylidene-~-amino~aaphthali~ide C,,H,O,:N*N:CH*C,H,(OH) is obtained ; it crystallises in small pale yellow prisms. N-Aminonaphthalimide and vanillin in presence of glacial acetic acid yield the additive product C,,H,O,:N*NH*CH(OH)*C,H,(OH)*OMe ; it crystallises i u tufts of yellow needles which soften and ball together about 220' and melt a t 226-227'. When i t is heated at 130-140' (or at 160') or boiled with glacial acetic acid it yields 4-hyd~oxy- 3-niethoxybenx ylidelne- N-c~minona~ht~aZimide C,,H60 :N* N CH*C,H,( OH)*OMe which crystallises in long colourless needles softens about 22S0 and melts at 231-232'.p- Met hoxybenxylidene-N-anainona~~t~aZi~ide 3 4- Dimethoxybenxylidene-N-aminonaphbhcLZimidc C1,H,O, N*N CH C,H,( OMe) is obtained by keeping an alcoholic solution of N-aminonaphthalimide and veratraldehyde for two days; it forms colourless needles m. p. 2 2 9-2 30'. Piparony 1 idene-N- aminonaphthalimide C,,H,O,:N~N:CH*C,H,:O,:CH obtained from piperonaldehyde in glacial acetic acid a t the ordinary temperature forms small colourless needles m. p. 256-257'. When N-aminonaphthalimide is boiled with an excess of p-benzo- q u inone in glacial acetic acid N-naphthlimido-p-benzoquinonernonoknine U,,~,O,:N*N:C,H,:O is obtained as a slightly brown microcrystalline precipitate. The compound is soluble in alkali hydroxides giving an orange or red coloration and is reprecipitated by dilute hydrochloric acid or carbon dioxide The substance dissolves in concentrated sulphuric acid giving a red solution with a violet tinge and is precipitated unaltered on addition of water.Condensation of 5(4)-Methylglyoxeline with Chloral. OTTO GERNGHOSS (Ber. 1912 45 509-526. Compare Abstr. 190% i 189).-The condensation of 4-methylgly oxaline with chloral is R. V. S.ORGANIC CHEMISTRY. i. 315 analogous to that with formaldehyde (Windaus Abstr. 1909 i 258) the chloral becoming attached to the ring in position 5 (or 4) namely CHGN-C*OH(OH)*CCl,. NH*gMe \ I and the hydrochloride of the corresponding acid contain an extremely labile chlorine atom. I n aqueous solution a t 0" the chlorine is precipitated completely by silver nitrate ; when the aqueous solution is evaporated the hydrochloride of t,he hydroxy-acid is formed qumtit.atively.This chlorine atom reacts with sodium methoxide with the formation of NHfMe N -C*CHCl*CO,Me The ester hydrochloride HCI,CH< NH*fiMe N -C*CH(OMe) C0,Me' the methoxy-compound HCI,CH< When the hydroxy-acid is warmed with dilute nitric k i d a mixture of two nitrates is obtained which are separated by boiling with 90% alcohol. The faintly basic nitrate of the a-ketonic acid is hydrolysed whereas the more basic nitrate of 4-methylglgoxaline-6- carboxylic acid remains in solution. forms a crystalline oxime When heated with miline carbon NH*iMe N -C* CO CO,H' The ketonic acid CH< with a characteristic sodium salt. formed. NH*1;7Mo N -C*CH:NPh' dioxide is eliminated and the base CH< When reduced with aluminium amalgam the hydroxy-acid is reformed.!5( 4)-Methylglyoxaline-4( 5)-carboxylic acid CH< NH*EMe is the N -0 COoH' main prodiict of the oxidation of methylglyoxalineglycollic kcid with conceutrated nitric acid. The ethyl ester of this acid is obtained synthetically on boiling thioglyoxaline with 10% nitric acid. The hydrobromide of 5(4)-methylglyoxcclineglycoUic acid crystallises in short pointed needles m. p. 184-185O (decomp.). The hydro- bromide of the ester is obtained in lancet-shaped crystals pointed at both sides which sinter a t 160° m. p. 166O(decomp.); the hydrochloride of the acid crystallises in four-sided prisms m. p. 183- 1 8 4 O (decomp.); that of the ester forms rhombic and lancet-shaped platelets which sinter at 1 4 7 O m.p. 150.5". 5 (4)-MethyZgZyoxuline- 4( 5)-gZycollic acid crystal lise s in well-f ormed lristrous plates and stunted prisms which become brown a t 205" m. p. 215q to a reddish-brown foam. The nitrate crystallises in long six-sided plates decomp. 150" ; the pl.osphotungstate separates in microscopic needles; the sodium salt forws plates. The copper salt yields narrow four-sided rods of a pale blue colour. 5(4)-Methylglyoxmline-4( 5)-chloroacetic acid h ydrochloride,. prepared by the action of acetyl chloride on methyl methylglyoxal~neglgcollate hydrochloride and isolated first in the form of the methyl ester hydro- chloride which crystallises in crossed needles sintering a t 165O m. p. 16'7" (decomp.) crystallises in stout lustrous four-sided rhombic plates which becomes yellow at 190° m.p. 204' (decomp.).i. 316 ABSTRACTS OF CHEMICAL PAPERS. 5( 4)-Meth~ZgZyoxaZina-4(5)-gZyoxyZic acid crystallises in short rods and needles which become brown at 230' and begin to decompose at 240'. The sodium salt forms transparent four-sided plates with oblique ends ; the nitrate has pointed crystals which begin to decompose at 200° ; the hydrochloride crystallises in six-sided plates which become brown a t 235' and decornp. at 242'. The oximu crystallises in needles which sinter a t 225O m. p. 228" (decomp.); it forms a characteristic sodium salt crystallising in thin flat needles m. p. 210' (decomp. to a black mass). ~ethylglyoxalineglyoxylic acid when reduced by aluminium amalgam in alcoholic aqueous sodium hydroxide solution is converted into meth ylglyoxalineglycollic acid. The a d of 5( 4)-methyZgZyoxuZine-4(5)-aZdehyde crystallises in sharp needles m.p. 224' (decornp. to blackish-brown drops) 5(4)-Methylglyoxaline-4(5)-car~oxylic acid prepared by oxidation of methylglyoxalineglycollic acid with concentrated nitric acid crystallises in long bhin matted ueedles m. p. 223' (decomp.) and sublimes in flat needles when heated above 200'. At the melting point carbon dioxide is eliminated and methylglyoxaline formed. The ammonizcm salt is not stable; the potassium salt has decornp. 238'. The hydro- chloride crystallises in lustrous platelets m. p. 230' (decomp.) ; the phosphotungstate is obtained in small thin four-sided plates. The ethyl ester prepared by heating the potassium salt with ethyl alcohol and ethyliodide crystallises in long rods with oblique ends m.p. 205-206O and is identical with the product obtained synthetically from et h y 1 2 -t hiol-4 (5)-me th y lglyoxaline-5 (4) -carbox y lat e - NH-fjMe SH'C~N-C*CO.Et' 1 The sodium salt crystallises in long slender needles m. p. 240'; the lzitrate forms four-sided plates m. p. 167' (decomp.) ; the hydro- chloride has m. p. 183' (some decornp.). The ester is hydrolysed on prolonged boiling with concentrated hydrochloric acid to 5(4)-metbyl- glgoxaline-4(5)-carboxylic acid. E. B. A. Constitution of the Supposed Pyrazolinecarboxylio Acid CARL BULOW (Ber. 1912 45 528-533. Compare Bulow thisvol. i 134).-Polemical. A reply to Bucbner (this vol. i 213). Pyrazoline compounds which contain no carboxyl group distil without decom- position whereas Buchner's compound very readily loses nitrogen when heated; it is not believed possible for the carboxyl group to make this difference.Buchner's pyrazolidine from ethyl phenylpyrazolinedicarb- oxylate boils without decomposition whereas the known pyrazolidines are very unstable. These and other reasons are quoted against assigning a pyrazoline structure to Buchner's compound. E. F. A. Hydantoins X. Action of Potassium Thiocyanate on Pyrrolidonecarboxylic Acid. 2 - Thiohydantoin-4 - propionic Acid. TREAT B. JOHNSON and HERBERT H. GUEST (Amerr. Chsm. J. 2912 47 242-251).-Jobpson and Nicolet (this vol. i 53) haveORGANIC CHEMISTRY. i. 317 shown that by the action of potassium thiocyannte on either glycine or acetylglycine in presence of acetic anhydride the same 2-thio-3-acetyl- hydantoin is produced and Johnson (J.Biol. Chem. 1912 11 97) has found thatl under similar conditions alanine and acetylalanine both yield the same Z-thio-3-acetyl-4-rnethylhydantoin. A study has now been made of the behaviour of potassium thiocyanate towards pyrrolidonecarboxylic acid in presence of acetic anhydride and it has been found that the corresponding cyclic thiohydantoin is produced. The thiohydantoin of pywolidonecarboxylic acid CH,*Q H*CO m. p. 206' (decomp.) forms long prismatic crystals and is hydrolysed by dilute hydrochloric acid with production of 2-thiohydantoim4- propionic acid (thiohydantoin of glutamic acid) xE:>CH* CH,*CH,*CO,H m. p. 1 2 2 O which crystallises in rhombic plates.The latter thio- hydantoin is readily desulphurised by chloroacetic acid with formation of hydantoin-4-propionic acid (hydantoin of glutamic acid) CH,<CO-N-CpH >CH*CH,* CH,*CO,H SJH-CO CO*NH m. p. 1 6 5 O which crystallises in hexagonal tabular prisms ; this com- pound is also produced but in smaller yield by the action of chloro- acetic acid on pyrrolidonecarboxylic acid thiohydantoin. At tempts were made to synthesise 2-thiohydantoin-4-propionic acid by the action of potassium thiocyanate on glutamic acid dissolved in water alcohol or acetic anhydride but without success. E. G. Theory of the Indigo Vat. ARTHUR BINZ and KURT SCHADEL (Ber. 1912 45 586-597. Compare Abstr. 1911 i 497).-The authors summarise the results of previous work in support of the view that in the formation of the indigo-vat the indigotin is not directly reduced to indigo-white but first combines with one or two molecules of sodium hydroxide (or other alkali hydroxide) to form an additive compound (compare Abstr. 1906 i '749) from which oxygen is then removed by the reducing agent (for example zinc) employed in the preparation of the vat C16H1002N2 + NaOH = C,,H,,O,N,,NaOH C,BH,OO,N,,NaOH + Zn = C,,H,,O,N,Na + ZnO.If this interpretation is correct the velocity of vat formation should be increased by replacing the free indigotin by the above-mentioned additive compound and this is found to be the case. Zinc iron and magnesium react much more rapidly on the additive compound with sodium hydroxide than on indigotin in the presence of the same amount of free alkali.Bromoindigotin and dibromoiudigotin react with sodium ethoxide in alcoholic solution yielding the compounds C16H190zN2Br,NaOH and C,,H,O,N,Br,,NaOH which are decomposed by washing with alcohol more readily than the corresponding compound of indigotin. Thei. 318 ABSTRACTS OF CHEMICAL PAPERS. alkali derivatives of the tetrahalogenoindigotins on the other hand are very stable. With respect to the fixation of indigotin in the fibre the authors consider that the first stage consists in the chemical union of the fibre with the indigo-white and that this union remains intact during the subsequent oxidation. It is very improbable that a colloidal complex with the fibre is first produced since it is found that colloidal indigotin cannot be fixed on the fibre.F. B. Bromo- and Methoxy-derivatives of Indigo tin. PAUL FRIED- LANDEB S. BRUCKNER and G. DEUTSCH (Annalelz 1912 388 23-49). -Dibromo- and dimethoxy-indigotins containing the substituents in positions 4 4’ 5 5’ 7 7’ and 6 6‘ have been synthesised from the corresponding o-nitrobenzaldehydes or anthranilic acids with the object of ascertaining the influence of the substituente on the colonrs of the dyes. The colqurs of the first three dyes in solution or on the fibre do not markedly differ from that of indigotin itself ; 6 6’-di- chloro- 6 6’-dibromo- and 6 6’-dimethoxy-indigotin however exhibit a very different reddish-violet shade. 6-Bromo-2-nitrotolusne m. p. 38* obtained from 2-nitro-o-toluidine by the Gattermann method in the cold is reduced by tin stannous chloride and hydrochloric acid to 6-bromo-o-toZuidine a yellow oil the acetyl derivative m.p. 163O of which is oxidised to bromoacetyk- anthranilic acid NHAc*C,H,Br*CO,H m. p. 2 2 1 O by potassium per- manganate a t 80’in the presence of magnesium sulphate. This acid is converted by boiling sulphuric acid (1 1) into m-bromoaniline (acetyl derivative m. p. 84O) but when hydrolysed by 10% sodium hydroxide yields 6-bromoanthranilic acid m. p. 136’. The latter is boiled with an excess of chloroacetic acid in aqueous sodium carbonate and the resulting 3-bromopheny?glycine-2-carboxylic acid is converted in the usual manner into 4 ; 4’-dibromoindigotin which crystallises from chloroform in blue needles with a copper lustre exhibits pronounced dichroism in solution and yields a normal vat with alkaline hyposulphite.6 5’-l)ibromoindigotin has already been prepared by Baeyer (Bey. 1879 12 1315). It is obtained by the direct bromination of indigotin in anhydrous solvents and can also be produced from 5-bromo- anthranilic acid. 4-Bromophenylglycine-2 -cas.boxylic acid has m. p. 2 27-2 2 8 O (decomp.). 6 6’-Dibromoiudigotin a constituent of the antique purple dye obtained from Mwex brandaris (Abstr. 1909 ii 262) has been prepared by Sachs from p-bromo-o-nitrobenzaldehyde (Abstr. 1904 i 593). The authors prepare i t in larger quantity from the bromo- anthranilic acid (acetyl derivative m. p. 21 7’). 5-Bromophenylglycine- 2-cccrboxylic acid m. p. about 236O is a yellow crystalline powder and yields 6-bromoacetyZindoxyl uo.p. 11 8 * 5 O by boiling with acetic anhydride and sodium acetate. Attempts t o prepare 7 7’-dibromo- indigotin from the bromoanthranilic acid have been unsuccessful. It has been obtained in very small yield by an application of Bauer’s isatin synthesis (Abstr. 1907 i 603). o-Bromo-oxamidide m. p. 205q isORGANIC CHEMISTRY. i. 319 boiled with phosphorus pentachloride in toluene and the resulting di-o- bromophen yloxaliminochloride m. p. l l O o yellow $321 :N*C,H,Br CCI:N*C,HABr' needles is heated at 100' with 100% su1;h;ric acid whereby 7-bromo- iaatin C,H,Br<CO)CO m. p. 192" reddish-yellow needles is obtained. 7-Bromoisatin responds to the indophenin test and by warm- ing in benzene with phosphorus pentachloride acd subsequently treat- ing the solution with hydrogen sulphide yields 7 7'-dibromoindigotin which crystallises in needles with a copper lustre. Indoxyl condenses with 5 7-dibromoisatin chloride in benzene t o form 5 7-dibromoindigotin blue needles and with 5 7-dibromoisatin in acetic acid t o yield red needles of dibromoindirubin C,H,Br,/ NH Co\C:C<gg>C,H,.2-Anaino-6-metl~oxybenxonitrile m. p. 141" colourless needles obtained by the reduction of 2-nitro-6-methoxybenzonitrile by tin stannous chloride and hydrochloric acid forms an acetyl derivative In. p. 176" and is not hydrolysed by acids or alkalis dilute or concentrated hot or cold but is slowly attacked by very concentrated sodium hydroxide a t 1 60-170° yielding 2-amino-6-methoxybenzamide m.p. 150". This substance unlike the nitrile reacts readily with chloroacetic acid in boiling concentrated sodium carbonate yielding S-methoxyphenyl- glycine- 2-carboxyZamide NH,* CO* C,H,(OMe) *NH* CH,* CO,H m. p. 208' (decomp.) yellow crystals from which sodium hydroxide at 170-1 90° or boiling acetic anhydride and sodium acetate (and atmospheric oxygen) produce 4 4'-dimethoxyindigotin needles with a copper lustre. 5 5'-Dimethoxyindigotin blue needles wi tb a copper lustre is obtained from 2-nitro-5-methoxybenzaldehyde acetone and dilute sodium hydroxide in the usual manner. 2-Acetylamino-p-cresol and methyl sulphate in alkaline solution yield the methyl ether OMe*C6H3Me*NHAc m. p. 95' (the corresponding ethyl ether has m. p. 126'). These ethers are oxidised to the corresponding acids by boiling aqueous potassium permanganate and magnesium sulphnte.4-Methoxymcetylanthranilic acid m. p. 199' (decomp.) and 4-ethoxyacetylanthranilic acid m. p. 182-183" yield by hydrolysis with dilute sulphuric acid (1 1) 4-methoxyanthmndic acid m. p. 166" (decomp.) (methyl ester m. p. 75') and 4ethoxyanthranilic acid m. p. 174" respectively. These acids react with chloroacetic acid iu boiling 10% sodium hydroxide the products yielding after acidifica- tion 5-methoxyphenyIgZycine-2-carboxylic acid CO,H*C,H,( OMe)*NH*CH,*CO,H m. p. 159-1 61' (decomp.) brown microscopic needles and 5-ethoxy- phenylglycine-2-carboxylic acid m. p. 166-167" red microscopic needles respectively from which the 6 6'-dialkyloxyindigotins are obtained in the usual manner. 7 7'-Dimethoxyindigotin needles with a copper lustre is prepared from the nitromethoxybenzaldebyde acetone and sodium hydroxide.c. s. NHi. 320 ABSTRACTS OF CHEMICAL PAPERS. Action of Thioacetic Acid on Cyanoguanidine (Synthesis of Thioliminomethyltriazine). ADRIANO OSTROGOVICH ( A t t i R. Accad Lincei 1912 [v] 21 i 213-217. Compare Abstr. 1911 i 1036).- When cyanoguanidine is heated with an ethereal solution of thio- acetic acid for about two hours until the evolution of hydrogen sulphide ceases 6-thioZ-2-irnino-4-methyZ- 1 3 5 -tviaxine C4H,N,S is precipitated. A further portion can be obtained from the soluti,on so that the total yield is 93%. The pure substance forms small colourless crystals which decompose without melting ; for it the formula N<C(sH).NH>C:NH or the tautomeric thionic form is suggested.The compound is soluble in acids in alkali hydroxides and in ammonia. CMe==N R. V. S. Researches on Purines. V. 2-Oxy- l-methylpurine. CARL 0. JOHNS (J. BioZ. Chern. 1912 11 73-79).-Five of the six isomerides of 2-oxymethylpurine have been already described. The sixth 2-oxy- l-methylpurine can be obtained from 5 6-diamino-3-methyldihydro- 2-pyrimidone. The potassium salt of nitrocytosine (5-nitro-6-amino- dihydro-2-pyrimidone) is methylated by methyl iodide and the product is found to be 5-nitro-6-amino-3-rnethyZdihydro-2-pyrimidone crystallising in slender prisms m. p. 274' (decomp.). When this is reduced with freshly precipit,ated ferrous hydroxide it gives a good yield of 5 6-diarnino-3-methyZdihyd~o-2-pyrir~zidone which in turn reacts with formic acid to give a fownyZ derivative the potassium salt of which when heated lost water and so formed the potassium salt of 2-oxy- 1 -methylpurine.This purine crystallises in flat prisms containing 2H,O; decomp. 280'. They effloresce in the air and become anhydrous over sulphuric acid. An aqueous solution gives sparingly soluble precipitates with platinum chloride and picric acid. The picrccte has m. p. 214' (decomp.). W. D. H. A Purine-Hexose Compound. JOHN A. MANDEL and EDWARD K. DUNHAM (J. BioZ. Chem. 1912 11 85-86).