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INORGANIC CHEMISTRY 135 Inorganic Chemistry. Direct Determination of the Atomic Weight of Chlorine with reference to Oxygen PHILIPPE A. GUYE and G. PLUSS (J. Chim. Phys. 1908 6 732-'768).-The atomic weight of chlorine with reference to oxygen has been determined by the complete analysis of nitrosyl chloride NOCI. Nitrosyl chloride was prepared according to Tilden's method (Trans. 1874 27 634) by distilling a mixture of perfectly dry nitrosulphonic acid aEd sodium chloride and purified by crystallisation and finally by fractional distillation. Contrary to the statement of Sudborough (Trans. 1891 59 655) aluminium is not attacked by gaseous nitrosyl chloride in the cold; above 500° however interaction takes place with formation of a white and a yellow substance the former being aluminium chloride.Selenium and sulphur are changed to the lower chlorides S,CL and Se2C12 by the action of gaseous nitrosyl chloride. Silver foil does not completely decompose the gas but the latter is decomposed quantitatively by heating with finely-divided silver a t 40O-5OO0 the chlorine being completely retained by the silver and nitric oxide liberated. The fact last mentioned has been taken advantage of for the quantitative analysis of the gas; the nitric oxide is split up and the oxygen retained by heated copper and finally the nitrogen is retained by heated calcium. The precautions taken to obtain accurate results are fully described. As a mean of five experiments the value Cl=35.438 is obtained It has m. p. 61° and b. p. - 5.6'.136 ABSTRACTS OF CHEMICAL PAPERS.from the ratio C1 0 and Cl= 35,471 from the ratio C1 NO (N = 14.01). The most probable value is Cl=35*46d obtained from the first ratio which compares with the value Cl=35.462 obtained by Edgar (H = 1.0076). From the experiments the value N = 14.006 is obtained for the atomic weight of nitrogen in good agreement with' the international value. The investigation is being continued. The Deacon Process. G. S. KURT VOGEL VON FALCEENSTEIN (Zeitsch. Compare Abstr. 1907 ii 19 538)-In the practical working of the Deacon process 40% of hydrogen chloride and 60% of air are led through the apparatus heated at 430'. Under these conditions 70-71% of the hydrogen chloride introduced is converted into chlorine and it is shown theoretically that this mode of working is the most economical under ordinary con- ditions.Much better yields are obtained however as may be anticipated from theoretical considerations when the issuing gas is freed from water by passing throixgh sulphuric acid and then passed through a second Deacon tube also at 430' ; in this way the yield is raised from 71% t o 83-85% and by repeating the procesa a third time to 87-89% only slightly less than the theoretical value. This method ought to prove economical on the technical scale ; as a matter of fact a British patent embodying the suggested improvement has been in existence since 1895. G. S. H. KLOPSTOCK (Chem. Zeit. 1908 33 21).-A sample of potassium chlorate which accord- ing t o the usual tests contained either active chlorine potassium chlorite or an obscure oxychlorine compound was found to be con- Action of Heat on Iodio Anhydride.MARCEL GUICHARD (Compt. rend. 1908 147 1306-1309 *).-As a preliminary to the determination of the atomic weight of iodine with direct reference to oxygen by analysis of iodic anhydride the effect of heat on the latter has been investigated. When heated above 3004 iodine and oxygen are given off and the undecomposed solid becomes brown. It is now shown that the brown colour is due to traces of iodine which along with oxygen is retained very energetically by the solid ; the brown colour is not modified by heating for some hours at 270° nor by treat- ing the solid with carbon disulphide benzene ether or fuming nitric acid. The only substances capable of removing the colour are those which are capable of dissolving the anhydride and combining with the iodine for example an aqueous solutiou of potassium hydroxide..physikaZ. Chem. 1909 65 371-379. The Active Substance of Chlorates. taminated with potassium bromate. L. DE K. G . S. Production of Ozone with Rotating Anodes. FRANZ FISCHER and KURD BENDIXSOHN (Zeitsch. ccnorg. Chern. 1909 61 13-39).- It has been shown previously (Fischer and Massenez Abstr. 1907 ii 162) that the best yields of ozone in the electrolysis of dilute sulphuric acid are obtained by the use of cooled platinum electrodes the surface of which is divided into narrow strips by non-conducting material. * and Xu.22. SOC. club. 1909 [iv] 5. 86-89.INORGANIC CHEMISTRY. 137 Rotation may be employed instead of internal cooling and several forms of apparatus are described having an anode rotating about a horizontal axis.The anode may consist of thin platinum wires or of platinum foil embedded in glass the edge being exposed by grinding so that the anode surface is a line only 0.1 mm. in breadth. The best form is a thiu disk of foil the edge only of which is exposed. Such an auode yields oxygen containing 23.4% by weight of ozone. Unlike the wire electrodes the yield of such a disk is not improved by rotaticn although rotation increases the life of the platinum by removing the warm acid from its fiurface. The greater efficiency is due only t o the narrowness of the anode surface. C. R. D. Ozone Apparatus. GUSTAV M~LLER (Chem. Zeit. 1908 32 1288 ).-A moditication of Berthelot's apparatus for submitting a slowcurrent of oxygen to the silent electric discharge in the annular space between two surfaces of an electrolyte.Hydrogen Sulphide Generator. W. TH. CLOUS (Chem. JVeekbZad 1908 5 889).-The generator consists of two tubulated aspirators connected at the bottom by a stopcock and at the top by a tube bent twice at right angles. I n the acidcontniner this tube ends just below the cork ; in the sulphide container it extends to the bottom. The acid container is fitted with a safety tube for introducing the acid and the J. V. E. sulphide container with a glass stopcock for drawini off the gas. A. J. TV. Compounds of Sulphur and Chlorine. ERNST BECKNANN [with F. JUNKER and THEODOR KLOPFER] (Zeitsch. physikal. Chem. 1909 65 289-337).-There are three well-defined chlorides of sulphur. Sulphur monpchloride S,CI is a yellow liquid b.p. .137-13S0 m. p. - 75" to - 76'. It has very little tendency to give off chlorine nor has it much tendency to unite with chlorine at the boiling point of the latter even in the presence of the dichloride but combination takes place at higher temperatures. Siilphur dichloride SCI is a dark reddish brown liquid b. p. 59'/760 mm. 22'/110 mm. and - 24O/4 mm. It undergoes consider- able decomposition when distiiled at atmospheric pressure but very little at lower pressures. It begins to solidify at - SOo and at - SSo forms a tallow-like solid orange-yellow in colour. It begins to fuse when the temperature reaches - 78O ; Dlj = lb622. Sulphur tetrachloride SCl is formed immediately when chlorine and sulphur dichloride are brought together a t low temperatures.It is separated from mixtures of the composition S 4C1 t o S 6C1 by freezing out the excess of chlorine being removed by centrifugal action. It solidifies completely at - 70° but only fuses completely between - 30' and - 20'. It has considerable tendency to lose chlorine and a t room temperature is probably to a great extent split up into sulphur dichloride and chlorine. The fact that the dichloride and tetrachloride do not fuse at the temperature of solidification is ascribed to the formation of isomeric or polymerised compounds. I n liquid chlorine at its boiling-point both S,C1 and SCI haw the VOL. XCVI. ii. 10138 ABSTRACTS OF CHEMICAL PAPERS. molecular weights corresponding with their formulz and the formula SCl has also been confirmed by cryoscopic determinations in xylene p - xylene ethylene dibromide acetic acid and bromiue.The freezing-point constant for S,CI is 53.6. In this solvent sulphur dichloride dissolves as SCl sulphur as S but the tetra- chloride is insoluble. The freezing-point constant for sulphur dioxide is 30.1. G. S. Action of Sulphur Chloride (S2C1,) on Metalloids and Metals. PAUL NICOLARDOT (Compt. !rend. 190s. 147 1304-1306. Compare Abstr. 19OS ii 1074).-Sulphur selenium white and even red phosphorus dissolve in sulphur chloride in the cold ; in the latter case rapid effervescence occurs. Antimony is attacked in the cold arsenic only on warming to 50° and then only slightly whilst carbon silicon and boron are not affected.The majority of the metals including the alkali and alkaline-earth metals are not affected by sulphur chloride even at 136". Silver copper and zinc are only slightly affected but tin aluminiuni mer- cury and iron are attacked. The action of sulphur chloride on iron has been studied in detail the proportion of the products being determined by a special method of analysis. The main products are ferrous chloride and sulphide In proportions depending on the conditions ; practically no ferric chloride is formed. G. S. ROBERT KREMANN and F. HOFME~ER (Monatsh. 1908 29 llll-l118).-With the object of ascertaining the composition of the hydrates formed by selenic acid the authors bave determined the freezing points of various mixtures of selenic acid and water.melting at 26" and H2Ye0,,4H,O melting a t - 51.7'. The eutectic data are recorded H,SeO and H2Se04,H20 + 19' and 91.5% selenic acid ; H,SeO,,H,O and H2Se0,,4H,0 - 56' and 74.0% selenic acid ; H,Se0,,4H20 and H,O - 83' and 43.0% selenic acid. Crystallisation of the tetra-hydrate is induced by the addition of the corresponding sulphuric acid hydrate indicating that these are isomorphous. Hydrates of Selenic Acid. Only two hydrates are indicated by the data H,SeO4,H20 * . H. M. D. Synthesis of Ammonia by means of Peat. HERMANN WOLTERECK (Conzpt. Terid. 1908 147 1402-1403).-The results of further experiments on the synthesis of ammonia under t h e catalytic influence of peat are described (compare Abstr. 1908 ii 174). After passing the gases over 50 grams of peat at 450" for four hours the ammonia produced amounts to 2.6-3-1 per 100 of the material burned.After four hours the percentage of nitrogen in the residue is greater than that in the peat but after six hours there is a diminution in the percentage of nitrogen present. Silicon Hydrides. PAUL LEBEAU (Compt. rend. 1909 148 i3-45.* Compare Moissan and Smiles Abstr. 1902 tii 318 560). -A large volume of mixed gases bas been obtained by the action of + and BUZZ. SOC. chinz. 1909 [iv] 5 89-91. G. 5.INORGANIC CHEMISTRY. 