-A preliminary note on a compound of adenine and hexose separated from a n extract of yeast. It forms sheaves of delicate acicular crystals and melts at 206'. Analysis shows close agreement with the figures calculated from the formula C,,H1,O,N,.A phenylosazone obtained from it yielded 15.3% nitrogen. The hexose has not yet boen identified. W. D. H. Existence of Complexes between Purine Substances and Sodium Salicylate. GIOVANNI PELLINI and MARIO AMADORI ( A tti R. Accad. Lirzcei. 1912 [v] 21 i 290-295. Compare Abstr. 1910 i 525).-By measurements of the depression of the freezing point of aqueous solutions of sodium salicylate to which caffeine and theo- bromine respectively are added the authors establish t h e existence of complexes similar to those formerly described. The tendency to their formation is more inarked than in the case of sodium benzoate and it is greater for caffeine than for theobromine. Measurements of the solubility in water at 25' and at 40' ofORGANIC CHEMISTRY. i.321 pharmaceutical L‘ sodium salicyla.te and caffeine ” show that the product is not a mixture as in tho case of “sodium benzoate and caffeirre,” but on this point further experiments are needed. R. V. 8. Xanthine Derivatives from Uric Acid. IV. Preparation of Xanthine and Hypoxanthine. ERNST E. SUNDWIR (Zeitsch. physiol. Chem. 1912 76 486-488. Compare Abstr. 1911 i 5S4).- Xanthine is formed t o the extent of 30-33% when uric acid is heated a t 2Q0° with oxalic acid in presence of much glycerol. Xanthine is converted into hypoxanthine by dissolving in excess of sodium hydroxide and shaking with chloroform at 60-70’ during two hours. E. F. A. Azoxy-compounds. ANGELO ANGELI and BRUNO VALORI (Atti R. Accad. Lincei 1912 [v] 21 i 155-165.Compare Angeli and Alessandri Abstr. 1911 i 1045).-1n the present paper two more pairs of isomeric nzoxy-compounds are described namely a- and P-p-bromoazoxybenzene and a- and ~-4-bromo-4’-nitroazoxybenzene. When azoxybenzene is treated with bromine without a solvent a-p-bromoazoxybenzene C12H90N2Br is obtained ; it forms straw- yellow crystals m. p. 73’ (previously given as 75’). Oxidation of p-bromoazobenzene with hydrogen peroxide in glacial acetic acid solution the mixture being kept at 40-50’ for some dsys yields a-p-bromoazoxybenzene m. p. 7 3 O identical with that above described and in addition P-p-bromoccxoxybenxene which forms yellow crystals m. p. 92’. It is not possible to convert the twop-bromoazoxybenzenes into each other directly and therefore they do not resemble the stereoisomeric azoxy-compounds of Reissert (Abstr.1909 i 435) but both the isomerides now described yield p-bromoazobenzene again on reduction with aluminium amalgam. a-p-Bronioazoxy benzene is not acted on by bromine but P-p-bromoazoxybenzene when treated with bromine yields 4 4’-dibromoazoxybenzene. The constitutions of the two substances may be derived from this fact because it is probable (in view of the formation of the bromo-derivatives about t o be described and of others already known) that a bromine atom attaches itself in the para-position in the nucleus in every NPh group The authors therefore ascribe to a-p-bromoazoxybenzene the formula whilst P-p-bromoazoxybenzene is NPh:NO*C,H4Br. When bromine is added to p-nitroazobenzene in the presence of traces of iodine 4-bromo-li‘-~zitroazobenzene C12H80,N,Br is obtained ; i t forms dark red crystals m. p.203’. The bromination cannot be effected in glacial acetic acid even in sunlight. The action of‘ nibric acid (D 1 -45) on p-bromoazobenzene yields the same 4-bromo-4’- nitroazobenzene. When a-p-bromorzzoxybenzene is greatly warmed with nitric acid (U 1-45) a compound CI2H8O3N3Br m. p. 99O is obtained; in this substance the bromine and the nitro-group are probably attached t,o the same benzene nucleus. Treatment of a-p-bromoazoxybenzene with concentrated sulphuric acid for an hour on the water-bath leads to the production of p-bromoazobenzene and 4-bromo-4’-hydroxyazobenzene. Ph*NO:N*C,H,Br,i. 322 ABSTRACTS OF CHEMICAL PAPERS.The addition of bromine to p-bromoaxobenzene yields 4 4’-dibromo- azobenxene CI2H8N2Br2 which forms dark orange-yellow cryst 1 s m. p. 204O. If this substance is kept at 100’ for twelve hours with hydrogeu peroxide 4 4’-dibromoazoxybenzene is obtained identical with t h a t prepared by brominating P-p-bromoazoxybenzene. a-4-Bromo-4‘-nitroazoxybenxene C,H,Br*NO:N*CBH,*N02 m. p. 194’ is obtained by keeping 4-bromo-4‘-nitroazobenzene in glacial acetic acid solutiou with hydrogen ,peroxide a t 100’ for a day. P-4-B~orno- 4‘-nitroaaox y benzene C,H Br N N 0 C6H4 NO is formed by treating P-p-nitroazoxybenzene NPh:NO*C,H,*NO (compare Angelo and Alessandri Zoc. cit.) with bromine in the presence of iodine in the warm; it crystallises in minute pale yellow prisms m.p. 203’. Nitric acid (D 1-45) reacts with P-p-bromoazoxybenzene yielding a-4-brom0-4’-nitroazoxybenzene identical with that above described. R. V. S. Scission of Aao-dyes by Halogens. MAXIMILIAN P. SCHMIDT (J. pr. Chem. 19 13 [ii] 85 235 -240).-p-Hydroxyazobenzene is converted by the action of chlorine or hypochlorous acid in aqueous solution into benzenediazonium chloride and 2 4 6-trichlorophenol and by bromine into benzenediazonium bromide and 2 4 6-tri- bromophenol. Sodium diazobenzenesulphonate when subjected to the same treat- ment also yields benzenediazonium salts (compare Fischer Abstr. 1878 302) and a similar decomposition has been observed in the case of a large number of azo-dyes. With respect to the mechanism of the reaction it is imagined that an additive compound with the halogen is first produced which then undergoes decomposition as shown in the following scheme R*N R*N*Cl R*N*Cl I1 -+ 1 -+ ],:I + HO*R*Cl.OH*R*N OH*R’*N*Cl N F. B. Aromatic Substances Containing Multivalent Iodine. LUICII MASCARELLI and B. TOSCRI (Atti R. Accad. Lincei 1912 [v] 21 i 145-151. Compare Mascarelli and Cerasoli Abstr. 1910 i ‘725 ; Mascarelli Toschi and Zambonini ibid. 831).-Attempts to prepare six-membered rings containing iodine have not been successful. Only in one case namely from the tetrazo-compound from 2 2’-diamino- 4 4’-tetramethyldiaminodiphenylmethane was a small quantity of a yellow powder obtained which had m. p. 220-225’ and showed the properties of an iodoniurn base. In the present paper Bome erndo- bisazo-derivatives (compare Diwal Abstr.19 10 i 703 781) are described which were obtained during the course of the work. When 2 2‘-diamino-4 4’-dichlorodiphenylmethane is treated with nitrous acid the tetrazo-compound ie obtained. This reacts with potassium iodide yielding 4 4’-dichloro-2 2’-di-iododiphenylmethane and a substance C,,H,N,Cl which crystallises in golden-yellow scales decomposing at 260-265O. To it is assigned the constitutionORU A N IC C H EM1 S'l'K Y. i. 323 Y compound when treated with sulphuric acid yields a crystalline substance (not analysed) which decomposes a t 249-252". Its alcoholic solution gives an intense green coloratioii with ferric chloride and t o it the constitution of 4 4'-dichZoro-2-hydroxyendotcxodiphenylrne~hone OH*C,H,Cl*CH<~ 6H3C1 is ascribed.N2 4 4'- Diohloro-2 2'-di-iododiphenyZmethaize tetrachtoride ICI,*C,H3C1*CH,* CGH,C1'IC4 is obtained in yellow crystals m. p. about 102' (evolving chlorine) when chlorine is passed through a chloroform solution of 4 4'-di- chloro-2 2'-di-iododiphenylmethane. It is a very stable substance a.nd does not form iodoso- and iodoxy-derivatives when treated with the reagents which usually effect that change and it was also impossible to obtain the di-iodoxy-derivative by oxidation with chlorine or with Caro's acid. R. V. S. Azo -dyes from Substituted Pyrroles. HANS PISCHER and E. BARTHOLOMAUS (Zeitsch. physiol. Chem. 191 2 76 478-485).-In view of their importance for recognising and chai*acterising blood and bile pigments the azo-dyes from a number of substituted pyrroles have been prepared by interaction with diazobenzenesulphonic acid.Monoazo-compounds were obtained in all cases. The cornpound S03H*C,H4*N,*C,NHMe2-COMe from 2 4-dimethyl- 3-acetylpyrrole crystallises in long lustrous red needles. The compound C15H170,N,S from ethyl 2 5-dimethylpyrrole- 3- carboxylate crys tallises in long greenish-olive rhombic needles. The compound C,,H,?O,N,S from 2 5-dimethylpyrrole-3-carboxylic acid separates in yellowish-brown needles. The comnpound C12H1305N3S from 2 5-dimethylpyrrole is obtained in tiny microscopic orange needles. The corresponding dye from 2 4-dimethylpyrrole crystallises in yellowish-brown needles. Hemopyrrole picrate has m. p. 125" (corr.); it does not readily condense with diazobenzenesulphonic acid. The free hEemopyrrole couples very readily however forming orange-yellow needles of the compound C!,H170,N,S ; i t dissolves iu concentrated sulphuric acid with a greenish-yellow coloration and is totally different from the azo-dye obtaiued from 2 4-dimethyl-3-ethylpprrole.E. F. A. Losses in the Isolation of the Monoamino-acids [from Proteins] by the Ester Method. 11. EMIL ABDERHALDEN and ARTHUR W EIL (Zeitsch. physiol. Chern. 1912 '77 59-74. Compare Abstr. 1911 i 1049).-The pure amino-acids either singly or mixed were esterified distilled and hydrolysed the amount recovered and the losses at each stage of the operation being determined. I n this way the proportion recovered was from glycine 62.5% from d-alaninc 70% and dl-leucine 80%.From a mixture of all five amino-acids there was obtained 50% of the glycine 57% of the alanine 66% of the leucine 58% of the glutamic acid and 40% of the I-aspartic acid. d-Valine isi. 324 ABSTRACTS OF CHEMICAL PAPERS. recovered to the extent of 68% I-phenylalanine only to the extent of 54%. It is considered that if these losses by the isolation of the monoamino- acids are taken into account the proteins are almost entirely composed of the already known constituents. I n presence of protein the yields are still less. E. F. A. Introduction of Iodine into Protein Derivatives. KERMANN PAULY (Zeitsch. physiol. Chern. 191 2 ’76 391-392).-Basic nitrogeuous substances exposed to the action of excess of iodine form brown periodides in which the iodine is only loosely attached.Iodo- protein compounds must be colourless and retain their iodine after treatment for a short time with sulphurous acid. The iodotryptophan described by Neuberg (Abstr. 1907 i 955) is considered to be a periodide; it is not possible to introduce iodine into tryptophan or monobenzoyltryp tophan. E. F. A. Estimation of Amino-groups in the Oxyproteic Acids of Normal Urines. J~ZEF BROWINSKI and STEPHANE D~BROWSEI (Bull. Acad. Sci. Cracow 1911 A 587-595 ; Zeitsch. pluysiol. Chern. 1912 7’7 92-106).-Determinations have been made of the ammonia and amino-nitrogen in the oxyproteic acids both before and after hydrolysis using Sorensen’s method of titration with formaldehyde. Urochrome and ollooxyproteic acid before hydrolysis contain about 2.7% of ammonia nitrogen and 2*4% and 6.4% respectively of amino- nitrogen.ccntiOxyproteic and oxyproteic acids which are not pre- cipitated by basic lead acetate contain no ammonia but 11.2% and 38.8% respectively of amino-nitrogen. It is believed that the last two acids constitute the greater proportion of the oxyproteic acids of urine. Hydrolysis with boiling hydrochloric acid leads to the formation of melanins and secondary products ; hydrofluoric acid can be used to effect hydrolysis a t the temperature of a boiling water-bath and with it a much larger proportion of amino-acid nitrogen is obtained. Melanin is formed from urochrome when hydrolysis with hydrofluoric acid is prolonged but not from any other of the oxyproteic acids. This is taken to indicate that the oxyproteic acids are not to be regarded as the mother substmces of the urinary pigment.The proportions of ammonia and amino-nitrogen given by the four acids when decomposed with hydrofluoric acid for twenty-four hours are as follow^ urochrome NH 8-7% NH 26.4%; dlooxyproteic acid NH 4*2% NH 76*9% ccntioxyproteic acid NH 3.2% NH 33.9%; oxyproteic acid NIT3 8.3% NH 80.5%. Haensoglobin. EUGIEN LETSCHE (Zeitsch. physiol. Chem. 1912 76 243-257. Compare Abstr. 1910 i 599).-The absorption number ( A ) of hemoglobin solutions that is the ratio of concentra- tion (c) to the extinction coefficient (e) should be a constant independent of the apparatus used and the observer if the method is to be used t o measure the concentration of haemoglobin solutions. Measurements made t o test this indicate the value 2.081 x 10-3 for A in agreement with Hiifner’s original determinations but differing from the value E.F. A.ORGANIC CHEMISTRY. i. 325 1.87 x 10-3 determined by Butterfield and previously used by the writer (Abstr. 1910 i 599) whose values must be corrected accordingly. The amount of carbon monoxide fixed per gram of haemoglobin is 1-36 c.c. which is in excellent agreement with the value 1.34 determined by Hufner and by Butterfield E. F. A. The Behaviour of Carbon Monoxide Blood to Certain Pre- cipitating Agents. KURT GESTEWITZ (Zeitsch. exp. Path. Ther. 19 1 1 Reprint 15 pp.).-Vegetable agglutinins such as ricin and phasin precipitate from carbon monoxide blood the carboxyhamoglobin in the corpuscles ; zinc and copper salts precipitate it free from the corpuscles.The copper precipitate (produced by adding 1% copper sulptiate solu- tion) in normal blood is brown in colour in carbon monoxide blood red which is quite characteristic to the eye; no spectroscopic investigation is necessary. The colour difference with zinc salts is not so striking. The zinc carboxyhaemoglobin can be readily dried and then remains undecomposed for weeks. W. D. H. The Cleavage of Nucleic Acid by Organ Enzymes. ALFRED SCRITTENHELM and KARL WIENER (Zeitsch. physiol. Chem. 19 12 77 77-85).-The experiments confirm on the whole the results of Levene and Medigreceanu and relate to the enzymes concerned in nucleic acid cleavage in various tlissue extracts; the products of cleavage inhibit the activity of the enzymes concerned.W. D. H. Yeast Nucleic Acids. V. Structure of Pyrimidine Nucleosides. PA(EBUS A. LEVENE and FREDERICK B. LA FORGE (Ber. 1913 45 608-620. Comrare Levene and Jacobs Abstr. 1911 i 96,51O).-The pyrimidine complexes in nucleic acid are very resistant towards the hydrolytic action of dilute mineral acids. When distilled with hydrochloric acid (D 1.06) for thirty-six hours furfuraldehyde is liberated slowly corresponding in amount with equimolecular propor- tions of ribose and base in the complex. When hydrolysed by hydro bromic acid in presence of bromine cytidine is converted into 5-bromo- uracil and d-ribonic acid. Uridine or cytidine when treated with bromine in aqueous solution yields a solution which reduces Fehling's solution and forms a crystalline precipitate when heahed with phenyl- hydrazine ; this behaviour indicates that the double bond has remained intact.When uridine is evaporated with concentrated nitric acid an anhydride of two molecules of nitrouridinecarboxylic acid is obtained which is )readily converted into its ethyl or butyl esters and when hydrolysed gives nitrouracil. Alkyl derivatives of uridine or cytidine could not be obtained. Both compounds are fairly easily reduced to dihydro-compounds which are very easily hydrolysed by mineral acids giving ribose and dihgdro-derivatives of the bases. It is assumed that the glucoside formation between ribose and the base involves position 5 in the base and that the contiguity of this to the double bond conditions the resistance to hydrolysis. The preparation of uridine has been simplified by conversion of thei.326 ABSTRACTS OF CHEMICAL PAPERS. ribose into glucoside which prevents its precipitation together with the base with lead acetate or barium hydroxide. Cytidine is conveniently isolated as the sparingly soluble nitrate m. p. 197'. Thefree base crystalliees in long needles which sinter at 220' m. p. 230" (decomp.) [a] + 29.63". 5-Bvo~nouridine is very similar to uridine ; it has m. p. 181-184" [a]2 - 15 '4'. Hydvoxyuridifie (corresponding with 5- bromo-4-hydroxydihydro- uracil) has m. p. 222-223°; the phenylhydrazide forms long citron- yellow needles m. p. 209'. The anhydride of nitrouridinecarboxylic acid C1,H,,Ol7N crystallises in short thick prisms decomp. above 200' ; the szlwer salt is amorphous. The ethyl ester forms slender needles decomp.above 200' ; the n-butyl ester sinters at 1 8 5 O m. p. 190-192'. Dihydrouridine is a colourless syrup [a] + 39.1'. E. F. A. Free Amino-groups of the Simplest Proteins. ALBRECHT KOSSEL and ALEXANDER T. CAMERON (Zeitsch. physiol. Chem. 1912 76 457-463. Compare Kossel and Kennaway Abstr. 1911 i 667).- Nitroclupeine obtained by nitration of clupeine yields a nitroarginine on hydrolysis. This nitroarginine when treated with nitrous acid by van Sly ke's process yields nitrogen corresponding withEthe decomposition of one amino-group. Since the amino-groups of guanidine and nitro- guanidine are !not decomposed by this reagent the reactive amino- group can only be that of the ornithine residue and the arginine groups of clupeine are linked in the following manner C0.N H-CO-NH-CH-CO-NH..I I C,H,*NH*C(NH)*NH2 C!!,H,* NH*C (NH)*NH I n further support of t h i s formula it is shown that clupeine behaves similarly to guanidine when nitrated it has the same acid-fixing power as the guanidine-groups in the molecule and lastly unchanged clupeine gives no nitrogen by van Slyke's process. Cyprinine the protamine of carp sperm contains a t least 30.3% of its total nitrogen in the form of lysine ; 23.6% of the total nitrogen is set free by nitrous acid. I n sturine about 6.9% of the total nitrogen is liberated ; this roughly corresponds to the total amount of lysine present but this quantity is not enough to make up all the acid-fixing groups of sturin. E. F. A. Electrical Transport of Colloids. LEONOR MICHAELIS and HEIN- RICH DAVIDSODN (Zeitech.physiol. Chem Z 9 12,76,385-387. Compare Pekelharing and Ringer Abstr. 1911 i 1051).-A criticism of the arrangement adopted by Pekelharing and Ringer in measuring the electrical transport of pepsin. It is regarded as important that the middle and side vessels should have exactly the same hydrogen ion concentration. E. F. A. Compounds of Amino-acids and Ammonia. VII. PETER BERGELL and PAUL BOLL (Zeatsch. physiol. Chem. 1912 76 464-467). -To establish whether the a.symmetric hydrolysis of leucinauide wasORGANIC CHEMISTRY. i. 327 brought about by a special enzyme or by the usual protein- or peptide- splitting enzymes the effect of the addition of N-hydrochloric acid to the enzyme solution has been studied. The enzyme hydrolysing silk peptone was but little affected those digesting casein and fibrin were only partly destroyed but that acting on leucinamide was entirely killed unchanged optically inactive leucinamide being recovered.Accordingly the last change is attributed to a specific enzyme. E. F. A Comparative Hydrolysis of Sucrose by Various Acids in Presence of Invertaee. GABRIEL BERTRAND M. ROYENBLATT and (Mme.) M. ROSENBLATT (Bull. Xoc. chim. 1912 [iv] 11 176-186. Compare Abstr. 1898 ii 128; 1909 i 272 ;Sorensen Abstr. 1910 i 147; Euler and Ugglas Abstr. 1910 i 345 796; Michaelis and Davidsohn Abstr. 191 1 i 1051 1052).-Previous investigations beginning with those of Kjeldahlin 1881 have shown that the act,ivity of invertase and other enzymes is modified by the presence of acids or alkalis but the conclusions arrived at as to the quantities-of acids or alkalis that are most effective and as to the general laws governing these actions have been very variable. I n the present investigation account has been taken of the alkalinity of the yeast extract and of the sucrose solutions employed and disturbing influences due to ihese causes and to variation in the yeast and the sucrose employed have been avoided. The results are summarised and tabulated in the original. They show that the acids grouped according to their basicity arrange themselves for activity a t optimum concentrations taking hydrochloric acid as 100 in the same order as for their catalytic activity on sucrose. Among the monobasic acids trichloroacetic dichloroacetic and lactic acids are exceptional in their behaviour. The monobasic acids become more active as catalysts in presence of invertase and this is also true but to a less extent for dibasic acids whilst for tribasic acid the inverse holds. No explanation can be given at present OF the exceptional behaviour of the three acids referred to already or of the great increase in catalytic activity shown by aromatic sulphonic acids in presence of invertase. T. A. H. Gellulase. HANS VON EULER (Zeitsch. angew. Chem. 1912 25 250-251).-A brief account of the work of earlier investigators on the action of bacteria and fungi on cellulose is given and the con- clusion is drawn that the hydrolysis of pure cellulose by enzymes derived from fungi or higher forms of plant life has not yet been demonstrated. It is shown in the present communication that cellulose-dextrins obtained by the action of strong sulphuric acid on cellulose are converted under the influence of an enzyme (cellulose-dextrinase) occurring in the extract obtained by pressing Merulius lacrimam into substances having a greater reducing action on Fehling solution ; that the change is brought about by an enzyme is demonstrated by the fact that very little change takes place if the extract is heated before being added to the cellulose-dextrin solution. W. H G.i. 328 ABSTRACTS OF CHEMICAL PAPERS. Synthetic Action of Enzymes. WILLIAM M. BAYLISS (Pvoc. physiot. Xoc. 1911-12 xl-xli ; J. Physiol. 43).-Using glycerol t o reduce the water content the synthesis by emulsin of quinol and dextrose to form arbutin can readily be observed in a week or less. A small degree of synthesis can readily be detected polarimetrically. This experiment lends itself well to class work. W. D. H. The Nature of Enzyme Action. 11. The Synthetic Pro- perties of Anti-Emulsin. WILLIAM M. BAYLISS (J. Phy~ioZ. 1912 43 455-466).-Intraperitoneal injection of emulsin does not give rise to any true anti-enzyme although precipitins for the proteins con- tained in the solution are produced. The inhibitory action of serum so obtained on emulsin is no greater than that of normal serum and is merely due to diminution of optimal acidity. Neither normal serum nor the immune serum has any synthetic action. Emulsin on the other hand will synthesise lactose and also the glucoside of glycerol. This synthesis is retarded by serum probably owing to diminution of acidity. Emulsin is not a protein. W. D. H. Influence of Protoplasmic Poisons on Reductase. D. FRASER HARRIS (Bio-Chem. J. 1912 6 200-202).-The activity o€ this intracellular enzyme is not affected by reagents such as chloroform sodium fluoride etc. which lessen bhe activity of or destroy protoplasm. W. D. H. The Nitration of Arsanilic Acid. LUDWIG BENDA (Bey. 1912 45 53-58).-The brownish-yellow substance obtained in addition to diazoarsanilic acid mononitroarsanilic acid and 8-trinitroaniline in the nitration of arsanilic acid has the composition C,H,07N,As. As the action of bromine in alkaline solution gives 4-bromo-2 6-di- nitroaniline (m. p. 15S0 compare Austen this Journ. 1876 ii 513) and the action of potassium hydroxide yields 3 5-dinitro-4-hydroxyphenyl- arsinic acid (Benda and Bertheim this vol. i 63) the compound must be 3 5-dinitro-4-aminophenyZa~sinic mid. I n the fact that it resists diazotisation it resembles s- t rini troaniline. D. F. T. Preparation of Aromatic Stibines. LUDWIG KAUFMANN (D.R.-P. 24031 6).-Triphenylstibine can be obtained in 80-90% yield and m. p. 5 3 O (Michaelis and Reese give m. p. 48') by boiiing triphenyl- stibine sulphide(100 parts) with absolute alcohol (450parts) and benzene (50 parts) during half an hour adding copper powder and continuing the heating during three hours ; on cooling the product separates in a pure condition The copper can be replaced by iron in the presence of ferric chloride or the mixture left at the ordinary temperature during about fifteen hours and finally boiled for one hour. F. M. G. M.

ISSN:0368-1769    

DOI:10.1039/CA9120200229

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 247 Synthesis of Hydrogen Peroxide. ALEXANDRE DE HEMPTINNE (Ber. 1912 4 3 230).-The author points out that he has previously obtained results similar to those recorded by Fischer and Wolf (Abstr. 1911 ii 1082) in their experiments on the syntbesis of hydrogen peroxide (compare Ann. mc. sci. Bvuxelles 1908 191 1). He has also found that X-rays and ultra-violet light have no effect on the reaction. T. S. P. T h e Catalytic Decomposition of Hydrogen Peroxide by Dichromates. ERNST H. RIESENFELD (Zeitsch. anorg. Chem. 1 9 12 74 48-51. Compara Abstr. 1908 ii 951 ; 1911 ii 107 ; Spitalsky ibid. 36 37).-Mixtures of chromates and dichromates decompose hydrogen peroxide catalytically the velocity being the sum of the velocities due to the chromate and dichromate separately.The calculated values of K= k + k = 460c + 137000c2 where c and c are the concentrations of chromate and dichromate respectively agree closely with those found by Spitalsky. When free chromic acid is present perchromic acid is formed which loses oxygen to form chromic salts. The quantity of chromic salt found agrees with that calculated. C. H. D. Solubility of Bromine in Aqueous Solutions of Sodium Bromide. JAMES M. BELL and MELVILLE L. BUCKLEY (J. ATMT. Chem. SOC. 191 2 34 14-15).-Determinations of the solubility of bromine in solutions of potassium bromide have been made by Worleg (Trans. 1905 87 1107). Joseph and Jinendradasa (Trans. 1911 99 274) have studied the colour changes in bromine solutions on addition of bromides.Solubility determinations have now been made of bromine in solutions of sodium bromide at 25'. The solubility curve resembles that obtained by Worley. I n dilute solutions the ratio of bromine to bromide is about Br NaBr but is greater for more concentrated solutions. I n the case of nearly saturated sodium bromide solutions the ratio is about 2.5Br2 NaBr. E. G. 17-2ii. 248 ABSTRACTS OF CHEMICAL PAPERS. Solubility of Iodine in Aqueous Solutions of Bromides of Potassium and Sodium. JAMES M. BELL and MELVILLE L. BUCKLEY (J. Amer. Chem. Soc. 1912 34 10-14).-Dawson and Goodson (Trans. 1904 85 806) studied the solubility of iodine in solutions of potassium bromide in nitrobenzene and came to the con- clucrion that complex perhalogen compounds were formed of the same type as those produced in solutions of the alkali iodides.An investigation has now been made to ascertain whether double compounds of iodine with sodium bromide or potassium bromide are formed in aqueous solutions at 25'. The method adopted was similar to that used by Worley (Trans. 1905 87 1107) in his determination of the quantity of bromine dissolved by potassium bromide solutions. It has been found that the increase in the solubility of iodine is about 10-2 mol. for each mol. of salt. I n concentrated solutions of potassium bromide the ratio is somewhat less and in concentrated solutions of sodium bromide considerably less than 1 O-,. These results show that if double compounds are formed at all they are present in only very minute quantities. E.G. Atomic Weight of Nitrogen. EUG~NE WOURTZEL (Compt. rend. 1912 154 115-1 16).-Five experiments have given for the atomic weight of nitrogen the figures 14,005 14.008 14.006 14.007 14.008 ; mean 14.007. The method involved determination of the weight of oxygen neces- sary t o convert a known weight of nitric oxide into nitric peroxide. A U-tube containing cooled liquid nitric peroxide as a solvent was weighed and a definite weight of nitric oxide passed in. Pure dry oxygen was then introduced and the increase in weight determined after removing excess of oxygen by evacuating the apparatus at the temperature of liquid air. The experimental details will be published in a subsequent communication. w. 0. w. Oxidation of Nitrogen to Nitrogen Oxides. WILLEM REINDERS and A.CATS (Chem. Weekblad 1912 9 47-58).-An investigation of the influence of temperature the composition and velocity of the gas- mixture and the nature of the catalyst on the oxidation of ammonia by air. The catalysts employed were platiiiised asbestos or glass or copper wire thorium oxide and pumice ferric oxide on glass or asbestos oxidised iron-gauze in glass or porcelain tubes or a porcelain tube without a catalyst. With platinum or iron oxide S0-90% of the ammonia is oxidised to nitric acid and nitrous acid. The form of the catalyst and the velocity of the gaseous mixture have little influence. For platinised asbestos or glass the best temperature is 600'; for ferric oxide 650-700°. Of the three reitations possible (1) 4NH3 + 50 = 4N0 + 6H,O (2) 4NH3 + 6N0 = 5N + 6H,O (3) 4NH + 30 = 2N + 6H,O the first is much accelerated by platinum or ferric oxide so that the gas-mixture should be in close contact with the catalyst.ReactionsINORGANIC CHEMISTRY. ii. 249 (2) and (3) do not require a catalyst but are much facilitated by glass or porcelain. The possibility of the formation of nitrous oxide is not overlooked but the experimental difficulties precluded its detection. A. J. W. Oxidation of Ammonia in Aqueous Solution. WILLEM P. JORISSEN (Chem. Weekblad 1912 9 58-60. Compare foregoing abstract).-A summary of methods for the oxidation of aqueous ammonia published during the period 1843-191 1. Synthetic Formation of Nitrous Oxide. A. J. W. CAMILLE MATIGNON (Compt. rend. 1912 154 203-206).-The author shows from thermodynamical considerations that the direct union of nitrogen and oxygen with production of nitrous oxide should be realisable at 3000O and 3000 atmospheres.Unless the gas was rapidly cooled however and removed from the sphere of action the yield would be only 0.1%. Electrochemical Oxidation of Some Hydraaine Salk J W. TURRENTINE and WILLIS A. GIBBONS (J. Amer. Chem. Soc. 1912 34 36-49).-Szarvasy (Trans. 1905 '77 606) studied the electro- lysis of hydrazine hydrate sulphate and chloride and found that in each case nitrogen and hydrogen were produced in quantities corresponding with the quantitative decomposition of the base It was considered probable that by varying the Conditions of electrolysis so that the conditions at the anode would simulate oxidising agents of varying activity other oxidation products than nitrogen and water would be obtained.Turrentine (Proc. Arner. Chem. Soc. July 1908) therefore electrolysed hydrazine sulphate in solutions of varying acidity with different current densities and at different temperatures. In experiments in which high current density low temperature and strongly acid saturated solutions oE the salt were employed azoimide was produced and its formation was attributed to the action of the persulphate ion. An investigation has now been made with hydrazine carbonate hydrochloride and hydrobromide. I n the case of the carbonate under conditions which would favour the formation of percarbonates the hydrazine suffered quantitative oxidation into nitrogen and water. I n the electrochemical oxidation of hydrazine hydrochloride and hydrobromide azoimide was not obtained under any conditions.At low temperatures and with low current densities only nitrogen and water were produced whilst at high temperatures and with high current densities considerable quantities of ammonia were formed I n certain experiments with the hydrochloride the conditions were such as should have led to the formation of chlorate ions. The production of chlorate seemed however to be rendered impossible owing to the reduction of the hypochlorite by the hydrazine present. E. G. w. 0. w. Iodides of the Elements of the Nitrogen Group. H. R. DOORNBOSCH (Proc. K. Akad. Wetensch. Amsterdam 1911 14 625-637).-By means of observations of the changes which occur oni. 250 ABSTRACTS OF CHEMICAL PAPERS.solidification of molten binary mixtures and of the melting-point phenomena the authors have investigated the nature of the iodides formed by antimony and arsenic. Antimonous iodide melting a t 170*8O is the only compound formed by antimony. The iodide is not perceptibly miscible with antimony and on addition of excess of the latter the liquid melt separates into two layers2 one of which is almost identical in composition with the iodide whilst the other contains 71.6 atom % of antimony. The transition temperature at which the two liquid layers are formed is 169O. The eutectic temperature is SO0 and the eutectic mixture contains 88.2 atom % of iodine. On the assumption that the iodine dissolved in antimonous iodide consists of diatomic molecules i t is calculated that the molecular heat of fusion of the iodide is 11 cals.This corresponds with a molecular lowering of the freezing point equal to 357O. The thermal diagram for mixtures of arsenic and iodine is similar to that for antimony and iodine. In this case two compounds are formed however AsI melting at 140°70 and As214 which a t 135-136' is transformed into a pair of immiscible liquids one of which has a composition differing only slightly from As21+ whilst the other contains 30.5 atom % of arsenic. Various observations are recorded in support of the view that the substance As214 is a definite compound and that it is formed by dissociation of AsI in accordance with 2Ad It may also be formed by the interaction of AsI and metallic arsenic in consequence of the occurrence of the reversible change represented by SAsI + 4As t 6As21,.From the thermal data obtained in freezing- and melting-point determinations i t has also been found that antimonous iodide and arsenious iodide form a continuous series of mixed crystals the solidus and liquidus curves meeting at a minimum temperature of about 135". Arsenious iodide and phosphorus tri-iodide form an isodimorphous series of crystals with a transition point at 73*5O whereas anti- monous iodide and phosphorus tri-iodide yield two distinct series the corresponding curves meeting in a eutectic at 56O. Ap214+12. H. M. D. Transformation of Other Forms of Carbon into Graphite. WILLIAM C. ARSEM (Trans. Amcr. Electrochem. Soc. 1913,20,105-119). -Conflicting statements exist as to the conversion of amorphous carbon into graphite by heat it being uncertain whether pure carbon is thus convertible or whether the intermediate formation of carbides is necessary.Graphite must be defined by its specific gravity 2.25 to 2.26 as many varieties of carbon of entirely different density yield products more or less resembling graphitic acid on oxidation. The specimens of carbon to be tested are very finely ground and heated in closed graphite crucibles to 3000-3300° for fifteen minutes. Petroleum coke with only 0.1 0% ash yields silvery-grey graphite D 2-26 Bituminous coke containing 10% ash is less perfectly graphitised but gives better graphite after extraction with fused sodium hydroxide and hydrochloric acid. Anthracite is very imper- fectly converted. Lamp black either alone or mixed intimatelyINORGANIC CHEMISTRY.ii. 251 with ferric oxide is converted into a black non-crystalline powder D 2.10 which yields a yellow graphitic acid with Brodie's test but has none of the characteristic properties of graphite. White diamond yields coke D 1.915 and not graphite. The tendency to become converted into graphite is quite independent of the quantity and nature of the mineral matter present. Solubility of Carbon Dioxide in Water and Certain Other Solvents at High Pressures. WILHELM SANDER (Zeitsch. physikal. Chem. 1912 78 5 13-549).-The solubility of carbon dioxide at 20° 35" 60° and looo in water and in a number of organic solvents has been determined at a series of pressures between 20 and 170 kilog./cm.2 by means of a Cailletet pressure apparatus.A t low temperatures the relationship between solubility and tem- perature deviates from Henry's law for all the solvents examined The solubility of the gas in ethyl and propyl alcohols benzene chloro- bromo- and nitro-benzene and toluene increases faster with increasing pressure in ethyl ether ethyl acetate and water slower than Henry's law requires. The law in question is more nearly followed when the volume of gas absorbed is referred not to the volume of the solvent but to that of the solution. As would be anticipated Henry's law is the more nearly followed the higher the temperature and at 100' the solubility of carbon dioxide in most of the solvents is proportional to the pressure. The solubilities diminish with increasing temperature except for nitro- benzene which appears to dissolve the same amount of carbon dioxide at 60" and at looo.For solvents which are chemically related such as benzene and chloro- and bromo-benzene the solubility of carbon dioxide diminishes with increasing atomic weight. The isotherms for the saturated solutions of carbon dioxide in ether and of ether vapour in carbon dioxide have been determined at 35O 60° and 100'. I n the neighbourhood of the critical point Henry's law is not even approximately valid. Experiments with Liquid Helium. Isotherms of Mon- atomic Gases etc. IX. Thermal Properties of Helium. H. KAMERLINOH ONNES (P'roc. K. Akad. Weterzsch. Amsterdam 19 11 14 678-684. Compare Abstr. 