139 hydrochloric acid on magnesium silicide. The first fraction yielded a gaseous product and a colourless liquid. The gas was again condensed and after repeated fractionation the hydrides SiH and Si,H were obtained pure. The latter hydride had the calculated density less than that found by Moissan and Smiles whose preparation was probably contaminated with a higher hydride ; practically pure Si2H6 boils about - 7’.The colourless liquid above-mentioned explodes violently in contact with oxygen and burns with a bright flame ; it is unsaturated and the probable formula is Si,H,. The spontaneous inflammability of the hydrides SiH and Si,H6 is probably due to the one last mentioned. Finally a small amount of solid which turned brown in air was observed in the apparatus; this may be a solid silicon hydride. G. S. Products of the Arc and Spark Electric Discharge in Liquid Argon. 11. Experiments with Hydrogen Titanium Tin Lead Antimony and Bismuth. FRANZ FISCHE~~ and GEORG l~~ovrcr (Ker. 1908 41 4449-4457.Compare Abstr. 1905 ii 1034).-Experimenth are described with tubes fitted with “outside ” electrodes which show that argon must contain at least 4% of air before the spectrum lines duc to admixed air appear. Furthur comparative exFeriments with argon (D 19.94) under 3.0 0.3 and 0.03 mm. pressure in these tubes shorn that under the higher pressures the “ red ” argon spectrum appears and the follow- ing lines not observed by Travers have been measured A 7600 7465 7380 7235 7130. At 0.03 mm. the red spectrum is no longer visible the blue appearing. Hydrogen argon and mixtures of these gases when subjected to the silent electric discharge at the temperature of liquid air undergo no change in volume and therefore no alteration in molecular condition. When titanium tin lead antimony and bismuth elements from the fourth vertical column of the periodic system are used as electrodes in the arc or spark discharge nitrides in small quantities are obtained which liberate nitrogen when heated in a vacuum and give ammonium salts when treated with acids.This result is due to air introduced into the apparatus; the nitrogen when removed by sparking with oxygen left not a trace of argon behind. W. R. Acid Sulphates. 111. JOH. D’ Am (Zeitsch. ctnorg. Chem. 1909 61 91-95. Compare Abstr. 1906 ii 351; 1907 ii 459).-The solubility of sodium sulphate in water in presence of varying quantities of sulphuric acid has been further examined. The transformation temperature of Na2S04,10H20 into Nn,S04 is lowered by the addition of sulphuric acid the lowest point reached being l(i.67Ok 0 07’.At this temperature the three solid phases Na,SO 1 OH,0-Na2S04- Na,H(SO,),,€€,O are in equilibrium with the solution. The transition point of NaESO,,H,O is found to be 5S.54O + O.OFiO,a temperature which is recommended as a thermometric fixed point. The isothermal at 25O was also determined. C. H. D. 10-2140 ABSTRACTS OF CHEMICAL PAPERS. Dissociation of Sodium Hydrogen Carbonate. SOURY (Compt. Tend. 1908 147 1296-1299).-The phase rule indicates that. in order that there may be a definite gas pressure over sodium hydrogen carbonate at. a definite temperattire four phases must be present for example vapour saturated solution and two solid carbonates in contact with the latter. Experiments were made in which a mixture of 27-54 grams of sodium hydrogen carbonate and 5.4 grams of water were heated a t looo and the pressure measured after removal of the carbon dioxide in successive portions.The t o t d volume of carbon dioxide obtainable from the above mixture is 3660 C.C. The tension of the carbonic acid decreases at first as the carbon dioxide is progressively removed but there are two periods of constant- pressure (1) from t h e removal of 260 t o 1760 C.C. of the dioxide ; (2) from 2560 to 3210 C.C. I n the first case the two solid phases are the hydrogen carbonateand a lower carbonate of the composition 3Na,0,4C0,,5H20 ; a t the second period of constant pressure the solid phases are in all probability the salt last mentioned and the normal carbonate Na,O,CO,,H,O. The dissociation pressure has also been determined a t dieerent temperatures and the results are represented graphically.G. S. Synthesis of Silver Nitrate and Determination of the Atomic Weight of Sulphur. GUSTAVE D. HINRICHS (Chem. Zentr. 1908 ii 1410 ; from Mon. Sci. 1908 [iv] 22 ii 454-460).-Stss’ synthesis of silver nitrate and Richard’s determination of the atomic weight of sulphur are criticised and studied in the light of the author’s method (Abstr. 1907 ii 945). From the investigation of Stas and Marignac and the correct placement of the errors absolute atomic weights have been arrived a t for silver at 108 nitrogen 14 and for oxygen 16. The opinion is held that matter is simple and chemical elements are combinations of simple matter having commensurable atomic weights.J. V. E. Atomic Weight of Silver. ANATOLE LEDUC (Compt. rend. 19OS 147 972-973).-An adverse criticism of a recent paper by Dubreuil (Abstr. 1908 ii 1035). Atomic Weight of Silver. LOUIS DUBREUIL (Comyt. ?end. Compare Abstr. 1908 ii 1035).-Polemical G . S. 1908 147 1300-1 302. against Leduc (previous abstract). G. S. True Atomic Weight of Silver. GUSTAVE D. HINRICHS (Conzpt. rend. 1908 147 1302-1303. Compare previous abhtracts).-In connexion with a recent paper by Dubreuil (Abstr. 1908 ii 1035) the author has given up his recently expressed view (Abstr. 1908 ii 573) that the atomic weight of silver is 107.875 and returns to his earlier opinion that it is exactly 108. ANATOLE LEDUC (Conzpt. Tend. 1909 148 42-43).-Polemical against Dubreuil and Hinrichs (compare G .S. Atomic Weight of Silver. previous abstracts). G. s.INORGANIC CHEMISTRY. 141 Warnerke's Modification of the Herschel Effect and the Preparation of the Substance of the Latent Image. A. P. H. TR~VELLI (Zeitsch. iuiss. Phoiograph. Photoyhysik. Photochena. 1908 6 438-448).-The film of an Agfa diapositive plate was removed placed between two sheets of parchment pdper and subjected to high pressure by beating i t with a hammer in a dark room. After this treatment the film was found to be more easily developed than before indicating that the a-silver subhaloid is insensitive to pressure. On the basis of this observation a method for the preparation of the a-subhaloid has been devised. Silver iodide .precipitated by an excess of potassium iodide and heated for a long time with ammonia is mixed with a saturated solution of silver nitrate to absorb the free halogen and pounded in a mortar. The formation of the subhaloid is facilitated by heating at about 80'.The subhaloid so obtained is leaf-green in colour ; the corresponding subbromide is a little lighter. H. RI. D. Old and New Subhalides. LOTHAR WOHLER and G. RODEWALD (Zeitsch. anorg. Chm. 1909 61 54-90. Compare Wohler and Kasarnowski Abstr. 1906 ii 22).-The evidence for and against the exiatence of subhalides in cnloured solid halides is discussed and it is shown that this explanation of the colour IS at least as probable as that of ultra-microscopic pat ticles of metal. The present research is directed to the isolation and recognition of certain subhalides as chemical individuals.Silver subfluoride Ag,F is prepared in a pure state by the action of silver on a warm solution of silver fluoride forms golden crystals and is quite stable i n dry air. It is insensitive towards even direct light and thus differs markedly from other silver halides. A pressure of 20,000 atmospheres is also without influence. At 90' the solid in a dry state or in contact with a saturated silver fluoride solution de- composes into silver fluoiide and silver. The heat of formation of Ag,F is 26.3 Cal. Its formation from the fluoride is not as Guntz supposed (Abstr. 1890 1055) endothermic but exothermic (0.7 Cal.). Silver fluoride shows a great increase of solubility at 50° due probably to a transition from the hydrate AgF,2H20 to the anhydroiis salt.Calcium subchloride observed incidentally by Borchers and Stockem (Abstr. 1903 ii 191 can only be prepared by heating calcium with dry calcium chloride in equivalent proportions in steel cylinders a t 900-1000° for twenty-four hours followed by rapid quenching i n solid carbon dioxide and treatment with ethyl iodide which allows of the separation of the subchloride and calcium by their density. The red crystals of CaCl heated to 810' and allowed to cool slowly show decomposition into chloride and metal. A small proportion of sub- chloride is sufficient to give a red colour to the chloride. The pure crystals have D20 2-08. Calcium subiodide Gal prepared by heating atomic proportions of calcium and iodine in a steel tube st 800° quenching rapidly and washing the mass with carbon disulphide forms brown crystals and,14 2 ABSTRACTS OF CHEMICAL PAPERS.like the subchloride decomposes if cooled slowly from SOO" yielding calcium iodide and calcium. Calcium subfZuoride CaF is prepared by heating calcium with calcium fluoride above 1400° the steel tube being protected by wrapping in platinum foil and coating with basic fire-clay. The pro- duct forms orange crystals D20 2.305 and is mucfi less readily attnrked by moisture than the subchloride or subiodide. All these compounds are stable only a t high temperatures decomposing into metallic calcium and the normal halicle when cooled slowly. C. H D. Formation of F u l m i n a t i n g Silver. A. SIEVERTS (Zeitsch. ccngew. Chenz. 1909 22 6-7).-A warning as to the danger incurred in working with ammoniacal silver solutions.Ten grams of silver nitrate were converted into oxide by potassium h j droxide and the precipitate was digested a t 40' with 45 C.C. of 6*70/; ammonia for ten minutes. On the surface of the liquid a white crust had formed and a heavy black powder was noticed a t the bottom of the utensil. I n order t o facilitate solution this was stirred with a glass rod when ft yiolont explosion took place doing much damage and seriously wound- ing the operator. Even clear solutions may give rise to explosions. L. DE I<. Crystalline Form of Calcium Carbonate Precipitated from Concentrated Solutions. EMIL HATSCHEH (Chem. Zeit. 1909 33 49).-From concentrated solutions of calcium chloride and with various reagents it is found that at all temperatures from 15' to the boiling point the precipitate consists almost exclusively of calcite.A t temperatures below 15" the carbonate is precipitated in granules which even when kept for some time under the mother liquor do not become crystalline. L. DE K. Experiments Showing the Formation of Nitrides of Barium Strontium Calcium and Aluminium. H. RUSSELL ELLIS (Chem. LVews 1909 99 4).-When the oxides of these metals are mixed with magnesium powder and ignited on an iron tray the magnesium replaces t8he other metal which as soon as i t is set free combines with the oxygen and nitrogen of the air. With barium oxide calcium oxide and strontium oxide the product obtained was quite yellow and when moistened with water smelt very strongly of ammonia; with riluminium oxide the product was black but also smelt strongly of ammonia when water was added. The presence of carbonate hydroxide and peroxide with the oxides of the alkaline-earth metals increases the violence of the reaction and hinders nitride formation. Calcium oxide if carbonate is present gives neither nitride carbide nor cyanide ; barium and strontium oxides contaiuing appreciable quantities of carbonates yield nitride cyanide carbide and possibly cyanamide.Excess of magnesium powder as a rule produces a laiger yield of nitride but never more than that which could be produced from the metal obtained from the oxide. The conclusion is drawn that the nitride produced is not that of magnesium because when magnesium h r n s in air either alone or admixed with the oxide of a metal notINORGANIC CHEMISTRY.143 forming a nitride less than 1% of nitride is obtained. Moreover magnesium nitride readily burns so that if great development of heat takes place it could not exist. Estimations of nitrogen contained in the product from igniting the following mixtures gave (BaO + Mg) 24.4% Ba,N,; (BaO + 2Mg) 43~~3% Ba3N2; (SrO + Mg) 33.7% Sr,N,; (SrO + 2Mg) 53.8% Sr,N ; (CaO + Mg) 33.6% Ca,N2 ; (CaO + 2Mg) 31.5% Ca,N2 ; (A1203 + 3Mg) 11.1% A1N. MARIO G. LEVI and S. CASTELLANI ( A t t i R. Accucl. Lincei 1908 Lv] 17 ii 613-617).-The authors have applied the electrolytic method formerly employed (Guxzetta 1907 37 ii 5G2) for the preparation of borates of sodium to those of other metals. I n the electrolytic cell employed the metallic salt solution containing the platinum anode was separated by a diaphragm from the boric acid solution in which the platinum cathode was placed.With calcium strontium and barium salts the crystalline cathode deposit and the first portions of the white flocculent material pre- cipitated in the cathode compartment have the composition RO,B,O2,4H2O (R = Ca Rr or Ba). I n the case of calcium salts the later deposits in the cathode chamber consist of the pyroborate CaB407,. but with strontium and barium salts these deposits have indefinite compositions as also do the precipitates obtained by the addition of alcohol to the cathode liquid. With magnesium salts the cathode deposit seems to consist of the borate I\IgR204 mixed with a large proportion of magnesium oxide; precipitation of the cathode solution by means of alcohol yields the borate 3Mg0,4B20 With salts of copper cadmium mercury lead iron and nickel no definite borates were formed.J. V. E. Certain Electrolytic Borates. T. H. P. Magnesium-Silicon Alloys. RUDOLF VOGEL (Zeitsch. ccmorg. Chem. 1909 61 46-53).-Molten alloys of magnesium and silicon readily pass through magnesia vessels and strongly attack porcelain ; it is therefore necessary to melt them in carbon tubes in an atmos- phere of hydrogen the porcelain tube enclosing the thermocouple being protected with a layer of carbon. The freezing-point curve fails from the freezing point of silicon to a eutectic point at 950" and 42% of magnesium rises to a maximum a t 1102O and 63.2% Mg corresponding with the compound Mg,Si falls to a second eutectic point at 645" and 96% Mg and again rises to the freezing point of magnesium.The compound Mg,Si forms glistening hard light blue crystals slowly attacked by concentrated siilphuric and nitric acids rapidly by dilute acids with evolution of hydrogen. Hydrochloric acid attacks it violently with evolution of silicon hydride. The microscopic examination of the alloys confirms the above con- clusions. C. H. I>. Solid solutions are not formed. Compounds of Magneeium and Sodium Sulphatss. A. S. QINSBERG (Zeitsch anorg. Chem. 1909 61 122-136).-'L'he144 ABSTRACTS OF CHEMICAL PAPERS. determinations of the freezing-point diagrams of the systems IL$O,-MgSO and Na,SO,-MgSO by the author (Ber. St. Petersburg Polytech.Inst. 1906 6) h;tve been confirmed as regards t h e first system by Nacken (Abstr. 1908 ii 692) but the second system gave somewhat different ie3ults. A re-examination of mixtures of sodium and magnesium sulphates has shown t h a t the equilibrium is very complicated. The freezing-point curve has a eutectic point at 44.8 mol. % MgSO and 670° and a break at 71.3 mol. % and 814'. a-Sodium sulphate forms solid solutions containing up to 35.8 mol. % MgSO,. The compound Na2S0,,3MgS0 melts with decomposition a t 8 1 4 O . Magnesium sulphate does not form solid solutions. The existence of two other compounds Na,SO,,MgSO and 3Na,SQ,,MgSO formed only in the solid state is also indicated. These compounds are identical with anhydrous blodite and vanthoffite respectively the former existing i n a- p- and y-modifications.Sodium sulphate only forms two modifications the transition point being a t 232'. C. 11. D. Gases Occluded in a Complex Brass containing Manganese which showed Numerous Flaws. G. GUILLEMIN and B. DELACHANAL (Compt. rend. l908,147,1309-1311).-The specimen of brass in question contained 60.15% of copper 34.76% of zinc 2.34% of manganese and small amounts of tin lead iron and aluminium and was full of small holes due t o escaping gas. Fifty grams of it were heated in a poicelain tube up to 1000° and the gas given off which amounted to 3.5 times the volume of the alloy collected and analysed. It contained 79.1% of hydrogen 3.9% of methane 8.9% of carbon monoxide and 8.1% of carbon dioxide. G. S. Variations in the Structure of Coinage Bronze during Working.FEDEEICO GIOLITTI and ERNESTO PANNAIN ( A t t i R. Accnd. Lincei 1908 [v] 17 ii 668-670).-'l'he authors have made a metallographic study of the bronze used for Italian coinage which contains 3.82% of tin 95.80% of copper and 0.38% of impurities (about 0.2% of lead). The polished surfaces of the specimens were treated repeatedly with hot 0.24% nitric acid each such treatment being followed by gentle polishing with chromic oxide. The cooled ingots before treatment conlcist of solid solutions a of heterogeneous concentration among which are scattered crystals of the solid solution /3. According to the equilibrium diagrams of alloys of copper and tin (compare Giolitti and Tavanti Abstr. 19G8 ii 946) bronze containing about 4% of t i n should consist entirely of the a-mixed crystals whilst in reality the above structure is nearer t o that given by a n alloy containing more than S% of tin. The presence of the /3-crystals is explained by the velocity with which the alloy cools.This velocity is not sufficiently slow to allow the first a-crystals rich in copper to react with the liquid which becomes less and less rich in copper and is in equilibrium with the crystals separating at continually lowering temperature so as to givefXORGANIC CHEMISTRY. 145 homogeneous mixed crystals. Nor is the velocity suficiently rapid t o prevent at 790° the reiction between the borders of the mixed crystals rich in tin and the residual liquid giving rise t o the P-mixed crystals. After re-heating for half an-hour at about 800° and tempering in cold water tbe heterogeneous masses of a-crystals are transformed into homogeneous crystals with a lamellar structure among which are still seen the p-crjstals.After flattening in the cold both the a- and @crystals are elongated i n the direction of the flattening. Subsequent re-heating and tempering are accompanied b y the appearance of a-crystals having a rectilinear outline these and> also the P-crystals being elongated by further flattening whilst successive re-heating and tempering bring back the former crystalline structure which undergoes only slight deformation during the final flattening. It is note- worthy that the P-crystals formed during the initial cooling of the alloy are pre- served through all the various treat- ments to which tbe ingot is suhjected.T. 13. Y. 5 4 New Apparatus for the Distilla- tion of Mercury. JOHANNES WETZEL (Cliern. Zeit. 1908 52 1228).-Mercury to be purified is placed in a the bent fd tube c is placed in a dish containing pure mercury and b is connected to a e( d / water-pump. By this means mercury is made to rise in both inner tube d and outer tube e until the mercury in e enters the bulbous enlargement i and is within &bout 2 cms. of the mouth of tube d . Water is made to circulate through the condensing head h and the mercury in i is heated by means of a gas ring g. After about thirty minutes 6 is closed and mercury vapour con- densing on the cold surface of h drops on to a float f. When sufficient mercury has collected to lift the float it falls down tube d assisting to more completely evacuate the distillation bulb i.By / ic I- this arrangement i may be almost com pletely evacuated and the purified mercury obtained at c. Mercury boils at 1 5 5 O when in the highest vacuum so that if the apparatus described is made of Jena glass there is little risk of it cracking Indicative of the rapidity of distillation it is mentioned that in ten hours nearly 23 kilos. of mercury may be obtained showing a great increase over Kasten's method generally employed which gives in the same time only about 24 kilos. of mercury. J. V. E.146 ,4ES'l'RA4C1'S OF CHEMICAL I'AYEliS. Use of the Colour Thermoscope. 111. [Silver-Mercury Iodide.] H. REBENSTORFF (Chem. Zentr. 1908 ii 1803; from Zeitsch. phys.-Chem.Unter. 1908 21 29 1-304. Compare Ludtke ibid. lo).-As a result of many physical and chemical experiments it has been ascertained t h a t a liberation of heat accompanies the trans- formation of yellow silver-mercury iodide at 45O into the oraage form. Both modifications of this substance are found t o exist in contact with one mother for quite a considerable time at 33-45'. Distribution of Scandium. WLADIMIR I. VERNADSKY (Bull. ,4 end. Sci. St. Yetersburg [vi] 190S 12'73-1274. Compare Kbei hard Abstr. 1 QOS ii 862).-A criticism of Eberhard's conclusions regard- ing the mineralogical distribution and f orniation of the scandium Aluminium. Analysis of Aluminium Powder. J ~ L E I~OHX- ABREST (Compt. Tend. 1908 147 1293-1296).-The propot tion of aluminium in commercial aluminium powder has been e,-timitted by its reducing action on ferric sulphate as previously described (Xbstr.1904 ii S44) and also by measurement of the hydrogen given OE when a known weight of it is treated with exces.i of Ilydrochloric acid. From A complete analysis it is further shown t h a t the specimen contains .95*930/ of total aluminium as well as iron silicon carbon nitrogen and 2.29% of oxygen the latter being obtained by difference. Froill the results of the two first methods of estimation corrected for the action of the impurities on the reagents it is shown that the specimen con- tains 92.5% of aluminium a s metal. The amount of oxide present deduced from this observation is 5*72% in excellent agreement with the direct determination. It is not certain that the oxide present is Al,O,.G. S. ROBERT MARC (Zeitsch. ccitorg. Chenz. 