1911 ii 487).-With the aid of the helium cryostat described previously the author has succeeded in measuring directly the critical temperature 5.25" (abs.). The following vapour-pressure data have also been obtained for liquid helium between the boiling point and the critical temperature Temperature ............ 4-28" 4.97" 5'10" 5-15" 5-22' 5.25 Pressure (mm.Hg) ... 767 1329 1520 1569 1668 1718 C. H. D. G. S. According to these numbers the vapour pressure increases very From the rapidly with the temperature above the boiling point.. above data the critical volume is calculated to be 0*00271. Monatomicity of Neon Krypton and Xenon. H. M. D. SIR WILLIAM RAMSAY (Proc. Roy. Xoc. 1912 A 86 lOO-lOl).-Measurementsii. 252 ABSTRACTS OF CHEMICAL PAPERS. have been made of the wave-lengths of sound in air neon krypton and xenon From these data the specific heat ratios obtained are neon 1.642 krypton 1.689 xenon 1.666.Within the limits of experimental error these numbers agree with the value 1.667 required on the assumption that the gases are monatomic. H. M. D. The Availability of the Potassium in “Rapakivi” and Pegmatitic Granites. OSSIAN ASCHAN (Zeitsch. anorg. Chenz. 19 12 74 55-73).-“ Rapakivi ” is a Finlaud porphyritic granite which weathers readily and leaves large easily separable masses of ortho- clase. Various methods have been proposed for rendering the potass- ium of these and other silicates available for manures. [With LAURI Lo~~a.]-Estimations of potassium and phosphates in (I) orthoclase from pegmatite at Sornas near Helsingfors ; (11) round rapakivi masges from weathered rock near Lovisa; (111) larger and less weathered masses from the same district; (IV) crystals from less weathered rock near Wiborg; (V) finer particles from the same rock; give I.11. 111. IV. v. K,O ........................ 13.44 9‘68 10.95 10.16 9.87% P,O ........................ 0.313 0.197 0.204 0-204 0’178% A small part of the potassium is extracted by heating on the water- bath with milk of lime whilst in a sealed tube at 150-180’ as much as 17% of the total potassium is rendered soluble and at 225’ in an autoclave 22% of the total. Sulphuric acid extracts up to 25% whilst hydrogen chloride at a red heat removes very little. Fusion with lime and sodium chloride at 900-1000’ renders 81% of the potassium soluble. Fusion with calcium chloride has much less effect.The residue has considerable value as a fertiliser. Experiments on the action of soil on the powdered felspar show that in the course of six to twelve months a t the ordinary temperature the potassium increases but the results are inconclusive on account of decomposition of the soil setting free phosphates and potassium salts. C H. D. New Alkali Phosphides of the Type M,P,. LOUIS HACKSPILL and ROBERT BOSSUET (Compt. rend. 1912 154 209-21 l).-A description of the preparation and properties of caesiurn rubidium potassium and sodium phosphidee having the general formula M,P,. Two or three grams of the metal and a large globnle of phosphorus are distilled successively into an evacuated tube and the mixture heated at 400-430’. A black mass is formed containing free metal but after 100 t o 150 hours this is lost by volatilisntion and the phosphide becomes reddish-brown.I n the case of the sodium salt it is necessary to heat a t 450’. At 0-100’ the four phosphides resemble cadmium sulphide in appearance but become darker at higher tempera- tures and are almost colourless when cooled in liquid nitrogen. They melt at about 650’ with decomposition and loss of phosphorus. They rapidly decompose in air and when treated with water yield a solid phosphorus hydride together with a small amount of phosphine and hydrogen. Potassium phosphide has D 2 approximately. w. 0. w.INORGANIC CHEMISTRY. ii. 253 New Compounds of Nitrogen and Hydrogen with Lithium. FRANZ W. DAFERT and R. MIKLAUZ (Monatsh. 1912 33 63-69.Compare Abstr. 1909 ii 882 ; 1911 ii 39).-0n exposure to sun- light lithiumimide decomposes according to the equation 2Li2NH = Li,N + LiNH the reaction being accompanied by the development; of a dark red colour. I n the action of nitrogen on lithium hydride of hydrogen on lithium nitride or of mixtures of nitrogen and hydrogen or ammonia on lithium hydride or nitride lithiumimide lithiumamide or trilithiumaniide or mixtures of these three substances are formed the final product depending on the temperature and other experimental conditions. The amide can be readily obtained by the action of ammonia on amorphous lithium nitride a t temperatures between 130' and 350° or on crystalline lithium nitride from 410' to 430° or on lithium hydride from 440-460° the changes taking place according to Li,N + 2NH,= SLiNEI and LiH + NH = LiNH + H,.At 450' lithiumimide reacts with hydrogen according to 3Li,NH + 2H2 = 2Li,NH + NH,. The trilithiumamide thus obtained reacts a t about 600' with nitrogen according to 4Li,NH2 + N = 6Li,NH + H,. The True Atomic Weight of Silver Deduced from the Laboratory Determinations of a Century. GUSTAVE D. HINRICHS (Conzpt. reizd. 1912 154 211-213. Compare Abstr. 1908 ii 573 574; 1909 ii 140 653; 1910 ii 285 844; 1911 ii 1080).-The extent to which values for the atomic weight of silver by Stas Marignac Maumenb Gallo the Harvard school and others differ from the whole number 108 is shown in diagrammatic form. The author considers that the manner in which these differences are distributed above and below 108 justify the conclusion previously arrived at that the true atomic weight of silver is 108'.H. M. D. w. 0. w Modifications of Silver. I. Mirror Silver. VOLKMAR KOHL- SCH~~TTER and EMILIE PISCHMANN (AnmaZen 1912 387 86-145).- True allotropy characterised by a different energy-content of the modifications does not occur in silver but .the physical properties of silver differ in a marked degree according t o the method of prepara- tion. la the present investigation the properties of silver mirrors prepared under different conditions are studied. Potential measurements with ammoniacal silver solutions against silver nitrate show that a part of the silver must be present as hydroxide and this part is of essential importance in mirror formation. It is shown that the reduction by tartaric acid or sugars always involves the formation of aldehydes and that in all cases colloidal substances are formed during the reaction. Reduction with ferrous salts or hydrogen causes deposition of the silver on the surface of the containing vessel but the deposit is black and does not take the form of a mirror.The reduction potential is not the determining factor as the substances which yield mirrors include those with both high and low reduction potentials. A low velocity of reduction is favourable,ii. 254 ABSTRACTS OF CHEMICAL PAPERS and the influence of traces of copper and other metallic salts in promoting the formation of mirrors is due to their retarding effect on the reduction. Adsorption of silver hydroxide by the walls of the containing vessel plays an important part and the formation of a mirror is favoured by prolonged contact with the silver solution before the reducing agent is added. Experiments with filter paper show that silver hydroxide is adsorbed to a greater extent than the other constituents of the solution.The surface tension is lowered by all the substances which serve as reducing agents and in some cases the surface tension diminishes with time. Silver mirrors prepared in presence of traces of metallic salts differ in appearance but consist in general of pure silver. Thin mirrors are transparent and are recognisable as colloidal (disperse) by means of the cardioid ultramicroscope The colloidal character is confirmed by the action of electrolytes very dilute acids and haloid salts dislodging the film without dissolving it.The electrolytic potential is the same as that of massive silver but the electrical resistance is greater and alters with the time in a manner which is characteristic of the reducing agent used. Silver films produced by electrical discharge in dilute gases show similar variations with the nature of the gas employed. C. H. D. Gelatin and Other Colloids as Retarders in t.he Reduction of Silver Chloride. WILLEM REINDERS and c. J. VAN NIEUWENBURG (Zeitsch. CI~ern. I n d . Kolloide 1912 10 36-40).-The addition of small quantities of colloidal substances to a ferrous citrate solution has been found t o have a very marked retarding influence on the rate at which silver chloride is reduced. The effect is exhibited by gelatin albumin agar-agar gum arabic and also by certain dyes such as acid- violet-6B.With Ponceau-3R there appears to be little or no retarda- tion however. In the case of gelatin and albumin the effect is well developed even in the presence of 0.001% of the colloid. With increasing concentration of the colloid the retardation increases and curves are drawn to show the influence of concentration. Of the two steps which are involved in the reduction process (a) dissolution of the silver chloride (b) reduction of the dissolved salt and precipitation of metallic silver it is shown that the colloids are without influence on the former and that the observed effect is due to retardation of the second process. From these experiments it appears that gelatin has a double function in the photographic process.It acts as an accelerator in the photo- chemical reduction of the silver halide (compare Abutr. 1911 ii 490) and as a retarder in the subsequent development. H. M. D. Double Carbonates of Calcium. MAURICE BARRE (Compt. r e d . 1912 154 279-280).-When precipitated calcium carbonate is boiled with a concentrated solution of sodium carbonate ortho- rhombic crystals are produced having the composition Na2CO,,CaC0,,2HO and not Na2C0,,CaC0,,5H,0 as stated by Fritsche ( J . pr. Chem.,INORGANIC CHEMISTRY. ii. 255 1864 93 339). The compound is not formed at 98' unless the solu- tion contains at least 21.06% of sodium carbonate. Under these conditions potassium carbonate gives a salt crystallising in prismatic needles having the composition K,CO,,CaCO,.This is readily hydro- lyeed by water and at 19' is only stable in solutions containing at least 59.25% of potassium carbonate. Barium and strontiu'm carbonates do not appear to form double salts with the alkali carbonates. The Conditions f o r the Formation of Magnesium Nitride from Air. CAMILLE MATIGNON and A. LASSIEUR (Chem. Zeit. 1912 36 30 ; Compt. mnnd. 1912,154,63-65).-When magnesium powder is heated to redness in a deep closed crucible the upper layer is con- verted into oxide and the lower into nitride. The reaction with nitrogen as shown by the fall of pressure in a manometer connected with the vessel containing the magnesium begins at 670° whilst the reaction with oxygen begins at 600' and is more rapid. If air is used and the vessel is heated to 620° the reaction ceases when all the oxygen has been absorbed.The behaviour in a crucible is thus accounted for. 0. H. D. Preparation of Magnesium Silicide and its Decomposition by Acids. ADOLPHE BESSON (Compt. rend. 1912 154 116-119).- A mixture of magnesium with half its weight of powdered quartz is stamped into an iron crucible and the reaction started by lighting some magnesium powder placed on the top. On treating the black mass of silicide with hydrochloric acid a gas is obtained containing 6-7% of silicon hydrides whereas Moissan's silicide gives only 445%. The amount OF silicon hydrides is not increased by using other acids but may be diminished as in the case of oxalic citric or sulphurous acids which yield only hydrogen.The hydrides are best prepared by decomposing the silicide under water in a large flask by pure hydro- chloric acid. A gas containing less than 0.5% of hydride (calculated as tetrahydride) is not spontaneously inflammable but fumes in air forming a colourless solid of variable composition H,Si,O or H,Si,O,. When this is heated in a vacuum water is lost and the colourless w. 0. w. residue has the composition of a suboxide of silicon. w. 0. w. Indian and Chinese Zinc. W. HOMMEL (Zeitsch. angew. Chem. 1912 25 97-100).-The history of the manufacture of zinc in India and China is dealt with the author drawing the conclusion that the metal was first obtained in Jndia the manufacture then being trans- planted to China which country then alone produced it until the middle of the eighteenth century.The analysis of a specimen of Chinese zincrecovered from the wreck of a ship which sank near Gothenburg in 3 745 gave the figures zinc 98.990% ; iron 0.675% ; antimony 0.245%. Copper nickel silver arsenic and lead were not present. The Ternary System Cadmium Chloride-Potassium Chloride- Sodium Chloride. HERMANN BRAND (Jahd. Min. Bed. Bd. 1911 32 627-700).-'l'his system has been investigated as a case of a T. S. P.ii. 256 ABSTRACTS OF CHEMICAL PAPERS. ternary system including binary compounds which do not melt with- out decomposition. The three components have the m. p.'s CdCI 562O KC1 774O NaCl 798'. The binary system cadmium chloride-potassium chloride contains two compounds CdCl,,KCI m. p. 431' forming a maximum on the freezing-point curve and CdCl2,4HCl which breaks up at 460° into KC1 and liquid. The two eutectic points occur at 382' and 34 mol.% KC1 and at 390' and 63 mol. % KCI respectively. The first compound forms rhombic crystals and eutectic structures are well developed. In the binary system cadmium chloride-sodium chloride only a single compound occurs CdCl,,ZNaCL which breaks up at 425' into sodium chloride and liquid. The eutectic point is a t 45 mol. % NaCl and 392'. Sodium and potassium chlorides form a continuous series of solid solutions the freezing-point curve having a minimum a t 654O and 50 mol. % NaCl. At a lower temperature the solid solution is resolved into its components the transformation curve having a maximum in the middle at 400'. Equilibrium is not entirely reached after some months a t atmospheric temperature.The compound CdCl,,KCl does not form solid solutions and the ternary system may thus be broken up into two systems CdC12- CdCl,,KCl-NaCl and CdCl,,KCl-NaCl-ECl. The space-model has been constructed by means of a complete thermal and microscopical analysis of these two systems. There are three ternary eutectic points at 354O 370' and 373' respectively. There are six surfaces of primary crystallisation. Ternary solid solutions are formed with small propor- tions of cadmium chloride and the presence of cadmium chloride raises the temperatures at which solid solutions of potassium and sodium chlorides are resolved into their compounds. The theory of ternary systems of this type is discussed very fully. C. H. D.The Binary Systems Cadmium Iodide-Potassium Iodide and Cadmium Iodide-Sodium Iodide. HERMANN BRAND (Centr. Mi%. 1912 36-32).-Cadmium iodide has m. p. 385' and potassium and sodium iodides have m. p.'s 678" and 653' respectively. The freezing- point curve of mixtures of cadmium and potassium iodides has a eutectic point a t 185' and 47.5 mol. % KI whilst the ascending branch has two breaks corresponding with the formation of the compound CdI,,2KI at 269' from crystals and liquid and with the transforma- tion of the u regular crystals of this compound a t 215' into the /3 doubly refracting modification stable at low temperatures. The freezing-point curve of mixtures of cadmium and sodium iodides is of a simple form and a compound is not formed. The eutectic point is at 287' and 47 mol.% NaI. The formation of solid solutions is not observed in either case. C. H. D. The System Cadmium-Tin. A. P. SCHLEICHER (Intern. Zeitsch. Metallographie 1912 2 76-89).-The freezing-point curve of the alloys of cadmium and tin consists of only two branches intersecting at the eutectic point at 177" and 67.6 atomic % of tin. y-Tin holdsINORGANIC CHEMISTRY. ii. 257 up to about 10 atomic % of cadmium in solid solution @tin much less. The transformation observed a t 127' corresponds with the breaking up of the solid solution into cadmium and P-tin. Cadmium does not retain more than traces of tin in solid solution. C. H. D. [The Behaviour of Certain Hydroxides towards Solutions of Alkylenediamines.] A Correction. WILHELM TRAUBE (Ber. 1912 45 164.Compare this vol. i 9).-The author points out that Hantzsch and Robertson (Abstr. 1909 ii 44) and also Dawson (ibid. ii l o l l ) have shown that ammoniacal solutions of cupric hydr- oxide contain the tetrammine base Cu(NH,),(OH),. E. B. Study of the Atomic Weight of Mercury through the Analysis of Mercuric Bromide. C. W. EASLEY and B. F. BRANN (J. Amer. C'hem. Xoc. 1912 34 137-147).-Easley (Abstr. 1909 ii 1013; 1910 ii 957) has determined the atomic weight of mercury by the analysis of mercuric chloride. The constant has now been re-determined by a study of mercuric bromide. Pure mercuric bromide was prepared by passing a current of nitrogen through liquid bromine and thus conveying bromine vapour into a chamber containing mercury at 300'. When the whole of the metal had been converted into the bromide the latter was heated at 235' and nitrogen passed through the apparatus to remove the excess of bromine.The salt was thus obtained in masses of needles and was completely soluble in water. The analysis of the bromide was effected by treating a solution containing a weighed amount' with sodium hydroxide and reducing by means of hydrazine hydrate or hydrogen peroxide so that the mercury was precipitated and the bromine ions left in solution. After the mercury had been removed by filtration the solution was treated with a slight excess of nitric acid and silver nitrate was added to precipitate silver bromide. The ratio HgBr 2AgBr was thus determined. The results of eleven experiments gave a mean value for the atomic weight of mercury 200.64 (Br = 79.92 ; Ag = 107.88) as compared with 200.62 and 200.63 obtained in the experiments with mercuric chloride (Zoc.cit .) . E. G. Fractional Crystallisation of the Picrates of the Rare Earths. LOUIS &l. DENNIS and C. W. BENNETT (J. Amer. Chem. Xoc. 1913 34 7-10).