1908 430 459).-The results described in the previous paper (this vol. ii 47) are untrustworthy owing to the fact which had previously escaped notice that Merck's alum is contaminated with xubidium and caesium. G. S. J. V. E corrrpounds found in the crust of the earth. z. K. Alum [Correction]. The Decomposition of Felspar by Water. W. FUNK (Zeitsch. angew. Chem. 1909 22 145-1 46).-Finely-powdered felspar forms a colloidal suspension with water chenlical decomposition taking place at the same time 8 s shown by the alkaline reaction of the water. The attack on coarser particles may be shown by staining with methylene- blue and washing when only the partly decomposed outer zone of each particle is found t o be btained.Carbon dioxide hastens the attack but lessens the tendency t o form colloidal suspensions. Fused felspar is more rapidly attacked then the natural mineral. C. I€. D. Variation of the Composition of Colloids formed in a Solution of Ferric Chloride according to the Conditions of Hydrolysis. LEOPOLD MICHEL (Compt. rend. 1908,147 1288-1290. Compare Malfitano and Michel Abstr. 1908 ii 1042).-FurtherINORGANIC CHEMISTRY. 147 experiments on the variation in the cornposition of the colloidal particles with the conditions of hydrolysis of ferric chloride are described. The proportion of chlorine in the particles is usultlly greater the more slowly the solution3 are warmed ; i t is the saialler the higher the temperature employed in hydrolysis and the leas concen- trated the solution.The effect of the addition of hydrochloric acid is t o diminish both the quantity of colloid formed and the proportion of chlorine in it. G. S. Hydrates and Acid Salts of Ferrous Sulphate. FRANK €3. KENRICK (J. Physical Chem. 1908 12 693-705).-The composition of a number of ferrous sulphates and their rmge of existence in contact with sulphuric acid solutions at room temperature have been deter- mined by solubility measurements in the usual way aud the results are represented in tables and diagrams. The composition of the solid phases could not be obtained directly owing to the difficulty of separating them from the liquid phase but this has been effected by a combination of two methods of indirect analysis which are fully described.The more important solid phases are as follows Fe0,S03,H,0 minute granular crystals is stable in contgct with solutions from S0,,2*18 6 H,O to S0,,7*93H20 above which the heptahydrate is formed 2Fe0,3SO3,aH,O (corn poai tion somewhat doubtf u1) forms small colourless hexagonal crystals and is stable between the limits of SO 1 *637H,O to S0,,2*186H20. Fe0,2S0,H20 occurs in well-formed crystals and is stable in contact with solutions from SO3,1.342H,0 to SO3,1.595H,O. F,0,4S0,,3H20 slender needles is stable in contact with solutions from SO,,1*122H2O to SO0,,1.342H,O. The solubility .of all the compounds in the liquid phases is very small the tetra- and hepta-hydrates excepted. G. S. Action of Hydrogen Peroxide on Metallic Sulphides. J. FERRER y HERNANDEZ (And.Fit?. Quim. 1908 6 476-484).- Precipitated nickel sulphide decomposes hydrogen peroxide solution (3%) containing a trace of acid nickel sulphate being formed; hydrogen peroxide solution rendered alkaline with sodium or potassium hydroxide does not however change nickel sulphide. Ammoniacal bydrogen peroxide rapidly dissolves nickel sulphide giving a deep blue solution containing a complex ion. Cobalt sulphide behaves like nickel sulphide with hydrogen per- oxide containing a trace of acid; in presence of sodium or potassium hydroxide however it is oxidised to cobaltic hydroxide. Ferrous sulphide is oxidised by hydrogen peroxide (acid) giving ferric sulphate or products formed by the hydrolysis of the latter. Msaganese sulphide is under similar conditions converted into the sulphate but in presence of alkalis manganese hydroxide and sulphur are formed.Zinc sulphide is oxidised by hydrogen peroxide con- taining a trace of acid to zinc sulphate; in presence of alkali soluble zincoxides are formed. W. A. D.148 ABSTRACTS OF CHEMICAL PAPERS. Borotungstic Acida. HIPPOLYTE COPAUX (Comnpt. rend. 1908 147 973-976. Compare Klein Abstr. 1883 23 786 ; 1884 559 1366).-Tmo complex borotungstic acids have been prepared as follows. To one part of normal sodium tungatate and 1.5 parts of boric acid suflicient water is added to form a clear solution at the boiling point. After some time a precipitate separates. The mother liquors are con- centrated more boric acid added a further precipitate is rejected and to the mother liquors which now contain complex borotungstic acids ether and 2 to 3 volumes of sulphuric acid are added and the mixture shaken.'l'he resulting oil is decomposed by cold water and on evaporn- tion in a vacuum the complex acid B2U,,28 W0,,6H20 +- 56H,O separates in hexagonal cryhtals. From the same solution the other acid is obtained as the insduble barium salt by addiug barium csrbon- ate; the barium salt is decomposed by sulphuric acid and the acid B,0,,24W03,5H,0 + 61H,O obtained in octahedral crystals by evaporation. The acid occurring in hexagonal crystals is hexabasic and not very stable ; the other acid is more stable and is isomeric with silicotungstic acid Si20,,24W03,4H,0 + 62H,O although the formuls do not correspond and the boiotungstic acid unlike the latter is pentabasic.G. 8. Preparation of Urano-uranic Oxide and a Standard of Radioactivity. HERBERT N. &ICCOY and GEORQE C. ASEMAN (Amey. J. $ci. 19OS [iv] 26 52 1-530).-Pure urano-uranic oxide U30b can readily be prepared by heating any higher or lower oxide of uranium for some time in air a t 700'. Uniform films of the oxide 7 cms. in diameter and weighing 0.6 t o 00s gram have been prepared in flat circular tin dishes or copper plates as previously described (McCoy and Ross Abstr. 19OS ii 80) ; the thickness of the tilm is such that the a-ray activity is definite and constant and the films are therefore suitable standards of radio- activity. The a-ray saturation current for such a standard film is 5.79 x 10-13 amp. per cm.2; from this result it is calculated that the total a-ray ionisation current of 1 gram of uranium is 4.61 x 10-10 amperes. G.S. Molecular Weight of Uranium Tetrachloride in Boiling Bismuth Chloride Solution. LEOPOLD RUGHEIMER and L. GONDER (Anrhalen 19OS 364 45-50).-The molecular weight of uranium tetrachloride in boiling bismuth chloride solution as determined by the special method already described is 373 as compared with the calculated value 380-3 for the formula UCI,. Reduction of Uranyl Chloride. WILLIAM ~ C H S N E R DE CONIRCK (Corn@. rend. 1908 147 1477-1478).-The author has made experiments to ascertain whether the reduction of uranyl chloride by hydrogen at a red heat can be used as a method for the determination of the atomic weight of chlorine. The results are not sufficiently concordant for 'the purpose.G. S. H. M. D.ISORGANIC CHEMISTRY. I49 Alloys of Silicon with Tin Lead and Thallium. S. TAJIARU (Zeitsch. unorg. Chem. 1909 61 40-45).-Liquid silicon and tin are miscible in all proportions and on coding pure stlicon separates the eutectic being practically pure tin. The freezing-point curve falls very slowly until about 80% Sn is reached. and then very rapidly. Silicon is not miscible to a n appreciable extent with either lead or thallium in the liquid state. Preparation of Chloride of Thorium. CAMILLE MATIGXON (Compt. rend. 1908 147 1392-1293 *).-The author considers that the use of a mixture of chlorine and sulphur chloride (S,CI,) as a reagent for the preparation of anhydrous chlorides such as that of thorium from the corresponding oxides.already recommended (Abstr. 1904 ii Y40) is preferable t o the employment of cctrbonyl chloride recently used by Chauvenet (this vol. ii 53). The value + 53.8 Cal. has been obtained for the heat of solution of thorium chloride (1 mol. in 2700 mols. of water) at lao as compared with + 56-75 Cztl. obtained by Chauvenet (Zoc. cit.). Spitting of the Acid Vanadates of Univalent Metals. WILHELM PRANDTL and HANS MURSCHHAUSER (Zeitsch. anorg. Chenz. 1908 60 441-445).-In a previous paper (Abstr. 190€' ii 46) the composition of the vanadylvanadates xM,O,(p - z)V,O,,zV,O present in the solid state after the evolution of oxygen from certaln alkali acid vanadates on solidification was determined and i t was shown that t h e volume of oxygen given off from the potassium and lithiurn vanadates was less tban the calculated amounts R result ascribed to t h e incompleteuesv of the respective reactions.To test this view the vnnadylvanndates in question have been repeatedly fused and allowed fo resolidify in an atmosphere free from oxygen. After 50 fwions the amount of oxygen given off from t h e potassium compound corre- sponds with the formula for t h i s compound previously given but even after 100 fusions the oxygen obtained from the lithium compouud is less than that corresponding v i t h the composition previously given 4Li,O,V,0,,7V2O aud it must therefore be assumed that the compound present has the formula 6Li,0,V2o,,11 V,O,. Action of Antimony Trichloride on Nickel Formation of NiSb. EMILE VIGOUROUX (Compt.rend. 1908 147 976-978. Com- pare Lossen Abstr. 1006 ii 361).-When nickel is heated in a tube at 800' and antimony trichloride passed over it a vigorous rpction takes place and nickel chloride and nickel antimonide are formed. The former is removed by treatment with water and the heating in antimony trichloride repeated until finally only the antimouide NiSb remains as a crystalline powder. When the heating is carried out at higher temperatures the residues become progressively poorer in antimony. The compound NiSb has also been prepared by direct combination of the elements. Nickel antimonide NiSb occurs in lustrous reddish-violet crystals which are non-magnetic and have Do=7*70. It fuses a t 1101~~ and C. €1. D. G. X. G. S. * and Bull. SOC. chim. 1909 [iv] 5 92-93,150 ABSTRACTS OF CHEMICAL PAPERS.decomposes at 1400'. I t is vigorously acted on by chlorine and by oxygen when heated to dull redness. It is not affected by concen- trated hydrochloric acid but is decomposed by warm concentrated sulphuric acid and by warm nitric acid. It is scarcely affected even by fused alkalis. G. s. Bismuthous Compounds. 111. WALTER HERZ (Zeitsch. U7ZOYg. ClLrrn. 1509 61 119-121).-The freezing-point determinations of Eggink (Abstr. 1908 ii 1043) indicate the existence of BiC1 and BiEr only andare thus in disagreement with the results of Herz and Guttmann (Abstr. 1908 ii 199) which showed maxima corresponding with the formulse BiCl and BiBr,. Both series of experiments gave concordant figures and the cause of the difference is unexplained.C. H. D. Dichloropalladous Acid. ITALO BELLUCCI and PIETRO DE CESARIS (Gaxxeitcc 1908 38 ii 602-614).-The addition of a silver salt to an aqueous solution of palladous chloride results in the precipitation not of silver chloride but of a compound correPponding with the formula PdCl,(OH*Ag),. The conclusion is hence drawn that the aqueous palladous chloride solution contains an acid termed dichloropalladous acid dissociated thus PdC1,/OH + 2H+. The silver salt and also the lead and thallium salts of dichloropalladous acids are obtained as amorphous precipitates having the formuls - 'OH [PdCI &OH),] Ag [ PdCI,(OH),J Pb Pb( OH) and [PdCl,(O€l),]Tl respectively. The silver salt is hydrolysed slowly by hot water and - - the- other two salts more rapidly.T. H. P. Pulverisation [Volatilisation] of Iridium in Viiater Vapour and Carbon Dioxide. Experiments to Determine the Density of Carbon Dioxide by the Method of Diffusion. FRIEDRICH EMICH (Monatsh. 1908 29 1077-1085).-The author's attempts t o measure the dissociation of carbon dioxide at -high temperatures by observing the rate of diffusion of the gas through an aperture in an iridium tube have not been successful because of the change in the aperture consequent on pulverisation of the metal. The rate of pulverisation of electricnlly-heated strips of iridium i n water 'vapour and carbon dioxide has been determined at a series of temperatures and under different gas pressures. The velocity of the process which is supposed to be due to the formation of a volatile oxide Ir04 increases rapidly with the temperature.In the case of water vapour the velocity increases when the pressure is reduced from 1 to 0.1 atmosphere. On the other hand for carbon dioxide the velocity increases when the pressure is reduced to 0-5 or 0.25 atmosphere and then increases on further reduction of the pressure. At 1900" the rate of pulverisation in carbon dioxide is almost twice as large as in water vapour whilst a t 2100" very little difference can be observed. This is said to be io agreement with the data relative t o the dissociation of the two gases. H. 31. D.INORGANIC CHEMISTRY. 151 complex Iridium Compounds. ALFRED \h7ERNER and 0. DE VRIES (Annabn 1908 364 77-1 2T).-The preparation and proper- ties of it number of iridium compounds mainly chloronitrito- ammino- nitrito- and chloroammino-compounds are described.8odium iridiotet~,acnitritodichZoride [ IrCI,(N0,),]Na3,2H,0 (salt A) one of the salts intermediate between [IrCl,]A13 and [Ir(N02),]M3 examples of which are already known has been prepared as follows 5 grams of sodium iridichloride Na21rCI,,6H20 are heated at 80-90' with 80 C.C. of water 40 grams of sodium nitrite added gradually and the solution warmed until i t becomes yellowish-red and transparent. After a time a salt A separates in well-formed orange crystals solubility 1 in 0.87 parts of water at 25". From the mother liquors other products have been obtained but not yet fully investigated. Salt A in smaller yield is also obtained by the action of sodium nitrite on ammonium iridichloride. Salt A has been obtained in the anhydrous form by crystallisation from dilute alcohol ; it occurs in small pale yellow crystals.The corresponding potassium salt [1rCl2(NOJ4]K3 is obtained by repeated crystallisation from solutions containing salt A and excess of potassium nitrate; it forms small light yellow crystals and is less soluble than the sodium salt. By double decom- position between salt A and ammonium chjoride a yellow crystalline precipitate was obtained which has not been fully investigated ; it is not the corresponding ammonium salt. The lead salt in an impure form was also obtaiued by double decomposition. Nitritoamminiridizcnz compound8.- 2'rinit~itotrianaminiridium IrC (N02)3(NH3)31 is obtained in thin lustrous colourless scales by heating 1 gram of salt A with 4 C.C.of 27% ammonia for eighteen hours in a sealed tube at 135-140" ; the solution is evaporated and the salt crystallised repeatedly. It is only freed from chloride with great difficulcg. most satisfactorily by boiling with sodium nitrite. It is not affected by boiling hydrochloric acid (1 l) sulphuric acid (1 5) or concentrated nitric acid but is decomposed when heated withaconcentrated sulpburic acid to 85'. One part of the compound dissolves in 2570 parts of water at 25' ; the aqueous solution is pi-actically a non-conductor. Dinitritotetramminiridium chZoride [Ir(N02)2(NH3)4]Cl is obtained by heating 5 grams of salt A with 20 C.C. of 27% ammonia- tor eighteen hours at 170" and evaporating the product on a water- brtth. The leaflets which first separate are contaminated with nitrite aud the salt is obtained pure by dissolving in water and crystallising repeatedly in the presence of hydrochloric acid ; solubility 1 in 16.8 parts of water a t 55".Its behaviour towards the mineral acids is in most cases similar to that of the salt last mentioned. The following com- pounds are prepared from the chloride by double decomposition generally with alkali salts. The bromide [Ir(N0,),(NH3),]Br,H20 occurs in colourless rods or prisms ; the anhydrous bromide obtained by recrystallisation in the presence of hydro bromic acid in colourless prisms. The iodide occurs in colourless leaflets crystals or prisms ; the sulphate [ Ir( N0,)2(NH,)4]2S04,~H90 in prisms or needles which become anhydrous on heating to 120'.The solubility is about 1 in 400 of water a t room temperature.152 ABSTRACTS OF CHEMICAL PAPERS. Nitritope?ztalnziitiniridiunz chloride [ IrN O,( NH3),]C12 can also be obtained by the action of ammonia on salt 8 but iu better yield by the action of silver nitrite on the aquopentaurmine chloride (compare Palmaer Abstr. 1896 ii 179 ; 1897 ii 44) ; it forms small colourless .crystals readily soluble in water. It is scarcely affected by boiling with nitric acid or aqud regia or by moderately strong hydrochloric acid. The iodide and the sulphute are both anhydrous and form aolourless needles. Acid n i t r i t o p e ~ t a m ~ ~ i ~ z ~ r i d ~ u ~ ~ ~ sulphate obtained by the action of concentrated sulphuric acid on the chloride forms colourless. transparent needles. The nitrite obtained by inter- action of the chloride and silver nitrite also forms colourless crystals. ChEoTonntmirriridium Compounds.-The compound [IrC13(NH3),] amears to be formed when trinitritot,riamlniniridium. [(IrN02(NH3),3SO*I,,3 H2SO.p I I [Ir(N0,)3(NHh] is heated with ammonium chloride and hydrochloric acid to 180° but attempts to obtain i t pure were unsuccessful. D ichZorotetram~~i?ziridiurn chloride [ IrCI2( NH,),]Cl,H20 is obtained by heating together 1 gram dinitritotetrammine chloride 1 gram ammonium chloride and 15 C.C. of concentrated hydrochloric acid for nineteen hours a t 140'. It occurs in light yellow needles and prisms which are finally purified by repeated cryst(r1lisation from water. It is not affected by boiling hydrochloric wid ; on heating with silver nitrite even the intra-radicle chlorine reacts. It does not lose all its water even on prolonged heating at 125-130°. The corresponding bromide yellow needles crystallises with 1H,O which it loses at 80'; the sulphate yellow scales has also 1H,O which it retains a t 12Go; the iodide yellow needles is anhydrous. By the action of iridium chloride arid of potassium iridium chloride on dichlorotetrammin- iridium chloride sparingly soluble precipitates are obtained but no pure salt has bee II isolated. The dichlorotetrammine compounds just described appear to be identical with those obtained by Palmaer (Zoc. cit.) by the action of ammonia on iridium chloride. G. S.

ISSN:0368-1769    

DOI:10.1039/CA9099605135

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

152 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemi strg. Fossil Goals. EDUARD DONATH (Chew. Zeit. 1908 32 1271-1273).-The extract obtained by treating coal from Rossitz near Brunn with carbon disulphide or chloroform is found to contain anthracene. chrysene and probably also carbazole indene and polymerised coumarones. The view put forward previously (Zeitsch. angew. Chenz. 1906 19 657) namely that the formation of coal is accompanied by a process of distillation under pressure and that coal consists of small quantities of a variety of pitch with the solid carbon material thus receives support. w. 13. G.MINERALOGICAL CHEMISTRY. 158 InfluenCe of Centrifugal Force on the Optical and Other Properties of Naphtha. MICHAEL A. RAKUHIN (J. Buss. Phys. C h m . Xoc. 1908 40 1583-1688).-The author has made experi- ments to ascertain whether the rotation of the earth has any effect on the properties of naphtha A closed tube containing a sample of Grosny naphtha Dlj 0.8791 having a carbonisation constant of 3/32% was spun for two hours in a centrifuge revolvirlg 3000 times per minute after which it was found t o have the carbonisation constant 1/8% and D1S 0.8768.Evidently a considerable part of the products of carbonisation had settled on the conical bottom of the tube. So that whilst natural filtration of naphtha' produces a diffefentiation of naphtha in a vertical direction an analogous process in a horizontal direction may be brought about by centrifugal force. The author considers that such action has some bearing on the formation of asphalte and may explain why asphaltes having a venous character are met with in some parts of the earth.T. H. P. Rinneite. H. E. BOEKE (Chern. Zeit. 1908 32 1228).-An anhydrous mineral having the composition FeCl2,3KCl,NaCIl has been found in considerable quantities at the Nordhausen Works. It crystallises in the hexagonal system; it decomposes when exposed to the air but is stable under petroleum. and when a hot saturated aqueous solution is allowed to Acool potassium chloride separates out. J. V. E. Analysis of Plumosite from Felsobdnya. JOSEF LOCZKA (Ann. Musei Nat. Hungarici 1908 6 586-590).-The material consists of a felted aggregate of dark steel-grey fibres with entangled quartz crystals. Neither the colour nor the lustre is affected by a 25% solution of sodium hydroxide proving the absence of stibnite (which under these conditions quickly loses its lustre and becomes red); with a 30% solution the material acquires a coloured tarnish although still retaining its lustre..It is not acted on by an 8% solution of potassium sulphide. S. Sb. Pb. Cu. Fe(Mn,Zn).* Insol. Total. 21-89 35.80 39-38 trace 2.87 0.50 100'14 * Mn about 0.12 Zn about 0.10 per cent. Analysis gave No iron-pyrites could be detected. The formula is deduced as 4PbS,FeS,3Sb,Ss [but the figures agree still more closely with the jamesonite formula 7(Pbt,Fe+)S,CSb2S (Abstr. 1907 ii 700)]. L. J. S. A Group of Manganates comprising Hollandite Psilomelane and Coronadlte. L. LEIGH FEBXOR (Rec. Geol. Survey India 1908 36 295-300).