-1n attempting to ascertain whether a separa- tion of the rare earths could be effected by the fractional crystallisa- tion of the picrates it was considered desirable to use mixtures of earths contaiuing members of the yttrium erbium and didymium groups. After removing cerium and thorium from such a mixture by chlorination and treatment with hydrogen peroxide the earths were precipitated as oxalates and the latter converted into the oxides by ignition. The oxides were converted into the hydroxides by dissolving them in hydrochloric acid and adding ammonia.The hydroxides were dissolved in hot solution of picric acid to form a neutral solution. The picrates were fractionally crystallised from theii. 258 ABSTRACTS OF CHEMICAL PAPERS. solution twenty-five final fractions being obtainek. The absorption spectra of these fractions were examined and the atomic weights determined by precipitating the earths as oxalates and finding the ratio R,O 3C,04. Curves were constructed to show the changes in the atomic weights and in the intensity of certain bands of the absorption spectra. The curves show that praseodymium and neodymium concentrated in the first few fractions but rapidly decreased after the sixth fraction ; a remarkable increase in the amounts of these elements however occurred in the tenth and nineteenth fractions and this peculiarity is being further investigated.Erbium and holmium were absent from the first six fractions but suddenly appeared in the eighth fraction. It is evident therefore that the fractional crystallisation of the picrates enables a rapid concentration of praseodymium and neo- dymium free from erbium and holmium to be effected and also a concentration of erbium and holmium containing but small amounts of elements of the didymium group. Preparation and Properties of Metallic Cerium. ALCAN HIRSCH (Trans. Amer. Electrochem. Soc. 191 1 20 5'7-104).- Cerium is best prepared by dehydrating ceric chloride in an atmosphere of hydrogen chloride and electrolysiog the fused chloride in an iron crucible which serves as cathode with a graphite anode.Sodium chloride potassium fluoride and barium chloride are added in small quantities to the electrolyte to increase the resistance of the bath and check decomposition. The ceriulu thus obtained contains about 2% of impurities consisting of iron and of cerium oxide and carbide. It may be purified by amalgamating with boiling mercury skimming off the undissolved impurities and distilling in a vacuum in a quartz vessel lined with magnesia. The metal has then D 6.92 and is almost as soft and malleable as lead. Its alloys with most other metals are hard and brittle but the alloy with antimony is soft and stable in air. The alloys with iron nickel tungsten manganese cadmium and several other metals yield sparks when struck.E. G. C. H. D. The Electrical Properties of Aluminium Alloys. WITOLD BBONIEWSKI (Ann. Chim. Phys. 1912 [viii] 25 5-125).-Most of the experimental results contained in this paper have been previously published (Abstr. 1910 ii 128 715 ; 1911 ii 115). The following further compounds are described Al,Fe Al,Mn and AI,Ni which are recognised by the electrical methods previously employed. Ternary alloys of copper aluminium and silver obtained by making binary mixtures of the compounds AlCu and Al,Ag have also been studied. A aeries of measurements of alloys of the composition AlCu fix the transition point at 580'. C. H. D. Sinhalese Iron and S t e e l of Ancient Origin. SIR ROBERT HADFIELD (Proc. Roy. Soc. 1912 A 86 94-100).-Specimens of iron and eteel obtained from the buried cities of Ceylon have beenINORGANIC CHEMISTRY.ii. 259 analysed siibjected to various mechanical tests and the micro- structure examined. The analytical data for the three specimens are as follows C. Si. S. P. Mn. Fe. Density. Steel chhel (fifth century) ...... traces 0.12 0.003 0.28 nil 99.3 7'69 Nail (fifth century) ........... traccs 0.11 nil 0.32 nil - 7-69 Native billhook ............... .. traces 0.26 0.022 0.34 traces - 7-50 The percentage of silicon is low that of phosphorus high whilst the absence of manganese is rather remarkable. The low percentage of sulphur indicates that a very pure fuel no doubt charcoal was employed in the production of the material. The micro-photographs and the mechanical tests show that the specimens represent wrought iron and not steel resembling somewhat the material known as puddled iron.According to the photographs the specimens contain a large amount of slag indicating that the material has not been subjected to anything like the amount of squeezing and forging that modern wrought iron undergoes. Some of the micro-photographs show martensitic structure in parts and the author considers that this affords evidence of quenching. Influence of Painting on the Rusting of Iron. XRIK LIEBREICH and FBITZ SPITZEB (Zeitsch. Elektrochem. 19 12 18 94-99).-The authors show by covering iron with a varying number of coat& of paint that a thick coating does not prevent rusting; on the contrary the greater the number of coats the greater the rusting.The requisite water probably comes in part a t least from the slow oxidation of the oil of the paint. The source of the oxygen also necezisary for rusting has not been discovered nor has any explanation been found for the fact that rusting is favoured by the thickness of the coating. All the paints tried had the same effect except one c~ntaining alkali. Fresh iron is positive towards painted iron at iirst but the positive value gradually diminishes and finally the fresh iron is negative to the painted iron. This appears to be due to the liberation of hydrogen on the iron. G S. First Crystallisation and Subsequent Physico-chemical Transformations in Iron-Carbon Alloys containing more than 4% of Carbon. NJCOLAUS M. VON WITTORF (J. Buss. Phys. Chew. Xoc. 1911 43 1613-1690).-The principal results of this extended thermal and micrographic study of iron-carbon alloys are as follows.Fusions containing 6*2-10% of carbon begin to crystallise at 2000-2380° with separation of a phase rich in carbon (PFeC,) which in unetched sections has a pale sulphur-yellow colour and a silvery reflexion. This phase is etched very slowly by nitric acid (1 4) and becomes coated with copper when treated with very dilute copper sulphate solution; after the action of nitric acid a dark residue is obtained. The same carbide crgstallises when the fusion is heated to 2600O and graphite dissolved in it. From somewhat below 2000' down to 1700° the first substance separating is pure cementite. H. M. 1>.ii. 260 ABSTRACTS OF CEEMICAL PAPERS.In the temperature region 1650-1330' burning of the fusion takes place this being particularly marked with a carbon-content of about 7%; stirring of the fusion is accompanied by the appearance of thin tabular crystals (1FeC) at the surface whilst in fusions heated to about 1600' these crystals assume the form of long arrows with angular projections. Fusions heated below 1700' always contain a metallic phase surrounding the arrows or a compound rich in carbon (4 Fee,) forming dendritic masses on a eutectic-like foundation. This compound is not appreciably etched by 4% alcoholic picric acid solution or by aqueous sulphuric acid (1 10 by weight) if the mass is hardened a t a tem- perature not below 1160° but unlike cementite it is etched energetically by 1 4 nitric acid.The quantity of this compound separating initially increases from 0 to 100% with increase in the concentration of the carbon from 4.1% to 5%. I n fusions containing 6% or 7% of carbon the basic mass of metal consists of this com- pound and of the arrow-like residuum (ZFeC) its composition being expressed by the formula Fe,C (5.03% C). The carbide Fe,C decomposes into y-solution and graphite below 1130O. Crystallisation of the stable eutectic in fusions containing more than 4.1% of carbon proceeds at about 1180O. The phases crystallising above 2000' (? FeC,) and a t 1600-1400' (1 FeC) decompose with separation of graphite. The points of disagreement between these results and those of Ruff and of Ruff and Goecke (Abstr. 1911 ii 897) which were published after the completion of the author's investigations are discussed.T. H. P. Triferro-carbide (Cementite) Fe,C. OTTO RUFF and EWALD GERSTEN (Bey. 1912 45 63-72).-Owing to the uncertainty as to the heat of formation of iron carbide the authors have carried out further work on the subject. The carbide was prepared as follows A mixture of 1000 grams of iron (C 4.13% ; Si 0.074% ; S 0.006% ; Mn 0.15%; P 0.20%; Cu 0.005%) with 100 grams of powdered arc- lamp carbon was heated for one hour a t a white heat and the fused mass then poured on to a large iron plate. After removing oxide and dross the cold fused mass mas finely powdered and digested at the ordinary temperature with N-acetic acid for four weeks and then for several weeks with N/S-hy drochloric acid. Any remaining carbon was then removed by levigation and the residual carbide washed with alcohol and ether and dried in a vacuum; it contained 6.69% C and 93.28% Fe (theory 6.67 and 93-33 resp.).I n appearance it was dark grey and consisted for the most part of fragments of globular aggregates of needle-shaped crystals; it was very brittle and could be powdered on the hand. The hardness lies between 3.3 and 3.3 so that it cannot itself be the came of the hardness of rapidly cooled steel which is probably due to the solid solution of the carbide in y-iron DZI= 7.396 the molecular volume being 24.34. The molecular heat of combustion determined in a bomb calorimeter was found to be 375.1 Cals. the products of combustion being carbon dioxide and ferrosoferric oxide. I n the actual combustions a mixtureINORGANIC CHEMIS'IRY.ji. 261 of ferrous and ferrosoferric oxide is produced from the analysis of which and the knowledge of the heat of combustion of ferrous oxide to magnetic oxide the necessary correction to be applied to the observed heat of combustion of the carbide can be calculated. The molecular heat of formation of ferrosoferric oxide was found to be 265.2 Cal. Pure Swedish iron (Fe 99*745%) and iron prepared from pure ferric chloride were used in these experiments allowance being made for the heat of combustion of the traces of impurities present in the Swedish iron. From the molecular heats of formation of ferrosoferric oxide and of carbon dioxide (from graphite = 94.8 Cal.) and from the molecular heat of combustion of iron carbide to ferrosoferric oxide and carbon dioxide the heat of formation of iron carbide (Fe3C) is found to be - 15.1 Cal. T.s. P. Chromic and Aluminium Nitrates. MILORAD 2. JOVITSCHITSCH (Monatsh. 19 12 33 9-lS).-By dissolving strongly heated chromic oxide in hot concentrated nitric acid of D 1.4 a solution is obtained from which the hydrate Cr,(NO,) 15H,O crystallises on cooling iu the form of dark brown prisms [a b c = 1.4250 1 1.1158 ; /3 = 9 3 O 1 0 ' ] . I n contact with dry air the crystals loso 6H,O with the formation of the grey-coloured hydrate Cr2(N0,),,9H,0. Under similar conditions the solution of strongly heated alumina in concentrated nitric acid gives rise to the nitrate Al2(N0,),,15H,O. These crystals like those of the corresponding chromic salt art3 quite stable when exposed t o the ordinary air.Crystals of aluminium nitrate containing a smaller proportion of water appear to separate from solutions of alumina in fuming nitric acid but these are very hygroscopic and the composition could not be determined. H. M. D. Preparation and Properties of Some Perchlorates. H. GOLD- BLUM and F. TEHLIKOWSKI (Bull. Xoc. chim. 1912 [iv] 11 103-111). -The perchlorates were prepared by dissolving the appropriate carbonate or hydroxide in perchloric acid and evaporating the solution obtained until crystallisation occurred. Analyses of the nickel and cobalt salts were made the metals being determined electrolytically after conversion into sulphates. The acid was estimated by electro- lysing a dilute solution of the perchlorate using a current of 0.1 ampere and 2.4 volts and titrating the solution when deposition of the metal was complete.Nickel perchlorate NiC104,5H20 m. p. 149O forms long green hygroscopic needles and is soluble in water alcohol or apetone. When heated a t 103" it becomes only partly soluble in these solvents; the insoluble matter is yellow and crydialline and is probably a basic salt. When kept in aqueous solution even at 0" the perchlorate undergoes hydrolysis depositing a flocculent precipitate of nickel hydroxide. Cobalt perclhrate CoC104,5H,0 m. p. 143O forms long red needles and resembles the nickel salt in properties but is more stable not being decomposed when heated at 103O nor when the aqueous solution is boiled. Chromium pevchlorate forms short green VOL.CII. ii. 18ii. 262 ABSTRACTS OP CEIEMICAL PAPERS. deliquescent needles and is very soluble in alcohol. Didymium perchlorate forms hopper-shaped aggregates of cubic crystals and is less soluble in alcohol than the other three perchlorates. T. A. H. Some Reactions and Compounds of Tin Tetrafluoride. LUDWIG WOLTER (Chem. Zeit. 1912 36 165)-Pure tin tetra- fluoride is a snow-white very hygroscopic crystalline compound. Gaseous ammonia combines with it a t 43' forming a white compound SnF,,NH which loses very little ammonia even at 400'. When tin tetrafluoride and ammonia are heated together in a sealed tube at 120-1 30° strongly refracting crystals of a second compound SnF4:2NH are obtained. Both compounds dissolve in water the solutions gradually becoming turbid.The pyridine compound obtained by heating the components in a reflux appaiatus forms white crystals of the composition SnF,,2CSNH,. Quinoline and aniline yield white additive compounds. Liquid hydrogen sulphide decomposes tin tetrafluoride in a sealed tube according to the equation SnF + 2H,S = SnS + 4HF. Chlorine compounds of phosphorus bring about an exchange of chlorine and fluorine. Metals react violently liberating tin and the formation of a difluoride is not observed. C. H. D. Arsenic-An timony Alloys. NICOLA P ~ A V A N O and PIETBO DE CESARIS (Intern. Zeitsch. Metalloyraphie 19 12 2 70-75).-0nly alloys containing from 0 to 40% of arsenic can be prepared under the ordinary pressure. Within this range a continuous series of solid solutions is formed the freezing-point curve having a minimum at 612O and 17'5% of arsenic. The alloys are microscopically homo- geneous.The compound Sb,As (Descamps Abstr. 1878 705) does not exist. C. H. D. Hydrosols of Coiumbic and Tantalic Acids and the Separa- tion of Columbium and Tantalum according to the Method of Weiss and Landeoker. OTTO HAUSER and A. LEWITE (Zeitsch. angew. Chem. 1912 25 100-103).-The hydrosols of columbic and tantalic acids are readily prepared by fusing columbiun or tantalum pentoxides with alkali dissolving the fused mass in water and dialysing the solution whereby a neutral liquid can be obtained. The bydrosols are comparatively stable remaining unchanged for weeks when preserved in stoppered flasks ; by concentration over sulphuric acid solutions were obtained which contained 1.346 grams of tantalum pentoxide and 2.571 grams of columbium pentoxide per litre.The disperse phase is negatively charged and the various precipitation reactions are described. It is specially noteworthy that they are very sensitive to sulphate chloride sulphite or nitrate ions and that the hydrosol of tantalic acid is readily precipitated by a current of carbon dioxide whereas that of columbic acid remains stable at all events for twenty-four hours. The sensitiveness towards the nitrate ion explains why Foote and Langley (Abstr. 1911 ii 72) were not able to obtain good results inMINERALOGICAL CHEMISTRY. i i 263 the separation of columbium and tantalum by the method of Weiss and Landecker (Abstr. 1909 ii 942) since according to this method potassium nitrate is added to the sodium carbonate used in the fusion. The authors find that satisfactory results are obtained when sodium carbonate aloue is used.T. S. P. Coagulation of Gold Hydrosols. ANT. GALECKI (Zeitsch. anorg. Chem. 1912 74 174-206).-The coagulation of gold hydrosols on addition of small quantities of electrolytes has been examined by means of the ultra-microscope and by measurements of the movements of the particles in an electric field. From these the conclusion is drawn that there is no essential connexion between the colour of the colloidal solutions and the size of the disperse particles. On the other hand the curves which are obtained when the calculated electric charges carried by the particles are plotted against the concentration of the electrolytes show that the electrostatic effects accompanying the coagulation process vary in a marked- manner with the nature of the electrolyte. H. M. D. Platinum Rhodium and Hydrogen. ADOLF SIEVERTS and E. JURHCH (Bey. 1912 45 221-229).-Using the method described previously (Abstr. 1911 ii 990) the authors have determined the solubility in platinum wire of hydrogen at atmospheric pressure and at temperatures up to 1340'. The solubility increases with rise in temperature ; platinum which has been saturated with hydrogen at a high temperature retains practically none of the gas when cold. At room temptratures massive platinum dissolves no measurable quantity of hydrogen. The absorptive power of platinum for hydrogen is much less than that of an equal weight of iron or nickel and is considerably less than that of copper; at 409" 100 grams of platinum wire dissolve 0.006 and a t 1342' 0.084 mg. of hydrogen at atmospheric pressure. A t constant temperature and under vary iug pressure the quantity of hydrogen absorbed by platinum wire is proportional to the square- root of the pressure Carbon monoxide and sulphur dioxide are insoluble in platinum. Precipitated rhodium when heated in a vacuum gives off a considerable volume of gas consisting of a mixture of carbon dioxide oxygen hydrogen and water vapour. Four grams of the metal which had been heated to a red heat did not dissolve a measurable quantity of hydrogen or carbon dioxide between 420' and 1020O. T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9120205247

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Min era 1 o g i c a1 C h e mi s t r y1 i i 263 A Suggestion for Mineral Nomenolature. HENRY S. WASHINGTON (Amer. J. Sci 1912 [iv] 33 137-151),-8 suggestion for a system of names (to supplement the present nomenclature 18-2ii. 264 ABSTRACTS OF CHEMICAL PAPERS. retained for ordinary use) which would indicate not only chemical and crystallographic characters but also indicate mineral relation- ships. The nature of this suggestion may be best indicated by selecting a few examples. Pyrite Gvoup (pyrides R(S,As,Sb) ; cubic pyritohedral) Pyrite ........... PeS,. ................. Iron sulpyride. Hauerite ......... MnS ............... Manganese sul pyride. Snialtite ...... CoAs .............. Cobalt arsenpyride. Cobaltite ......... Co(S As) ......... Cobalt sularsenpyride.Narcasite Group jmarcasides R(S As) ; orthorhombic) Marcasite.. ....... PeS ............... Iron sulmarcaside. Rammelsbergite NiAs ............... Nickel arsenmarcaside. Spinel G ~ o u p (spinelates R”R”’,04 ; cubic) Spinel ............ MgAI,O ............ Magnesium alumispinelate. Magnetite ...... FeFe,O ............ Ferrous ferrispinelate. Chroruite.. ...... FeCr,O ........... Ferrous chromispinelafe. Datolite Group (datolates R”3R”,Si,0,0 ; monoclinic) Datolite ......... H,CA,B,S~,O,~ ... Acid calcium bori-datolate. Euclase ......... H,Gl,AI,Si,O ... Acid glucinum alumi-datolate. Gndolinite ...... PeGl,Y,Si,O ... Ferro-glucinum yttri-datolate. Apatite Group (apatates R”5( F,Cl)( [PI As,V]O,) ; hexagonal) Apatite ........ Cab( F Cl)( PO,) ...Calcium phosphapatate. Miinetite ........ Yb,Cl( AsO,) ...... Lead arsenapatate. Vanadiiiite ...... Pb5Cl(V0,) ...... Lead vanadapatate. I;. J. S. Paraffins from a Yorkshire Coal Seam. JULIUS B. COHEN and CORNELIUS P. FINN (J. SOC. Chew&. Ind. 1912 31 12-14).-Analyses of a dark brown semi-solid material obtained from the Haigh Moor seam of the Hemsworth Collieries showed that the substance consisted of a mixture of liquid and solid paraffins. The liquid fractions obtained on distillation under low pressure contained probably members of the series from C,,H to C,,H,,; from the solid fractions the following paraffins were isolated C20H42 C32H46 U23H48 C24H50 c25H529 C20H54 [Goldfleldite and Faniatinite from Goldfield Nevada.] FREDERICK LESLIE RANSOME (Zeitsch. Kryst.Min. 1912,50,188-189 ; from Prof. Paper US. Geol. Surv. 1909 No. 68 1-258).-In a monograph on the geology and ore-deposits of this district the following mineral analyses are given. The name goZdJeZdite is proposed for a massive lead-grey mineral with bright metallic lustre and conchoidal fracture; H=3-3$. Analysis I by Palmer corresponds with the formula 5Cu,S (Sb,Bi As),(S,Te) and C32HGG. w. P. s. S. Te. Sb. As. Bi. Cu. Fe. Au. Ag. Insol. Total. 11. 30’5 - 11.3 10’2 - 44.8 3.2 - - - 100’0 A massive reddish-grey mineral is shown by analysis 11 by Schaller An I. 21-54 17.00 19’26 0.68 6’91 33-49 - 0’51 0.18 2-00 101’57 to be in composition midway between enargite and famatinite.MIXERALOGICAL CHEMISTRY. ii. 265 analysis is also given of crystallised bismite (Schaller and Ransome Abstr.1910 ii 220). L. J. S. Lorandite from Wyoming. AUSTIN F. ROGERS (Amsr. J. Sci. 19 12 [iv] 33 105 -106).-This thallium mineral TI ASS previously known only from Allchnr in Macedonia is recorded from the Rambler mine near Encampment in southern Wyoming. A single small deep red crystal was found with realgar and orpiment on a matrix of iron- pyrites and barytes. The identity of the mineral is proved by crys- tallographic measurements and by chemical and spectroscopic tests. L. J . S. The Chemical Constitution of Titaniferous Iron Ores. WILHELM MANCHOT and B. HEFFNER (Zeitsch. anorg. Chem. 1912 74 79-85).-Zt has not been decided whether titaniferous iron ores have the constitution FeO,TiO or Fe20,,Ti,0 on account of the difficulty of determining the state of oxidation of the titanium.Two specimens have now been examined (I) a coarse titaniferous ore from Ekersund and (11) a large crystal of ilmenite from Ural. The titanium is estimated by fusion with potassium hydrogen sulphate reduction of the iron with sulphurous acid and precipitation of titanic acid by boiling. The total iron is estimated in a solution reduced by sulphurous acid and the ferric iron iodometricnlly in a solution prepared by meaus of hydrochloric acid in absence of air Ti. Total Fe. Fe”’. Mg. Ca. S. I. ............ 16-12 44’50 22.76 0’66 0-25 0.28 II. ........... 29.81 34.71 9.38 - - 0.08 The ratio Ti:Fe”:Fe”’ is for I 1 :1*1147 1.215 and for 11 1 0.7312 0,2706. The ferric iron in I1 is probably due t o secondary oxidation and the ratio Ti02:Fe0 thus approaches 1 :1 in both cases.It has been shown by Manchot and Richter (Abstr. 1906 ii 272) that cdmpounds containing tervnlent titanium evolve hydrogen with alkalis. Hydrogen is not however evolved by the action of alkalis on ilmenite. The reaction of ilmenite with sulphuric acid is also quite similar to that of a mixture of titanic acid and a ferrous salt. The conclusion is drawn that titaniferous iron ores contain only titanium dioxide and not titanious compounds C. H. D. Chemico-mineralogical Section of the Older Salt Beds in the Berlepsch Mine at Stassfurt. OTTO RIEDEL (Zeitsch. Kryst. Min. 1912 50 139-173).-Samples of the salts were taken a t intervals of a few metres ranging from the top t o the bottom of the deposit (a total thickness of 184 metres) and representative of the various well-known zones.The materials being mixtures of various minerals are regarded as rocks and as such are subjected to a combined mechanical and chemical analysis with the object of determining the relative proportions of the several minerals present. I n the mechanical analysis the powdered materials were fractionated according to density by a heavy liquid (tetrabromoethane and toluene).ii. 266 ABSTRACTS OF CHEMICAL PAPERS. The aeparated grains were identified by means of their optical characters and by micro-chemical tests and after drying at 44-45O the different fractions were analysed. The chemical and mineralogical results obtained with thirty-six samples are tabulated and curves are drawn.The mineral species identified include halite anhydrite. polyhalite kieserite carnallite loeweite vantlhoffite langbeinite and sylvite. An analysis of vanthoffite ( 3Na2S0,,MgS04) gave the following results; the calcium is due to a little intermixed polyhalite and some loeweite is also perhaps present so,. Na. Mg- Ca. K. Total. 70.81 24-46 4.83 0.09 0.10 100.29 The conditions of formation of the deposits are discussed and the conclusion is drawn t h a t the temperature was not less than 72". The order of crystallisation of the various minerals was much influenced by the supersaturation of the solution. Pickeringite from Thuringia. H. HEW VON WICHDORFF (Centr. Mirz. 1912 42-43).-White or yellowish-white balls of pickeringite consisting of fine silky fibres occur in crevices in the slates quarried near Lehesten in the duchy of Saxe-Meiningen D 2.2 anal.I and 11. Similar material has also recently been observed in the alum-shales of the Wetzelstein near Saalfeld ; anal. 111 by Eyme. These analyses agree closely with the usual formula MgS0,,A1,1,S~),),,22H20 I.. J. S. SO,. A1,0,. Fe,O,. NnO. MgO. H,O. Total. I. ......... 37.76 12-14 - trace 4.55 45-45 99.90 11. ......... 38.09 12'22 - trace 4'62 45.44 100.37 III. ......... 37'31 11.22 1.66 - 5-04 44-88 100'11 The mioeral has been produced by the action of sulphuric acid formed by the decomposition of iron-pyrites on the shale. L. J. S. The Melting Point of Spodumene. EURD ENDELL and REINHOLD RIEKE (Zeitsch. anorg. Chem. 1912 74 33-47).-Lithium silicates have in general a high velocity of crystallisation.The data referring to the melting point of spodumene Li,0,A1,0,,4Si02 are very divergent. The only temperature which can be regarded as the true melting point is t h a t at which the mineral passes from the anisotropic to the isotropic-amorphous condition the liquefaction of the amorphous substance and diminution of its viscosity being a gradual process. The mineral has been examined by heating to various definite temperatures cooling rapidly and determining certain of the physical properties. The specific gravity is unaltered by heating to 920° but is diminished from 3.147 t o 2.370 a t 980". Double refraction disappears after heating the powder to 980" or with very fine powder at 950". Sections of the mineral remain almost unchanged even after heating to 1000°.The mean refractive index of crystalline spodumene is 1.66 and that of the glass 1.51'3 the discontinuity occurring at 920-980". The heating curve shows a marked discontinuity at 950". Spodumene glass has at the melting point a viscosity almostMINERALOGICAL CHEMISTRY. ii. 267 equal t o that of the crystals and it is only at 1250-1300° that the viscosity diminishes so far as to show softening of the glass. The melting point is therefore 950° and natural spodumene which is always monoclinic must have been formed below 9.50". C. H. D. [Bentonite from Laramie Wyoming.] NELSON HORATIO DARTON and C. E. SIEBENTHAL (Zeitsch. Kryst. Min. 1912,50 187-188; from Bull. U.S. Geol. SUTV. 1909 No. 364 1-81).-1n an account of the geology and mineral resources of the Laramie basin the following analyses are given of a kind of clay called bentonite.This is pale yellow to pale olive-green with a waxy lustre and a conchoidal fracture; it becomes dull on exposure to air. It forms beds with sometimes a thickness of 5 feet. SiO,. A1,0,. Fe,O,. MgO. CaO. Na,O. E20. H,O. Total. 59.78 15.10 2-40 4'14 0.73 - - 16'26 98-51 58.25 24.70 2'61 1.30 1-61 - - 11-00 94.47 66'5 23.9 3'1 1.0 0-5 - - 5.0 100.0 64.0 24.0 3.2 1.5 0.6 - - 6.7 100.0 60.18 26.11 2.54 - 0 -80 10.26 99-63 60.18 26-58 1-01 0.23 1.23 - 10'26 99-49 L. J. S. v - Allophanoids. STANISLAUS J. THUGUTT (Centr. Min. 191 2 35-41; from Spraw. Pow. iVc6uk. Wursxawa 1911 4 222-228. Compare Abstr. 1911 ii 210).-A reply to Stremme (Abstr. 1911 ii 406).It is maintained that the allophanoids (that is clays of the allophane balloysite and montmorillonite groups) represent defi i t e compounds and are not merely mechanical mixtures of colloidal hydrated alumina and silica. Analyses are given of pseudomorphs after augite from Bilin Bohemia consisting of mixtures of cimolite and anauxite. L. J. S. Lavas of the Active Volcano at Reunion. ALFRED LACROIX (Compt. rend. 1912 154 251-2.57).-8 number of analyses were carried out to ascertain whether the predominance of vitreous lavas at the summit of a volcano and the greater abundance of crystalline ones near the base is associated with differences in the chemical composition of the two varieties. I. Mean of analyses of three normal ancient lavas and fived' modern ones three being crystalline and the others vitreous.11. An abnormal modern lava very rich in peridote SiO,. A1,0,. Fe,O,. FeO. MgO. CaO. N%O. K20. TiO,. P,O,. H,O. Total. I. 48'22 14'74 2.24 9-38 7.01 12-26 2-23 0'89 2.72 0'36 0.06 100*11 11. 43.82 10-10 2'98 10-44 20'89 7-66 1.44 0.62 2.07 0.21 0.02 100-25 The results show that the crystalline condition of the lava is independent of the chemical composition. The abnormal lava resembles more closely certain Tahiti rocks than any hitherto described. It appears to be a felspathic picrite rather than zt basalt and is distinguished by the abundance of very large macled crystals of olivine containing grains of magnetite. The mineralogical characteristics of highly crystalline stalactites andii. 268 ABSTRACTS OF CHEMICAL PAPERS stalagmites of lava are described.Chemically they do not differ from the normal rock but probably owing to more rapid cooling are lacking in crystals of olivine. w. 0. w. Composition of the Mineral Water of Bad Diirkheim G. RUPP (Zeitsch. Nahr. Genussrn. 1912 23 56-59).-An analysis is recorded showing the quantities of mineral constituents in t h i s water. The results obtained agree with those found by analyses in the year 1860 as regards the chief constituents but the earlier analyses make no mention of the appreciable quantities of arsenic present in the water; as the general composition of the water bas not changed arsenic has probably been present in the water for some time. The amount of arsenic found in the present analysis was 0.01735 gram of arsenic trioxide per kilo. of the water (compare Abstr. 1907 ii 485). w. P. s. New Analyses of Water from the Dead Sea. A. FRIEDMANN (Chem. Zeit. 1912 36 147. Compare Stutzer and Reich Abstr. 1907 ii 791).-The samples were taken by the author (I) at a depth of half-a-metre and (11) a t a depth of 3 metres near the north-west end of the Dead Sea the temperature of the water being 2 7 O and that of the air 34O. I n a 30 cm.-high measuring cylinder both samples of water were clear and transparent with a tinge of blue colour; they possessed a bitter saline taste were alkaline to litmus and lead acetate paper was blackened when held near the mouth of the cylinder. Analysis gave (percentage by weight) Total solids CaCO after drying iron org. D1-5. at 140'. NaCI. KCI. CaCI,. MgCI,. NaBr. CaSO,. matter. I. 1-1241 23.8500 7-8550 1.5208 3.6800 10.0299 0.5200 0'1460 trace 11. 1.1336 24.1309 7'9325 1'4318 3'6903 10'3125 0.5212 0'1412 trace T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9120205263

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 268 ABSTRACTS OF CHEMICAL PAPERS Physiological Chemistry. Action of Ironron the Mobile Oxygen of Blood. GIUSEPPE ROCCHI (Chem. Zentr. 1911 ii 1870; from Arch. B'arm. sperim. 1911 12 317-324).-That portion of the oxygen in blood which is com- bined with hsmoglobin and may be estimated by reducing agents is termed mobile oxygen by the author. Results of experiments on dogs showed that the injection of iron (6 to 12 mg. per kilo. of body-weight) resulted in a diminution of the mobile oxygen during the first thirty minutes followed by an increase in the next two hours. Experiments in zn'tro also proved that the addition of ferrous sulphate to blood increased the quantity of mobile oxygen. Probably the activity of the oxydases is increased. w. P. s.PHYSIOLOGICAL CHEMISTRY. ii.269 Iron in Blood. HERMANN W. FISCHER and E. BRIEGER (Zeitsch. phylsikal. Chem. 1912 78 582-628. Compare Abstr. 1910 ii 856). -The paper does not deal directly with iron in blood but with certain colloidal systems containing iron saks and ‘‘ protective ” substances which favour the retention of iron compounds in the colloidal con- dition. It is shown that in many respects these soIutions behave like solutions of hemoglobin. Their behaviour towards hydrogen peroxide (which may be regarded as oxygen under high pressure) has been investigated in detail. The rate of decomposition of the peroxide WAS followed by measuring the oxygen evolved and i n most of the experiments the solutions were not shaken. The results are only qualitative. The decomposition of hydrogen peroxide in acid and alkaline ‘‘ protected ” solutions was investigated. As protective agents glycerol and other hydroxyl compounds were used.I n acid solution the protective substance is oxidised and the iron reduced ; in slightly alkaline solution on the other hand the protective substance is not attacked brit the iron is oxidised to ferrate. The iron compounds obtaincd in acid soliltion are unstable and have characteristic colours. One of these compounds which i s deep violet in colour appears to be intermediate in composition between ferrous and ferric salts ; in other words it corresponds with magnetic oxide of iron. A number of experiment’s with different protective agents are described. The ferrate solutions obtained by oxidation in weak 31 kaline solu- tion are so similar in behaviour t o hzemoglobin with regard to colour power of absorbing oxygen etc.that it is assumed that the mechanism of oxygen absorption is similar in the two cases. On this basis it is suggested that the capacity of hemoglobin to take up oxygen forming a peroxide depends on its being nearly neutral. When the blood reaches a part of the body where carbon dioxide is being given off it becomes more acid; the peroxide is then unstable and decomposes giving up oxygen. This theory is also applied to the action of muscles. The Glucose of Blood-serum. LEONIDAS DOXIADES (Biochem. Zeituch. 191 2 38 306-309 j.-When 20-30% dextrose solutions are treated with blood-serum there is an increase in the optical rotation and a diminution of the reducing power for Allihn’s copper solution.These facts together with certain results obtained by the isolation of the osazones lead the author to believe that maltose is produced and t h a t the blood-serum contains a synthesising enzyme. A Simple Coagulometer. HENRY H. DALE and PATRICK P. LAIDLAW (J. Path. Bact. 191 2 16 351-362).-The coagulation time can be accurately determined in a drop of human blood drawn from a finger prick. It is collected in a capillary tube containing a shot ; t h e end point is the moment when the shot no longer moves when the tube is held vertically. I n comparative observations the bore of the tube the size of t h e shot and the temperature must be constant. The time SO determined in normal individuals only varies by a few seconds. Administration of calcium salts or of adrenaline and a milk diet made no appreciable difference.G. S. S. B. S. W. D. H.ii. 270 ABSTRACTS OF CHEMICAL PAPERS Gastric Acidity. JUSTIN WINTER (Compt. rend. 1912 154 72-73. Compare Abstr. 1910 ii 786).