-Hollandite (Abstr.1907 ii 701) has recentJy been described as a manganate of manganese barium and iron corre- sponding with the hypothetical acid H4Mn05 an acid suggested by Laspeyres in 1876 to explain the composition of psilomelane. It is VOL. XCVI ii. 11154 ABSTRACTS OF CHEMICAL PAPERS. here pointed out that the new mineral coronadite (Abstr. 1905 ii 96) may also be referred to the same acid the formula being Mn,,Pb,R”,( MnO,),,. These three minerals therefore form a group of manganates. L. J. S. Whewellite from Schlan Bohemia. FRANTI~EK SLAV~H (Bull. Intem. Acad. Sci. Bolkhe 19OS 13 9 pp.).-A crystallographic description is given of some large (up to 37 mm. across) twinned crystals of whewellite found with crystals of nnkerite and barytes in a fault-breccia in the Theodor coal mine near Scblan. The individual crystals have D 2.223 2.222 2,229.Analysis by J. Milbauer agrees with the formula CaC,O,,H,O CaO. c20,. H&* Total. 38’46 49.65 12-12 100.25 L. J. S. Study of Hydrated Silicates. FERRUCCIO ZAMBONINI (Rend. Accad. Sci. Fis. Mat. Nupoli 1908 [iii] 14 148).-The author has examined about thirty hydrated silicates with reference to the condition of the water present the main results being as follows. Thaumasite contains only water of crystallisation and is t o be regarded as CaSiOB,CaO03,CaS04,.l 5H,O. Pyrosmalite regarded up to the present as an orthosilicate is a metasilicate (S103)2[R(OH),Cl],H2. Ekmanite is not allied to pyrosmalite but is an altered chlorite. Calamine contains only 4 a mol. of water of constitution its probable formula considering its crystallographic relations with berwandite being Zn2(ZnOH)2Si,0,,H20.Cordierite has no water of constitu- tion. Dioptase is not an acid orthosilicate but a metasilicate with dissolved water. Katapleite does not contain water of constitution and is the sodium salt of a zircon-silicic acid; the same is the case with elpidite. The water present in steensfrupite and epistolite is not water of constitution. Sopiolite which is regarded as a meta- or an ortho-silicate contains absorbed water and must be given the formula &!tg2Si30,,n€€,0. The minerals collected together under the name of deweylite have so far as the water present is concerned properties analogous to those of sepiolite but must be distinguished as deweylite Mg,Si30i,,6H,0 and pseudodeweylite Mg,Si207,3H,0. T.H. P. Optical Characters of Minerals of the Amphibole Group and t h e i r Relation to the Chemical Composition. STEFAN KREUTZ (Sitzungsber. AT. Akail. Wiss. Wien. 1908 117 Abt. I 877-972).- Detailed determinations mere made of the optical constants of a number of minerals of the amphibole group; analyses are given of the following I griinerite from Ld Mallihre dep. Var.; 11 tremolite from Switzerland ; 111 actinolite from Zillerthal ; IV richterite from LHngban Sweden ; V hornblende from Russell New Y ork ; VI pargasite from Pargas Finland ; VII and VIII basaltic hornblende fiotn Lukow Bohemia.MINERALOGICAL CHEMISTRY. 165 Total less Si02. TiO2. A1203. FezOs. FeO. MnO. CaO. MgO. K20. Na20. H20. F. Ofor F Sp. gr.I. 47-17 - 1 0 0 1.12 43'40 0'08 1 9 0 2.61 0.07 0.47 2.22 0'07 10008 3 518 11. 58'22 - 1.37 0'04 0.01 0.04 12.95 23.97 0.04 0'24 2 17 0.17 999.5 2 9SO 111. 56'38 - 1.23 0'15 5.26 0'30 12-41 21.74 0.22 0'48 1-96 0.09 100'18 3'044 IV. 56'01 - 0-14 2'14 - 5'81 8'29 20 99 0.47 3.69' 1'94 0'18 99 69 8.044 v. 54-75 - 2'23 0'85 1'49 0'15 11'36 22'54 1'10 2-40 2'16 0'85 99'50 5.033 VI. 46-38 0'05 10 83 0.76 1'56 0.04 12.24 ' 20'78 1.38 2'69 0.91 1'82 100.68 3.095 VII. 39-60 2'50 18'51 5.50 2'26 0'74 12'57 14'11 1.87 2'58 0'26 0'10 100'63" - VIII. 39'90 2-90 17'03 4'14 4'00 0.23 12.70 14.39 3-11) 2'51 0'48 - 100 47 - * c02 0.07. No definite relation can be traced between the chemical com- position and the optical characters of the amphiboles except in tremolite-actinolite.The strength of the double refraction for instance does not vary progressively with the percentage of iron; and even in the colour of the material there is no such relation for the highly ferruginous grunerite is pale yellow whilst others containing less iron are dark green and glaucophane is blue or violet. The amphiboles are therefore not to be considered as mixtures of simple salts such as FeSiO? Al2Si3Og etc. but are complex compounds Composition of the Sand from the Eruption of Vesuvius April 1906. GIULIO PARIS (Chem. Zentr. 1908 ii 1287 ; from Stuz. sperim. agmr. ital. 1908 41 321-328).-Sand collected two days after the eruption had the following percentage composition C1. SO,. Si02. Pe,O,. CaO. MgO. G O . Na,O. NiO. 41'45 12.67 0.25 4'05 3.58 2.5 7'48 27'51 0.46 and the acidity calculated as hydrochloric acid was 7.68%.Casoria (Ann. Iz. Scuolu Super. Agyic. Portici 1907 7) considered from his analysis that it contains a new nickel mineral as suggested by Tschermak s double salts. L. J. 5. SiO NiO. MgO. Co Fe A] Ca. Water. Volatile. 35'014 44.75 4.528 trace 4.528 9.81 - together with a small quantity of magnesium hydroxy-oxide and another silicate of the composition SiO,. NiO. Ma@. Co Fe. Water. 39.756 19.348 26.808 trace 13.888 The a+h that fell in the Province of Avellino had I) 1.215 and contained an average of 0.6% phosphoric acid and 10% of alkali of which latter 50% was soluble in acids. Some specimens contained varying quantities of nitrogenous substances which liberated ammonia when heated with soda-lime.w J. V. E. Composition of the Ash and Lapilli from the Eruption of Vesuvius April 1906. NAPOLEONE PASSERINI (Staz. sper. agrar. ital. 1007 40 40-53).-8 sample of ash (1) and lapilli (2) were found to have the following composition K20. Na,O. NgO. CaO. FeO. FezOs A1,03. P20,. SO,. TiO,. SiO,. Cl. I. 5-43 3'54 4'76 10.80 4.01 4'41 17'84 0-66 0-17 1-02 46-72 0-34 11. 2.53 3'54 3.28 16.92 4-81 4.71 13-64 0.63 0'10 1-31 47'60 0.16 The acidity is only slight and is mainly due to volatile acids 11-2156 ABSTRACTS OF CHEMICAL PAPERS. (hydrochloric and sulphurous) which soon disperse' if the ash is left exposed to air and not ploughed in. The ashes resemble qualitatively those examined by Vauquelin and by Lavini in 1822 and 1829 respectively. The proportions of the different constituents vary howover considerably (compare Lacroix Abstr. 1906 ii 555).Lavas of the Last Eruption of Vulcano Lipari Islands. ALFRED LACROIX (Compt. Tend. 1908 147 1451-1456).-During any one period of eruption the magmas of Mt Peke of Vesuvius and of Xtna have in each case proved to be almost constant in chemical composition. From the various published descriptions of the products of the 1888-1889 eruption of Vulcano this would however not appear t o hold good; but two analyses now given of trachyte with anorthoclase augite and olivine are practically identical. Analyses are also given of microsanidinite occurring as enclosures in the trachyte of glassy rhyolite and of leucite-tephrite from Vulcanello. L. J. S. N. H J. M. Investigations on the Eruptive Basic Rocks of Northern Sardinia.AURELIO SERRA (Atti R. Accad. Lincei 1908 [v] 17 ii 597-602).-The rocks of the Fenosu district of Northern Sardinia have a felspar basis which exhibits inclusions of augite hyperstbene magnetite biotite apatite and ilmenite. The following is the chemical composition of the rock SiO,. A1,0,. Fe,O,. 48.72 22.56 1'08 MgO. K,O. Na,O. 2.68 2-05 4-66 I n the region of S'Adde contains large crystals of FeO. MnO. TiO,. P,05. CaO. 3'71 0.77 0.50 0-50 10*00 H,O (at 110'). H,O (at red heat). Total. 0.84 1 -88 99-87 de S'Ulmer the rock which is dark grey felspar (labradorite) smaller crystals of augite together with inagnetite biotite apatite and hypcrsthene and has the following composition SiO,. A1,0,. Fe,O,. FeO. MnO. TiO,. P205.CaO. 52.13 20'55 5.13 1-86 0.71 0'40 0.27 9.22 MgO. K,O. Ns,O. H,O (at 100"). H,O (at red heat). Total. 2.07 2-90 3.35 0'40 1'22 100.21 The two rocks belong t o the same eruptive magma Rocks from Central Borneo. T. H. P. J. SCHMUTZER (Proc. K. Akad. H'etensch. Amsterdam 1908 11 398-41 5).-Detailed descriptions and analyses by M. Dittrich are given of (I) glassy amphibole-dacito; (11) ditto ; (111) biotite-amphibole-andesite ; (IV) aplitic micro- granite the first three rocks being from the Muller Mtns. and the last from &It. KElam. SiO,. TiO,. AJ2O3. Fe,O,. FeO. MgCL CaO. Na,O. K20 H,O. Total. I. 66.16 0'50 15-39 1'25 1-72 0.90 3-47 3'94 2.00 4'94 100.27 11. 65*72 0.48 15'06 1.35 1.80 1-57 4-18 4'24 1.07 4'46 99.99 111. 62-78 0.56 17-16 1-96 2-31 2.32 4-84 4.11 2.15 1'12 99*58* IV.72'44 trace 16'51 0.24 0'52 0.05 2'47 4-54 2'13 1'26 100.16 * Including PzOs 0'15 ; MnO,,. 0'06 ; BaO 0-04. L. J. S.PHFSIOLOGICAL CHEMISTRY 157 Meteoric Iron. WALTER FXAENKEL and GUSTAV TAMMANN (Zeitsch. aizo4.g. Chem. 1908 60 416-435).-A typical specimen of meteoric iron contains three structure elements (1) bars of kamacite formed of hexahedral crystals containing about 6% of nickel; (2) taenite the crystals of which contain about 33% of nickel; (3) plessite a mixture of taenite and kamacite. From this structure it would appear that there is a break in the solubility oE nickel in iron from 6 to 33% of nickel but these metals form a continuous series of mixed crystals under ordinary conditions. The authors attempt to account for the differences in the structure of ordinary nickel- iron ores and meteoric nickel-iron of the same composition.Osmond and Cartaud (Abstr. 1904 ii 135) have suggested a hypothetical diagram for meteoric iron according to which the latter is more stable than ordinary nickel-iron alloys. The authors now show however that when meteoric iron is heated without access of air the kamacite first changes into granular crystals and then the taenite begins to disappear doubtless owing to the diffusion of the nickel into the altered kamacite. The change in they field is slow at 700° but rapid a t 1400O. The change in question takes place even in the a field ; after heating meteoric iron for two hundred holm at 420° granulation of the kamacite is observed although not with the same certainty as a t higher temperatures. It is shown indirectly however that the change must take place and hence that meteoric nickel-iron is unstable at the ordinary tem- perature. In order to find whether heated meteoric iron corresponds in properties with ordinary nickel-iron alloye the magnetic properties of the two substances have been compared. When heated meteoric iron loses its magnetic properties at about the same temperature as the ordinary alloy of the same composition but as different pieces of meteoric iron from the same large piece not previously heated lose their magnetic properties at very different temperatures this result is not conclusive Attempts to prepare meteoric iron artificially or to account for its structure did not lead to any definite result. It is probable that the iron in kamacite has not crystallised a t first in the ordinary ( y ) form. The paper is illustrated with 16 photomicrographs. G. S.

ISSN:0368-1769    

DOI:10.1039/CA9099605152

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

PHFSIOLOGICAL CHEMISTRY Physiological Chemistry. 157 Ionic Equilibrium in the Animal Organism. 11. The Influence of Carbon Dioxide on the Division of Electrolytes between the Blood-corpuscles and Plasma. KARL SPIRO and LAWRENCE J. HENDERSON (Biochem. Zeitsch. 1908 15 114-12q.- ‘$be explanation of Zunta’s observation that the passage of carbon158 ABSTRACTS OF CHEMICAL PAPERS. dioxide into blood increases the alkalinity of the plasma as determined by titration has been ascribed to the selective action of the living membrane. The phenomenon can however be explained as a purely physico-chemical process. If a dialysed globulin solution is mixed with sodium hydrogen carbonate a solution of the hydrogen carbonate placed in a dialyser inside the former solution and carbon dioxide be led into both liquids the alkalinity of the inner liquid increases. This can be explained by assuming that the following reaction takes place Na-globulin + H,CO = NaHCO + H-globulin.This in- crease of sodium salt increases the osmotic pressure of the inner liquid t o compensate for which water passes out from inside and the carbonate passes to the inside and thus increases the alkalinity. In the case of blood a similar reaction takes place between the proteins and carbon dioxide when the latter is passed through. I n the corpuscles the protein content is higher than in the plasma and a reaction then takes place between potassium phosphate and carbonic acid leading to the formation of potassium monophosphate and potassium hydrogen carbonate. As a result the osmotic pressure of the corpuscles becomes greater tban that of the serum.Water will therefore have a tendency to pass from the corpuscles to the plasma and as the cell walls are not permeable to the cations the system will be “ neutralised” by a wandering of anions chlorine ions passing into the cells and OH+ and -HCO ions into the plasma. A plasma will therefore be obtained with smaller chlorine content and greater alkalinity. S. B. 2. Coagulation of Blood. JOHN MELLANBY (J. Physiol. 1908,38 28-1 1 a).-Many of the experiments recorded do not support Morawitz’s views on the causes of blood-coagulation. Fibrinogen is always associated with prothrombin and therefore solutions of this substance may be coagulated by kinase and calcium chloride or by fibrin-ferment.The residual fluid after coagulation contains fibrin-ferment generated from the prothrombin by kinase and calcium chloride; if however fibrin- ferment is used as the coagulant the residual fluid contains prothrombin but no ferment. The action of calcium is considered to be specific. Salts which inhibit coagulation may precipitate calcium salts and those which do not precipitate calcium salts may restrain coagulation by holding fibrin in solution or by depressing the action of calcium and kinase on prothrombin. Plasma and serum contain a large amount of anti-fibrin ferment but not an anti-kinase ; the former is very susceptible to the action of alcohol. Serum usually contains no prothrombin. The activity of Schmidt’s fibrin-ferment depends mainly on the presence of kinase and calcium salts in it.Gamgee’s ferment solution is one of fibrin-ferment dissolved out by sodium chloride solution from the fibrin which had adsorbed it. Serum-globulin (in the author’s sence) is probably derived from the decomposition of fibrinogen under the influence of fibrin-ferment. Serous fluids contain the same substances but in smaller quantity than the bird’s plasma which was employed in most of the present experiments ; they there- fore coagulate on the addition either of kinase (prepared from testis) or of fibrin-ferment. W. D. H.PHYSIOLOGICAL CHEMISTRY. 159 Haemagglutination and Hsmolysis. M. VON EISLER (Centis. Bakt. Pur. 1909 48 ii 679-68l).-Polemical against von Lieber- mann; the views put forward by this author (Abatr. 1908 ii 865) are different from those originally propounded by him but very similar to those of Landsteiner. G.B. Seromucoid. HUBERT W. BYWATERS (Blochem. ZeitscA. 1909 15 382-343).-Blood was coagulated in slightly acid solution by means of steam. The filtrate from the coagulutn was concentrated and the solution thereby obtained submitted to dialysis. It was then filtered and after further concentration acidified with acetic acid and thrown into three times the volnme of alcohol. The crude seromucoid obtained in this may is pigmented and the author describes a method of purification by means of sulphur dioxide. I n properties seromucoid is similar to ovomucoid but differs from the latter by the intensity with which it gives Hopkins and Coles’ glyoxylic acid reaction and by the fact that no scission of sulphur takes place when treated with concentrated alkali hydroxide.It gives most of the other characterintic protein reactions. It contains 47’6% C 6.8% H 11.6% Y and 1.75% S. There is 25% carbohydrate in thermolecule ; this was isolated as a hydrolysis product in the form of glycosamine. The quantity of seromucoid in the blood is small ; a method is described tor its quantitative estimation; it increases after a meal rich in carbohydrates-in the case of dogs from about 0.3 to 0.9 gram per litre of blood. I n spite of its small quantity the carbohydrate it con- tains accounts for about 10% of the total circulating in the blood and the results obtained justify Yavy’s hypothesis that after carbohydrate i~igestion n part enters the circulation in combination with proteins. Seromucoid was also isolated from the mucous membrane of the intestine. S.B S. The So-called ctAlbumose” in Normal Blood. HUBERT W. BYWATERS (Biochem. Zeitsch. 1909 15 344-349).-The author criticises the methods by which previous observers have arrived at the conclusion that albumoses exist in the blood. He concludes that albumoses are absent and that what has been regarded as albumose 111 in reality seromucoid. D. E. JACKSON (Amer. J. Physiol. 1909 23 226-245).-If the blood of a dog poisoneJ with adrenaline is injected into another or the same animal it produces a rise of blood-pressure provided the rise of pressure in the first dog still persists. But if the blood-pressure in the first dog has regained its normal level which is usuallyin about a minute after the injection the blood of that dog will no longer produce a rise of pressure when injected into a second animal.The Effect on Blood-Pressure of I- d- and dl-Suprarenine (Adrenaline). EMIL ABDERHALDEN and FRANZ M~LLER. The Resolution of dGSuprarenine into its Components. FRANZ FLACHER (Zeitsch. physiol. C?4em. 1908 58 185-188 189-194).-1n S . B. S. Prolonged Existence of Adrenaline in Blood. W. D. H.160 ABSTRACTS OF CBEMICAL PAPERS the first paper Cushny's statement that I-adrenaline has a powerful effect on blood-pressure that d-adrenaline has a feeble effect and that d l adrenaline has an intermediate effect is confirmed. I n the second paper the methods are described for the resolution of synthetic &adrenaline into its optically active components.The methods used consisted in the growth of the mould Penicillium glaucum and in the fractional precipitation of salts. Under the latter head the tartrates gave the best resnlts. The naturally-occurring I-adrenaline gives a crystallisable tartrate The rotatory powers of the two substances are [.IF6 - 51.40° and + 51*8S0 respectively. W. D. H. Influence of Quinine on Phagocytosis Tn. GR~NSPAN (Centr. Bakt. Par. 1908 i 48,444-450').-Weak (less than 0.002%) solutions of quinine have no appreciable influence on phagocytosis in vivo ; a 0.002% solution increases it and a 0.1% solution diminishes it. Egg- albumin leads to no increase of phagocytic activity The intracellular Staphylococci appear to be living as judged by their staining reactions.Further work is in progress as some of the results are regarded as questionable. W. D. H. Phagocytosis. HEINRICH BECHHOLD (Chern. Zentr. 1908 ii 1269-1270 ; from Miinch. med. Woch. 19OS 55 1777-179$).- The inhibiting action of sodium hydroxide on the phenomenon ia lessened by the presence of serum and still more so by the unaltered1 blood Relatively large quantities of lactic acid do not act in this way even although they produce microscopic alterations of the. phagocytes; oxygen and carbon dioxide have no effect and carbon monoxide has no inhibitory effect. Various colloidal materials were investigated but they were unable to influence phagocytosis as serum does; the colloidal properties of serum per se therefore play no part in the phenomenon The action of pepsin and pancreatin is stimulated by lactic acid. w I).H. Salivary Secretion. IV. Influeno6 ~f Non-electrolytes. A. JAPPELLI (Zeitsch. B i d 1908,61 435-459),-Stroagly hypertonic solations of non-electrolytes injected into the blood-stream raise the osmotic pressure of the blood and also after a short time inorease ths concentration of the electrolytes in that fluid. The organism appeara to have the power to maintain the osmotic pressure and also the proportion between electrolytes and non-electrolytes at a constant level. The physico-chemical properties of the submaxillary saliva obtained by stimulation of the chorda tympani nerve appear to be independent of the osmotic concentration of the blood but they am influenced by such electrolytes and non-electrolytes as are permeable.through the secreting cells. Dextrose is not permeahle sucrose an& lactose only slightly so ; these substances hardly alter the saliva at all although owing to the greater amount of salts which pass into the blood from the tissues when they are present they do so indirectly leading to the production of a saliva rich in salt. An excess of sodium ions in the blood however inhibits salivqi-y activity. W D. H,PHYSIOLOGICAL CHEMISTRY. 161 Action of Peroxides on the Digestive Organs. Toamr (Chenz. Zentr. 1908 ii 1275 ; from Berl. klin. Woch. 1908 45 1528-1532). -The three substances investigated hydrogen peroxide magnesium peroxide and sodium percarbonate favour gastric secretion. Hydrogen peroxide (0.1 to 1%) has no effect on the action of ptyalin pepsin trypqin or amylopsin.The other two substances have also no effect but magnesium chloride favours the action of diastatic ferments in virtue of the chlorine ion. Concentrated solutions of hydrogen peroxide produce profuse secretion of mucus but dilute solutions have no effect on the gastric mucous membrane. \V. D. H. Action of Hydrocbloric Acid on the Secretion of Ferments of the Stomach and Pancreae. R. EHRMANN and R. LEDERER I(C?rem. Zentr. 19OS ii 1274 ; from Bed klin. Woch. 1908 45 1450-1452).-1n opposition to the statements of earlier investigators the administration of hydrochloric acid either with or after a test meal produces no increase in the secretion of pepsin. The amount of trypsin secreted by the pancreas is also lessened and Pawloff’s view that hydrochloric acid acts as a specific stimulus for pancreatic secretion is regarded as incorrect.W. D. H. The Influence of Acids on the Calcium Metabolism of Herbivora. E. GRANSTROM (Zeitsch. physiol. Chem. 1908 58 195-213).-Rabbits were fed on various diets (cream wheat) and hydrochloric acid or phosphoric acid added to the food. The effect on calcium excretion in urine and faeces was investigated ; both during inanition and after feeding the calcium in the urine is increased by acid ; the amount in the faeces falls except in two cases of phosphoric acid feeding but the influence of this acid on the faeces is far from clear. Suggestions are made regs-rding the therapeutic uses of acids in man. W. D. H. Carbohydrate Metabolism. JOHAN E.JOHANSSON (Chem. Zentr. 1908 ii 1373 ; from Scand. Arch. Physiol. 1908,21,1-34).-1n men,. carbohydrate food produces an increase in the output of carbondioxide but the amount varies considerably; in doses beyond 150 grams no further increase occurs. I;Eevulose causes twice as great an increase i n carbon dioxide excretion as the same amount of dextrose. Conditions affecting the output which were investigated are (1) previous state of hunger or not ; this largely depends on the amount of glycogen storage; and (2) adiabetic oondition here the results are very inconstant. W. D. H. R6le of Inorganic Phosphbrus in Nutrition. EDWIN B. HART ELMER V. MCCOLLUM and J. G. FULLER (Amer. J . Physiol. 1909,523 246-277).-8 number of young pigs were fed on normal diets on diets containing a minimal amount of phosphates and on diets containing an excess of these salts.In some experiments nuclein lecithin and phytin were used but these did not give any better results than iporganis phosphates. A low phosphorus intake is162 ABSTRACTS OF CHEMICAL PAPERS. prejudicial to growth ; increase of phosphorus chiefly leads to skeletal growth. There is no evidence of the synthesis of nuclein and other organic phosphorus compounds from inoiganic phosphates. W. D. H. Changes of Phosphatic Nutrients in the Human Body. E. KOCH (Bied. Zentr. 19OS 37 858 ; from St. Petersburg Med. FPoch. l906,400-402).-1n general inorganic and son-protein phosphorus is not utilised. It is possible however that inorganic phosphorus may be utilised if organic phosphorus is excluded from food for a long time.N. H. J. M. The Importance of Chlorides in the Life Processesof the Organism. HERMANN FRIEDRICH GRUNWALD (Zentr. physiol. I 908 22 No. 16 reprint).