-The author qiiotes the results of experiments carried out on a dog. After special test meals the stomach contents were removed by a sound and their acidity and hydrochloric acid content determined. The conclusions drawn are that hydrochloric acid is produced in three successive stages the first of which involves formation of neutral organic hydrochlorides the second corresponding with the acidification of these substances and the third to their dissociation with production of free hydrochloric anid. The last stage does not occur when the animal is fed on water or sugar solution alone but requires a stronger stimulus such as that supplied by meat or other nitrogenous material or by the irritation caused by experimental gastric fistulae.The effect of the latter has not hitherto been taken sufficiently into account in such observations w. 0. w. The Hourly Chemical and Energy Transformations in the Dog a f t e r an Abundant Meat Diet. H. B. WILLIAMS J. A. RICHE and GRAHAM LUSK (Proc. Anzer. pliysiol. Soc. 1911 xxxiii-xxxiv ; Amer. J. Physiol. 29)-A calorimeter of great accuracy (Atwater-Rosa type) was ueed. A dog was fed on 700 grams of meat a t noon and next da.y its metabolism measured between 10 and 11 a.m. A t mid-day i t received 1200 grams of meat and it was returned to the calorimeter.Heat production and other factors were then determined hourly for twenty hours. Direct and indirect calorimetry agreed perfectly. Heat production rose largely and this was proportional to the nitrogen eliminated in the urine and not to the quantity of material in the intestine. The carbon which was retained from the protein must have been retained as glycogen for if it had been retained as fat oxygen absorption would have been 10% less than it was. Glutamic acid added to a standard diet did not increase heat production. W. D. H. Creatine and Creatinine Metabolism. CHARLES G. L. WOLF (J. BioZ. Chem. 1912 10 473-478).-A discussion of previous results from which the conclusion is drawn that a disturbance of carbohydrate metabolism (emphasised by Mendel and Rose) or a disturbance of liver fiinctions (as in dogs with Eck’s fistula) will not alone explain the excretion of creatine. The other processes which contribute to this end will be considered later. W.D. H. Creatine and Creatinine Metabolism in Dogs During Feeding and Inanition with Special Reference to the Function of the Liver. C. TOWLES and CARL VOEGTLIN (J. Biol. Chew. 1912 10 479-497).-’J!he view is taken that the liver does not play the important r6le in creatine metabolism which is ascribed to it. Sometimes creatine appears in the urine after the administra- tion of creatinine ; occasionally it is the other way round ; possibly the reaction is a reversible one. On a fixed diet creatinine excretion is kept constant by an adjustment between its production in kntabolism and its destruction by enzymes.The portion excreted by the kidney is the part which is not destroyed. W. D. H.PHYSIOLOGICAL CHEMISTRY. ii. 271 Retabolism of Histidine. HENRY D. DAKIN and ALFRED J. WAKEMAN (J. Bio?. Chm. 1912 10 499-502).-1t has been shown previously that acetoacetic acid can arise from aromatic amino-acids such as tyrosine. It is derived from four adjacent carbon atoms two in the side-chain and two in the cyclic nucleus. The histidine molecule shows four carbon atoms similarly placed and that it also may form acetoacctic acid is confirmed by experiments on the perfusion of dogs’ livers ; the perfusion fliiid consisted of blood to which histidine carbonate was added ; after fifty minutes there was a slight increase in the acetoacetic acid of the issuing fluid.The histidine molecule is probably first resolved into ammonium carbonate (which may then form urea) and acetoacetic acid (which may then undergo further oxidation reduction or hydrolysis) and a urea group derived from the nitrogen atoms of the ring. This would accord with the experiments of Abderhalden and Einbeck and oE Kowalewsky who found that when histidine is given to dogs urea was apparently the only kntabolic product excreted. W. D. H Protein Metabolism from the Standpoint of Blood and Tissue Analysis. OTTO FOLIN and W. DENIS (J. Biol. Chem. 1912 11 87-95).-Many observers consider that the fate of amino-acids after absorption is mysterious because so little is discoverable in the blood. As a matter of fact the non-protein nitrogen of the blood does rise and fall in reference to absorption but the amino-acids pass rapidly to the tissues and for a time accumulate there.Their deamidation in the liver does not occur so ra.pidly as some observers have considered. I n the present preliminary paper experiments are described which give analyses of the blood and certain tissues especially muscle after the absorption of urea glycine the abiuretic product’s of pancreatic digestion and egg-albumin from the intestine. There is also a comparison of the blood (portal and systemic) in fasting and fed cats. The increase of non-protein nitrogen is quite manifest after absorption. The new note struck is that the tissues act as a storehouse or reservoir for a time and this mill have to be reckoned as an importrant factor in theories of protein metabolism The full publication of methods etc.is deferred. R61e of Proteins in Growth. THOMAS B. OSBORNE and LAFAYETTE B. MENDEL (Proc. Amer. phpsiol. Xoc. 1911 xii ; Amer. J. Physiol 29. Pull details i n PubZication 156 Part 11 Camegie Inst. of Washington 191 l).-Some proteins are adequate for maintenance and growth ; others are not. Maintenance and growth moreover must be distinguished. The experiments were made on rats and single proteins were added to their diet (protein-free milk). I n promoting growth casein lactalbumin egg-nl bumin edestin glycinin and glutenin are adequate ; zein gliadin and hordein arc3 inadequate. Gliadin and hordein are adequate for maintenance zein is not. The inadequate proteins are all deficient in two or more of the usual amino-acid complexes.W. D. H. Studies in Nutrition. IV. The Utilisation of the Proteins of the Legumes. LAFAYETTE B. MENDEL and MORRIS S. FINE (J. B i d . Chem. 1912 10 433-458. Compare Abstr. 1911 ii 1109 ; this vol. ii 63).-In comparison with the other vegetable proteins W. D. H.ii. 272 ABSTRACTS OF CHEMICAL PAPERS. investigated the legume proteins are less well utilised This is explained in part in the case of soy bean flour and a preparation from white beans by the presence of cellulose and hemicellulose; but this explanation cannot apply to phaseolin (a protein isolated from the white bean) or to globulin separated from the pea. W. D. H. Studies in Nutrition. V. The Utilisation of the Proteins of Cotton Seed.LAFAYETTE €3. MENDEL and MORRIS 8. FINE (J. Riol. Chem. 1912 11 1-5).-E'raps states that S8% of the proteins of cotton seed are utilised by steers and sheep. A lower figure (67-75%) was obtained in the present experiments on dogs. W. D. H. Studiee in Nutrition. VI. The Utilisation of the Proteins of Extractive-free Meat Powder; the Origin of Fecal Nitrogen. LAFAYETTE B. MENDEL and MORRIS S . FINE (J. Biol. Chem. 191 2 11 5-26).-The meat residue employed was supplied by Armour & Co. and was a light brown powder. The utilisation of its nitrogen by dogs was distinctly lower than that of fresh meat. The faxes were relatively rich in nitrogen which indicates a loss through tho excrements. On ordinary meat diet protein utilisntion is at least 95% and the resulting faxes are for the most part of metabolic origin.Very little nitrogen comes from the intestinal juices for these are mainly re-absorbed. This however will depend on the rate of peristalsis and that in time is influenced by the mass and character of the intestinal contents. Hence if indigestible material is added to meat peristalsis is accelerated and more metabolic products will escape absorption. If the material added is non-nitrogenous the nitrogen % of the fzeces will be lower ; but if the comparatively indigestible material is nitro- genous the nitrogen concentration will be higher. If both types are present the amount of nitrogen may be indistinguishable from that found in meat faeces. W. D. H. The Formation of Organic Phosphorus Compounds from Inorganic Phosphates in the Animal Body.GUSTAV FINGERLING (Bzochern. Zeitsch. 1912 38 448-467).-'L'he animals experimented on were ducks which were fed during one season on foodstuffs nearly free from organic phosphorus compounds with addition of organic phosphates and in another season on foodstuffs rich in organic phosphorus compounds. The weights of the egg laid and their con- teDt in lecithin-phosphorus and nucleic acid-phosphorus were esti- mated. From the results little difference was observed in both the quantity and composition of the eggs laid under different conditions from which the conclusion was drawn that the organism can synthesise organic phosphorus compounds from inorganic phoshates. 8. B. a. Absorption of Fat by the Stomach in the Salmon. CRARLES W. GREENE (Proc.Amer. physiol. SOC. 19 11 xxxvi-xxxvii ; A Ither. J. Physiol. 29).-Young salmon were fed with olive oil per rectum.PHYSIOLOGlCAL CHEMISTRY. ii. 273 Subsequent microscopic examination after suitable fixation and staining showed that fat globules were present in the surface epithelium of both the cardiac and pyloric regions of the stomach. W. D. H. Absorption of Fat by the Mammalian Stomach. CHARLES W. GREENE and WILLIAM F. SKAER (Proc. Amer. physiol. Soc. xxxvii-xxxviii; Amer. J. Phgsiol. 2Q).-In dog cat and rat the evidence that fat absorption occurs in both regious of the stomach is similar to that adduced in the case of the salmon (see preceding abstract). W. D. H. Data from Two Fasts Each Exceeding One Hundred Days in Length in the S a m e Dog.PAUL E. HOWE and PEILIP B. HAWK (Pvoc. Amer. physiol. Soc. 1911 xiv; Amer. J. Physiol. 29).- The initial fast gave the animal a sort of resistance which enabled i t to resist more successfully the demands made on it by the second. The loss oi' weight and the rapidity of the loss were much less in the second period of inanition. How do Isotonic Sodium Chloride Solution and other Parthenogenic Agents Increase Oxidation in the Sea Urchin's Egg? J. P. MCCLENDON and PHILIP H. MITCHELL (J. Biol. Chern. 1913 10 459-472).-The main conclusion reached is that hydroxyl ions in t h e medium increase the rate of oxidation in the egg-cells. W. D. H. The Differences in the Composition of the Brain Substance in Normal and Starving Animals. KAFFAELE PALADINO (Biochem. Zeitsch.19 12 38 443-447),-In experiments carried out on dogs it was found that the water conteut in the brain of fasting animals was higher than that of normal animals. Parallei with the increase of water there is a diminution of ether-soluble substances. No differences could be detected in the quantities of the other brain constituents (cholesterol proteins lecithin). The Liver and Regeneration of Fibrinogen. WALTER J. MEEK (Proc. Amer. phpsiol. SOC. 1911 xix-xx ; Amer. J. Physiol. 29). -Fibrinogen was estimated as fibrin. Dogs were bled the blood whipped and then re-injected ; fibrinogen is regenerated rapidly and 100% increase was noted in three hours. After an Eck fistula and ligature of the portal vein this occurred more slowly; but if the other blood supply the hepatic artery was also tied regeneration did not occur and the fibrinogen left in the blood rapidly disappeared.Whether the liver itself forms fibrinogen or by means of a hormone influences the formation of this substance elsewhere is uncertain. W. D. H. S. B. S. W. D. H. The Effect of Eck's Fistula on Bile Formation. SAMUEL A. MATTHEWS (Proc. Amer. physiol. Xoc. 191 1 xxvii-xxviii ; Amer. J. Physiol. 29).-Dogs become jaundiced after ligature of the bile ducts and generally die within a fortnight. If however a biliaryii. 274 ABSTRACTS OF CHEMICAL PAPERS. fistula is also made no jaundice develops although the animals suffer from digestive troubles. If further an Eck’s fistula is established bile flows from the biliary fistula for five or six days and then ceases and no jaundice comes on.If the ducts are ligatured and then after the onset of jaundice an Eck’s fistula is established the jaundice clears off and the dogs become fairly healthy in a few days. It therefore appears that the portal blood contains the substance out of which the liver makes bile or which stimulates it so to do. W. D. 8. The Place of Retention or Reconjugation of the Amino- acids in the Body. ALBERT WOELFEL (Pvoc. Amer. plrysiol. Soc. 1911 xxxviii-xxxix ; Amer. J. Physiol. 29).-If the mediation of the liver or of the intestinal mucosa is necessary for the regeneration of protein out of its cleavage products then after shunting these organs out of the circulation introduction of amino-acids should lead to increase of amino-acid or of ammonia in blood and urine.Dogs were used with Eck’s fistula and the hepatic artery tied; solutions of amino-acids were then introduced into I the washed-out intestines; two hours later the animals were killed and the blood and urine collected. Small increases of nmino-acid nitrogen were found in both fluids which were far from commensurate with the amounts absorbed. The same results were obtained from dogs with coeliac axis and mesenteric arteries tied the amino-acids being introduced intravenously. I n other words the tissues in general manifest an avidity for amino-acids and presumably use them for the regenera- tioa of their protein constituents. HARELY J. CORPER (J. Biol. Clhem. 1912 11 27-35.)-Eatimations of water nitrogen ether- soluble material phosphorus etc. are given in averages from the examination of three normal dogs’ spleens.The purines obtained per kilo. of spleen were W. I). H. Chemistry of the Dog’s Spleen. In fresh spleen. in absence in presence Gram. of air. of air. After autolysis After autolysis Guanine 1 ‘09 - - Adenine.. ................... 0.62 - - Hypoxanthine ............ 0’15 0.017 0.004 Xanthine .................. 0’04 1.69 0.09 Uric acid .................. - 1-69 Oxydase guanase and adenase are present but uricase was absent. The Ash of Smooth Muscle. LEON A. RYAN and EDWARD B. NEIQS (Proc. Amer. phyeiol. Soc. 19 1 1 xv ; Arner. J. Physiol. 29). -The smooth muscle of the pig’s stomach contains less potassium and phos- phorug and somewhat more sodium and chlorine than the striated muscle of the same animal but the differences are not great.The Absorption of Fat in the Salmon’s Muscles and its Resorption During the Migration Fast. CHARLES W. GREENE (Proc. Amer. physiol. Soc. 1911 xxxix-xl; Amer. J. Yhysiol. 29)- The salmon stores large quantities of fat in its tissues before it begins .................. - W. D. H. W. D. H.PEY SIOLOQICAL CHEMISTRY. ii. 275 l o fast on entering fresh water. The storage is chiefly in the muscles and the stored fat gradually diminishes until the animal dies after spawning but it is never wholl$ consumed. The storage in the constantly active fin muscles is slight and is chiefly inter-muscular. Eat is thrown into the fibres of the great lateral muscle and kept there in strikingly uniform amount during the entire migration period.This is uo doubt used by the muscle as a source of energy. W. D. I€. Studies on Chicken Fat. I. Occurrence and Perman- ence of Lipase i n the Fat of the Common Fowl (Gallus domesticus). MARY E. PENNIKGTON and JOSEPH S. HEPBURN. 11. Oxidation of Chicken Fat by means of Hydrogen Peroxide. JOSEPH S. HEPBURN ( J . Amer. Chem. Soc. 1912 34 210-222).- Experiments are desciibed which show that lipase occurs in the fat of fowls and is the cause of the fat becoming hydrolysed. Immediately after the bird has been killed the fat exhibits little or no lipolytic activity and it is therefore probable that during life the lipase exists in its -zymogenic form. After death however the enzyme becomes active and the acidity of the fat increases The change occurs less rapidly below Oo than above that temperature.It has been found that the lipase still retains its activity after the fowls have been frozen for as long as eighty-nine months. When fowls are kept in the frozen state the saponification and Hehner numbers of the fat both increase and this change must be due to oxidation. I n view of Dakin's work (Abstr. 1908 i 119) on the oxidation of ammonium salts ol fatty acids with hydrogen peroxide experiments have been made on the action of this reagent on the fat o€ fowls. It was found that the acidity of the fat always increased and that the saponification and Hehner numbers also increased simul- taneously the effect produced being thus the same as that which takes place in the fat when submitted to prolonged freezing. The increase of the saponification value is attributed to the formation of slightly lower homologues of the acids of the fresh fat and that of the Hehner number to the formation of aldehydes and ketones.The corresponding changes in the fat on prolonged freezing are probably due to the action of enzymes. E. G. The Origin a n d Destiny of Cholesterol in the Animal Organism. VIII. The Cholesterol Content of the Liver of Rabbits Under Various Diets and During Inanition. GEORGE W. ELLIS and JOHN A. QARDNER (Pvoc. Roy. Soc. 1912 B 84 461-470).-The total free and combined cholesterol per kilo. of body-weight is remarkably constant in rabbits fed entirely on bran which has been extracted with ether and may be taken as represent- ing the normal cholesterol content of the liver under conditions in which the body-weight is kept constant but no cholesterol or phytosterol is absorbed with the food.After a period of feeding on green food a small increase is noticed indicating that some phytosterol has been absorbed from the food and appeared in the liver in the form of cholesterol. A marked increaseii. 276 ABSTRACTS OF CHEMICAL PAPERS. in the total cholesterol of the liver is noticeable when cholesterol is administered either with the food or by injection into the peritoneal cavity and also when the animals are kept in a state of inanition and are living on their own tissue. These experiments afford further support for the hypothesis previously formulated (Abstr. 1909 ii 498) that cholesterol is a constituent constantly present in a11 cells and that when the cells are broken down in the life process the cholesterol is not excreted as a waste product but is utilised in the formation of new cells.W. J. Y. The Course of the Daily Excretion of Ghlorides ir the Urine. ADOLF HERRNANNSDORFER (PJiiger’s Archiv 19 12 144 169-228).-The excretion of chlorine rises in the morning but is independent of breakfast or the previous evening meal. Meals produce a rise about half an hour later and this is followed by a fall accompanying the formation of the hydrochloric acid of gastric juice. An hour later the curve again rises due to the alkali content of the food. Administration of solutions of sodium chloride has no influence on the excretion; the organic substances in the diet have also no effect. The alkali of the food is all excreted within twenty-four hour&.Potassium ions produce a sinking of the urinary chlorides; this element is held fast by the body especially if it is previously poor in chlorine. Chlorine and water excretion were parallel. Abnormally large intake of protein produces diuresis and increase of urinary chlorides. W. D. H. The Influence of Magnesium Salts and Sodium Acetate on the Acidity of t h e Urine. L. DE JAGER (Biochem. Zeitsch. 1912 38 294-305).-It has been shown by the author that after ingestion of calcium salts a double decomposition takes place with the sodium phosphate the calcium phosphate formed being stored up in the body. A t the same time alkali is withdrawn from the body and to restore equilibrium the urine becomes acid. A similar action follows the ingestion of magnesium salts. I n this case the author assumes that double decomposition takes place between magnesium salt and calcium phosphate in the alimentary tract as a consequence of which (in the case of magnesium sulphate) magnesium phosphate and calcium sulphate are formed of which the former is more readily resorbed.The magnesium phosphate in the intestines exerts an acid action as a consequence of which alkali is withdrawn and the urine becomes acid. In the case of ingestion of sodium sulphate calcium sulphate and sodium phosphate will be formed. Of these the latter is more readily absorbed and on the first day of the experiment the content of urine in ammonia free acid and total acidity showed marked diminution whereas there was an increase of phosphoric acid.Similar results were previously obtained after ingestion of sodium phosphate. After ingestion of magnesium oxide the first effect was that due to alkalis generally after which the effect was that of a magnesium salt. S. B. S.PHYSIOLOGICAL CHEMISTRY. ii. 277 Elimination of Amino-nitrogen from the Depancreatised Dog. HENRI LABB~ and L. VIOLLE (Compt. rend. 1912 154,73-75. Compare this vol. ii 69).-As a result of about three hundred experiments on normal dogs fed on lean meat the daily urinary excretion of nitrogen in the form of amino-acids was found to vary from 0.053 to 0.065 gram. In the case of a dog from which the pancreas had been almost completely removed the daily elimination corresponded with four to seven times this amount.The ratio of amino- acid nitrogen and total nitrogen moreover was about four times greater with the depancreatised animal than in the normal dog. These results are of clinical interest in connexion with pancreatic disease. w. 0. w. Metabolism in an Experimental Fever with Special Reference to Creatinine Elimination. VICTOR C. MYERS and G. 0. VOLOVIC (Proc. Amer. physiol. Xoc. 1911 xviii-xix ; Arner J. Physiol. 29). -Fever was produced in rabbits by inoculation with the bacillus of hog-cholera. The excretion of creatine ran parallel to body-tem- perature ; so also did total nitrogen and urea. Creatinine elimination increased by 30% reaching its climax with the highest temperature. Creatinine excretion followed the crisis. The increased creatinine elimination is regarded as representing endogenous protein meta- bolism which is abnormally intense owing to the rise in temperature.The presence of creatine suggests the exhaustion of the normal glycogen store of energy and perhaps measures the amount of abnormal endogenous protein metabolism. W. D. H. Cell Stimulation by Prolonged Ingestion of Alkaline Salts. FREDERICK P. WILSOK (Bio-Chem. J. 1912,6,162-170).-1n mice fed on food mixed with sodium hydrogen carbonate or alkaline sodium phosphate marked wasting occurred ; post mortem the testis was found to be the only organ affected the cells showing evidence of great stimulation. In female mice there was no corresponding change in $he ovaries. I n rabbits wasting also occurred but there were no changes in the generative organs.W. D. H. Calcium Resorption and Calcification. MASAHIKO TANAKA (Biochem. Zeitscli. 191 2,38 285-293).-1n continuation of the former work(Abstr. 191 1 ii,907) the author from histological investigations of animals after injection of calcium salts finds that the calcifications are of the character of metastasis that is to say the calcium salts were either taken up by the blood and spread about or the dissolved calcium salts were resorbed and a secondary decomposition then took place either in the immediate neighbourhood of the injection area or at greater distances from it. In the latter case the striated muscular tissue showed a special disposition for the formation of calcium deposits. I n the kidneys the calcifications had the appearance of secretion deposits. The chemical nature of the salts had no effect on the character of the calcifications and the inflammation and formation of the giant cells surrounding calcifications appoared to be ordinary inflammatory reactions.S. B. S. VOL. CII. ii. 19ii. 278 ABSTRACTS OF CHEMICAL PAPERS. The Relation of Calcium t o t h e Gardio-Inhibitory Function of the Vagus H. H. HAGAN and J. K. ORMOND (Proc. Amer. physiol. Xoc. 1911 x i ; Amer. J. Physiol. 29).-In frogs and turtles the presence of calcium in the perfusion fluid is essential for the production of ‘vagus inhibition of the heart. If the amount of calcium in the Eolution of sodium chloride is too small for the purpose vagus action is restored by the addition of a small amount of potassium chloride. W. D. H. Pharmacological Action of Vanadium.D. E. JACKSON (Pvoc. Amer. phpsiol. Xoc. 191 1 xxiii-xxiv ; Amer. J. Physiol. 20)- Vanadium produces gastro-intestinal irritation increased intestinal peristalsis and a rise of blood-pressure more lasting but less pronounced than that caused by adrenaline. Constriction of the arterioles is present in kidney intestine and spleen but not in the leg. This action is peripheral not central E. WACE CARLIER (Bio-Chem. J. 1912,6 182-199).-The effects of allyl compounds on respiration blood pressure and heart are illustrated by numerous graphic records. The toxic action is very great and is due to the allyl in the compounds but is increased in some cases and lessened in others by the substances with which it is combined. Garbanlido-acid Formation.WALTER WEILAND (Biochem. Zeitsch. 19 12 38 385-392).-MThen leucine and other amino-acids are treated with carbamide they readily form carbamido-acids. If leucine is added to urine and the solution boiled carbamido-leucine is formed. A certain amount of the carbamido-acid is also formed when the solution is evaporated a t a temperature not exceeding 42-45’. The author suggests that certain amino-acids can be identified by the preparation of these derivatives which are in some cases more readily prepared than the naphthalenesulphonyl compounds. W. D. H. Phyaiology of Ally1 Compounds. W. D. H. S. B 5. 11. GUSTAV EMBDEN and ERNST SCHMITZ (Biochem. Zeitsch. 1912 38 393-40S).-By perfusing the ammonium salts of a-keto-acids through the liver the corresponding a-amino-acids are formed. By the per- fusion of the ammonium salt of pyruvic acid alanine was obtained whilst the ammonium salt of phenylpyruvic acid yielded phenyl- alanine that of p-hydroxyphenylpyruvic acid tyrosine and that of a-hydroxyisohexoic acid and the corresponding keto-acid leucine.Tyroeine and alanine were isolated in the form of the naphthalyl- sulphonyl derivative and leucine and phenylalanine in the form of the corresponding carbamido-acids (see preceding abstract). The surviving livers of dogs and dog’s blood were employed in the experiments the perfusion apparatus already described being used and the perfusion lasted generally ninety minutes. Full details as to the methods of preparation of the substances perfused and the methods of isolating the products formed are given by the authors The amino-acids were obtained in optically active forms.The Synt,hetic Formation of Amino-acids in the Liver. S. B. S.PHYSIOLOGICAL CHEMISTRY. ii. 279 The Synthetic Formation of Amino-acids in the Liver. 111. The Formation in the Liver of Amino-acids not Obtainable by Protein Hydrolysis. KURA EONDO (Biochern. Zeitsch. 1912 38 407-413).-1n addition to amino-acids which are obtained by the hydrolysis of proteins of the body other amino-acids can be synthetically formed in the liver by the perfusion of the corresponding a-keto-acids. The author has succeeded in this way in obtaining a-amino-m-butyric and a-amino-n-hexoic acid by the perf usion of the ammonium salts of a-ketobutyric and a-ketohexoic acids. For the preparation of the latter substance the method of Bouveault and Locquin was used.The butyric acid derivative was isolated in the form of the naphthalenesulphonyl compound and the hexoic acid derivative in the form of the carbamido-compound. Both the synthetic acids were optically active. The technique employed was The S y n t h e t i c Formation of Amino-acids in the Liver. IV. The Formation of Alanine from Glycogen. HANNI FELLNER (Biochern. Zeitsch. 1912 38 414-420).-As it is known that the a-hydroxy-acids and the corresponding keto-acids give rise to amino- acids by perfusion of the ammonium salts through the liver it was also conceivable that amino-aci+ could be formed directly from carbohydrates which on perf usion through the liver by themselves give rise to a-hydroxy-acids (lactic acid) if ammonium salts were at the same time present.The author has in fact succeeded in obtaining alanine by perfusing livers containing abnormally large amounts of glycogen the amino-acid being formed if a t all only in very small quantity when a glycogen-poor liver is perfused. The Behaviour of d-a-Glucoheptonic Acid in the Organism of the Rabbit Dog and Man. KOHSHI OHTA (Biochem. Zeitsch. 1912 38 421-433).-The investigations with this acid were under- taken in view of the fact that its lactone is a sweet substance which has been employed instead of sugar in the case of diabetes. The acid on treatment with dilute hydrochloric acid is readily converted into its optically active lactone and by determining the polarisation of urine after this treatment the amount excreted could be readily ascertained. In the various experiments on man 12.3% up to 50% of the acid was excreted unchanged; in the case of dogs up to 70% was burnt up in the body although there were considerable individual differences.In the case of rabbits there were also considerable individual variations but more than 80% was utilised in the organism. The Physiological Action of the Four Isomeric Piperonyl- acrylbutylamides. HERMANN THOMS and F. THOMEN (Biochm. Zeitsch. 1912 38 492-496).-Thc isobutyl derivative has been shown by the authors to exist in the root-bark of Fagara xccnnthoxy~oides (this vol. i 115). I t has also been obtained synthetically. In addition the authors have also prepared the corresponding normal secondary and tertiary butylamides and have submitted these the same as that described in the preceding papers.s. B. 8. 5. B. S. The acid was also in certain cases directly isolated. S. B. S. 19-2ii. 280 ABSTRACTS OF CHEMICAL PAPERS. substances to physiological investigation by Kobert and Rost a summary of whose report is communicated. All substances act in a similar way exerting a narcotic action. Antagonism between Salts and Anaesthetics. I. The Conditions of the Anti-stimulating Action of Anaesthetics and of their Protective or Antitoxic Action. RALPH S. LILLIE (Arne?*. J. Pkysiol. 1912 29 372-397).-Isotonic solutions of sodium chloride cause in Arenicola larvae strong muscular contractions and a loss of pigment ; anastbetic concentrations of ether chloroform alcohol and chloretone prevent both ; that is they prevent stimulation and increase of permeability.This protective or antitoxic action resembles that of calcium or magnesium chloride. Chloral hydrate urethane benzene xylene and toluene act in the same direction but less powerfully and more gradually. The Metabolic Influence of Ether Anasthesia. E. I;. Ross and PHILIP I;. HAWK (Proc. Arne?.. physiol. ~ o c . 1911 xvii-xviii ; Amer. J. Physiol. =).-Ordinary and ‘‘ dehydrated ” ether both pro- duce in dogs after two hours’ inhalation a glycosuric condition if the carbohydrate of the diet is entirely replaced by meat ; but when the diet contains 3.3 to 4.1 grams of carbohydrate per kilo. of body-weight this does not occur. Narcotics and Local Anaesthetics. 111. The Stability of the Bases of Local Anaesthetics in Solution.OSKAR GROS (Arch. exp. Path. Pharm. 1912 67 126-131).-Cocaine is rapidly decomposed in solution and so if kept will produce a smaller effect on nerve than the hydrochloride; this will probably explain how Symes and Veley (Abstr. 1911 ii 508) obtained results which differ from the author’s. S. B. S. W.D. H. W. D. H. Alypin and novocaine are more stable in the free atate. W. D. H. Narcotics and Local Anmsthetics. IV. T h e Action of Novocaine Salts OSKAR GROS (Arch. exp. Path. Pharrn. 1912 67 132-136).-Experirnents on the frog’s sciatic nerve show that the salts of novocaine act more powerfully as anasthetics the more they are hydrolysed in solntion that is the more base is liberated. Arranged in order of activity the salts investigated were borate hydrogen carbonate secondary phosphate acetate and chloride.W. D. H. The Action of Protracted Cocaine Administration in Animals. JULIUS GRODE ( A ~ c h . exp. Path. Pha~rn. 19 12 6’7 172-190).-Although there is evidence that in man habituation to the use of cocaine occurs the present experiments on dogs cats and guinea pigs show that in these animals there is not only no habit- uation but there is an increase in their sensitiveness towards the drug. W. D. H. The Influence of Various Alkaloids on the Capacity of t h e Liver for the Formation of Urea in vitro. GIOVANNI BATTISTA ZANDA (Chem. Zentr. 19 12 i 156 ; from Arch. Farm. sperim. 1911 12 418-423).-The amount of urea formed by the liverPHYSIOLOGICAL CHEMISTRY. ii. 281 in vitro is increased by cocaine when present in the fluid to the extent of 0*1-0*25% ; quantities of 0.5% have no influence whereas 1-2% has an inhibitory action. Morphine (even in doses of 0.1%) quinine quinidine and strychnine exert an inhibitory influence.S. B. S . Action of Adrenaline on Blood-vessels. S. OGAWA (Arch. exp. Path. Pharm. 1912 67 89-110).-Experiments on the frog and on isolated organs (kidney intestine skin and muscle) show that the typical action of adrenaline is constriction of blood-vessels but in very low concentrations the effect may be dilatation or dilatation may follow the primary constriction; this is probably clue to an action on the vaso-dilator nerves. The action of d-adrenaline is weaker than that of I-adrenaline. W. D. H. Glycoeuria Produced by Subcutaneous and Intra-muscular Injections of Adrenaline.I. S. KLEINER and SAMUEL J. MELTZER (Proc. Arner. physiol. s'oc. 1911 xxvi-xxvii ; Amer. J. Physiol. 29). -Intravenous injections of adrenaline is the least favourable method of producing glycosuria. The view that any method which favours rapid absorption of this substance into the blood is unfavour- able t o the production of glycosuria is supported by experiments which show that intra-muscular injections (rapid absorption) in rabbits produce less glycosuria than subcutaneous injections (slow absorption). W. D. H. The Toxic Effect of Oxalates and the Physiological Action of Calcium. OSCAR LOEW (Bioclaem. Zeitsch. 1912 38 226-243).-. Neutral potassium oxalnte is poisonous to the lowest animal organisms and also to plants with the exception of the very low species of alge and moulds which have no physiological needs for calcium.There appears therefore to be a relationship between the toxicity of oxalates and the physiological function of the calcium. Observations show that the toxic action takes place in the nucleus and chloroplasts from which the conclusion is drawn that a combination with the calcium takes place in these parts. Physiological facts indicate that this combination also takes place in the cell nucleus of animal organisms. S. B. S. Toxicity of Arsenic Compounds Employed in Thera- peutics. ANTOINE MOUNEYRAT (Con~pt. rend. 191 2 154 284-286. Compare Abstr. 1903 ii 444).-Experiments on rabbits with in- jections of salts of diaminodihydroxyarsenobenzene and its dichloro- and di-iodo-derivatives show that other conditions being the same the danger of a fatal result increases as the interval between successive injections is diminished.After death arsenic is found in the liver and muscles but is specially localised in the nervous centres. w. 0. w. Grayanotoxin the Poisonous Constituent of Leucothoe Grayana Max. 0. KUBO (Arch. exp. Path. €'harm. 1912 67 11 1-1 17).-Grayanotoxirc was separated from the leaves of theii. 282 ABSTRACTS OF CHEMICAL PAPERS. ericaceous Japanese plant named above. It is neither a glucoside nor an alkaloid. It cry stallises in colourless needles melts at 222-223O and has the empirical formula C,HI,O,. It causes fibrillary twitcbings in frog’s voluntary muscles and finally paralyses motor nerve-endings. It acts on the frog’s heart like aconitine. It cis easily absorbed in the rabbit and in the dog causes vomiting however administered. It causes motor paralysis and kills by stopping the respiration. W. D. H. Cynanchotoxin the Poisonous Constituent of Cynanchum caudatum Maxim. and Phytolaccotoxin. K. IWAKAWA (Arch. exp. Path. Phccrrn. 1912 6’7 118-125).-Cynanchotoxin is prepared from the root of the plant and is used therapeutically in Japan. It belongs to the picrotoxin group. It produces convulsions and slow- ing and finally stoppage of the heart acting on centres in the central nervous Bystem. Experiments on frogs and warm-blooded animals are described and details given of the lethal doses. Phytolaccotoxin previouely-described as the active constituent of Phytolucca acino8a is the same substance. Doubt however has been thrown on its presence in P. acz’nosa and there is some reason to think that the plant from which it was obtained was in reality C. caudaturn. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9120205268

出版商:RSC    

年代:1912

数据来源: RSC