-Rabbits were fed on a chlorine free diet and then excreted urine which was almost chlorine-f pee. After adminis- tration of diuretin however large quantities 1 gram or more of sodium chloride were excreted. After four or five doses the animals exhibited characteristic symptoms of poisoning-weakness shivering paresis of the hind limbs and gradually increasing paralysis termin- ating in death in four or five days. The chlorine in the blood sank t o a half or even a third of the normal and in the latter stages of the poisoning re-administration of chlorine was ineffective in saving the animal.Control animals which had received 1 gram of sodium chloride with the diuretin kept perfectly healthy. The toxic symptoms are therefore due to loss of chlorine to which von Wyss has ascribed the effects of sodium bromide poisoning which produces similar symptoms. S. B. S. Influence of High Body-temperature on the Decomposi- tion of Sugar in the Animal Body. HERMANN HOHLWEG and F. VOIT (Zeeitsch. Riol. 1908 51 491-510).-An elevation of the body-temperature to over 40' by artificial means (warm chamber) leads t o an increase in the metabolism of protein and an increased excretion of nitrogen. This may be lessened or prevented if a sufficient amount of carbohydrate is also administered. Respiratory ventilation is enormously increased and the excess of combustion falls on the sugar.This occurs also if the sugar is given subcutaneously and even if sugars (such as sucrose) which are burnt with difficulcy under normal conditions are chosen. W. H. D. Chemistry of the Brain. A. RIELANDER (Chem. Zentr. 1908 ii 1371 ; from Zentr. Physiol. 1908 22 377-380).-The basic constituents precipitable by phosphotungstic acid were investigated after hydrolysis by hydrochloric acid. Histidine arginine lysine and choline were obtained; also bases with a heavier molecule than choline. W. H. D. Chemico-physical Investigations on the Crystalline Lens. FILIPPO BOTTAZZI and Noh SCALINCI (Atti R. Accud. Lincei 1908 [v] 17 ii 566-571. Compare this vol. ii 7l).-When thePHYSIOLOGICAL CHEMISTRY. 163 crystalline lens of a dog or rabbit is suspended in dry air it loscm in weight rapidly for four to six hours and then slowly.Notwithstanding tbe great loss in weight which amounts to 30*42-49.25% in four hours the lens does not become opaque but only wrinkles so that the opacity of the lens is not due to desiccation alone. When the desiccated lens is immersed in water vapour it increases in weight very slowly the original weight of tbe lens not being attained even after eighty to ninety hours; in some cases a slight loss in weight occurs during the first few hours of immersion in water vapour. When the desiccated lens is immersed in water the increase in weight is rapid during the first two hours after which time the water is only taken up very gradually. T. H. P. Physiology of Glands.X. The Liver in Different Nu- tritive Conditions. LEON ASHEB and PAUL BOEHM (Zeitsch. Biol. 1908 51 409-434). -Feeding on protein proteoses and amino-acids (alsnine and aspartic acid) increases the size of the liver cells ; the most marked effect was obtained with proteoses. Feeding with fat causes the appearance of fat globules in the cells. Feeding with the proteins and especially with proteoses leads not only to an increase in the size of the cells but to appearances which are figured showing they have been stimulated to activity. Alanine and aspartic acid do not seem to act as stimuli in the same way. The view that proteoses are absorbed in part as such is supported. W. D. H. Salts of Muscle. FUMIHIKO UBANO (Zeitsch. Biol. 1908 51 483-490. Compare Abstr. 1907 ii 978).-some analytical figures are given of the total ash and proportion of sodium and potassium in the frog’s sartorius before and after washing with sugar solution ; this method gives the proportion of salts in the muscles themselves as distinguished from that due to the adherent blood and lymph. A discussion of Overton’s views on the osmotic properties of muscle is also given.W. D. H. Physiological Function of the Arborescent Glands of the Female Generative Apparatus in the Cockroach. L. BORDAS (Compt. r e d . 1908 147 1495-1:497).-The larger of the above glands secretes a milky fluid containing large numbers of minute octahedra of calcium carbonate which serve to form the walls of the oo t hem. G. B. Protein Baaes of the Sperm and Ovaries of the Tunny Fish and their Products of Hydrolysis.SERAFINO DEZANI (Giorrt. R. Accad. Med. Torino 1908 14 reprint).-The dried sperm of the tunny fish after removal of the fat was found to contain 15.87% of nitrogen of which 20-22% is dissolved by 2% sulphuric acid in the form of a base answering to the reactions of that isolated by Ulpiani (Abstr. 1903 i 215). On hydrolysing the base 49074% oE the nitrogen present was accounted for as follows 6.79% as ammonia 3.86% as histidine 37.02% as arginine and 2.07% as lysine. The composition of the base present in the sperm of the tunny fish hence164 ABSTRACTS OF CHEMICAL PAPERS. differs from the mean composition of the protamines in its small proportion of arginine and its large proportion of ammonia. Excepting a s regards the arginine which is always present t o the extent of less .than 30% in the histones the base resembles in composition rather the latter than the protamines.The sperm also contains a nucleic acid which was obtained as a gelatinous white mass turning brownish-yellow on drying in a vacuum and containing N 14.10% and P 3.10%; this proportion of phosphorus is lower than in any other nucleic acid known. The dried ovaries of the tunny fish after remol-a1 of the fat contained 13.65% of nitrogen. Dilute sulphuric acid dissolved 4.46% of the total nitrogen in the form of a base which was obtained as an amorphous white powder becoming oily in the air. The base dissolves sparingly i n cold water and more readily iu hot water especially i f acidified with sulphuric acid; it gives the biuret reaction and Millon’s reaction after the lapse of some timo and is precipitated by concentrated ammonia picric acid .phosphotungstic acid and platinum chloride solutions.16.71% of its nitrogen is present as basic nitrogen 2.23% as histidine 0.95% as arginine and 13.53% as lysine. The moleculeof this base has a more complex composition than that of the base present in the sperm a fact in accord with Kossel’s hypothesis according to which the male sexual cells with their purely fecundating function contain the more simple proteins whilst the female cells which have to supply nutriment to the new individuals contain more complex protein substances. The ovaries contain a nucleic acid which mas separated as a white powder dightly soluble in hot water .giving an acid solution with which lead acetate or copper acetate gives an abundant precipitate. The acid contains 13.31% of nitrogen and 9.36% of phosphorus and is hence a true nucleic acid.T. H. P. Influence of Sugars on the Secretion of Milk. GIOVANNI PIANTONI (Chem. Zentr. 1908 ii 1784-1785 ; from Arch. Farm. spes.. 1908,7 329-336).-The subcutaneous injection of small quantities of mono- and di-saccharides in a goat produced an increase in the amount of milk secreted without altering its composition. Larger quantities lessened the secretion and the amount of sugar and fat in it causing also polyuria and the passage of lactose into the urine; this was intensified by repeating the injection daily. Polysaccharides do not have this action. W. D. H. The Variability of Milk.The Influence of the Addition of Various Salts to Fodder on the Composition and Quantity of the Milk. GEORG VON WENDT (Chem. Zentr. 1908 ii 1881 ; from Skand. Arch. Physiol. 1908 21 89-145).-Sodium chloride chalk sodium phosphate magnesium bromide and calcium glycerophosphate when added to fodder do not influence in any definite way the composition of milk. Calcium hydrogen phosphate often increases the quantity of milk and generally to a slight extent the calcium. The variability in the composition of the milk of cows of different breeds and iv different periods of lactation i s generally about tbe s a p . ThePHPSIOLOGICAL CHEMISTRY. 165 protein content as lactation proceeds in contrast to the other con- stituents does not diminsh. The phosphorus nitrogen and caseinogen contents are the least variable ; then come calcium fat and lactose ; then chlorine whilst potassium and albumin are the most variable constituents.S. B. S. Ionic Equilibrium in the Animal Organism. I. The Equili- brium of Acids and Bases in the Urine. LAWRENCE J. HENDERSON and KARL SPIRO (Biochem. Zeitsch. 1908 15 105-1 13).-The ionisation constant of the two acids P-hydroxybutyric acid and acetoacetic acid which occur under pathological conditions in the urine mas determined. This was done by ascertaining the relative amount of salt and freo acid which was present when a certain tint of an indicator was attained and comparing it with the amount of free acid and salt present in another acid of which the ionisation constant is known when it gives under the same conditions the same tint.From the equation ( H ) + = C( HA)/iKaA where C = ionisation constant divided by the grade of dissociation of the salt and HA and NuA the quantities of acid and salt present it is possible t o calculate the relative quantities of acid and salt present with different hydrogen ions. These concentra- tions in urine and blood have been determined under various normal and pathological conditions. As a result it was shown that in blood even in acidosis all or almost all the hydroxybutyric acid is combined as salt whereas in urine a considerable quantity is free. The acidity of the urine prevents a large loss oE alkali from the body of carnivora and the kidneys possess the capacity of holding back adout half the alkali when it exists i n the form of salts of those acids which occur in diabetes.s. B. s. The Physiological Basis of Radium Emanation Therapeutics. F. NAGELSCHMIDT and F. L. EOHLRAUSCH (Biochem. Zeitsch. 1908 15 123-1 63).-The radioactivity of urine and faxes of patients after ingestion of radioactive solutions was determined also that of the liver bile and blood of rabbits. The following conclusions were arrived at The radium emanation is a gas which can be resorbed by the lungs stomach and alimentary canal but not under ordinary con- ditions by the skin. The greatest part of this gas leaves the system within a relatively short space of time chiefly in the expired air; a small quantity can be detected in the faxes and also minute traces in the liver and bile probably existing here as residual activity.The blood showed no radioactivity but i t is possible that the gas is evolved from this fluid only in a vacuum. The therapeutic significance of these results is discussed. Elimination of Radium Bromide [in the Organism]. A JABOIN and BEAUDOIN (J. Pharm. Chim. 1909 [vi] 29 15-23).- The elimination of radium by the animal organism was studied; 0.05 mg. of radium bromide given in solution to a rabbit by the mouth was wholly eliminated in four days. Lecithin Choline and Formic Acid. GIUSEPPE FRANCErINr (Chem. Zentr. 1908 ii 1785 ; from APCJL. Farm. sper. 1908 7 371-399). -In rabbits fed on lecithin the amount of this substance increases in S. B. S. G. B.166 ABSTRACTS OF CHEMICAL PAPERS. the liver and muscles but not in the brain ; this goes on for two weeks after the administration of lecithin ceases.Small quantities of glycero-phosphoric acid pass into the urine also formic acid but not choline. In the faeces the amount of lecithin increases; glycero- phosphoric acid increases in the liver and muscles. W. D. H. Elimination of Nitrogen a f t e r the Administration of Glycine Asparagine and Glycyl-glycine Anhydride. PIHEBUS A. LEVENE and P. A. KOHN (Amer. J. Physiol. 1909 23 324-343).-This is a contribution t o the attempts now being made t o determine the r6Ze played by individual cleavage products of the protein molecule. If glycine is given the increase of excreted nitrogen begins earlier than when protein is administered ; all the glycine nitrogen is removed as urea within twenty-four hours.Asparagine more nearly approaches protein in its behaviour where nitrogen retention may last seventy- two hours. Asparagine also is not so rapidlg absorbed as glycine. On the hypotheeis that the slow excretion was due to the CO*NH group in asparagine glycyl-glycine anhydride which contains two CO-NH groups should be eliminated more slowly still ; the experiment was frustrated by the death of the dog but there was no evidence that there was any change into glycine or urea W. D. H. The Effect of Muscular Work on the Excretion of Endo- genous ,Purines. ERNEST L. KENNAWAY (J. Physiol. 1908 38 1-27).-During unaccustomed muscular work the output of uric acid is lessened whilst that of purine basesis increased the total output of purine substances being about normal.A greatly increased output of uric acid follows the work. If the work is repeated the changes noted show a progressive diminution but they reappear when another kind of muscular exercise is taken up. The increase in purine bases is attributed to defective oxidation but is not modified by inhalation of oxygen. The output of these bases exhibits diurnal variations similar to but less marked than those which occur in connexion with uric acid. The amount of the latter tends to vary inversely and that of the bases directly with the volume of the urine. The experiments are considered to support Leathes’ contention that muscular work leads to an increased formation of uric acid. W. D. H. The Purine Substances Normally Excreted in Man (when neither Tea nor Coffee have been taken).The late MARTIN KRUGER (Biochem. Zeitsch. 1909 15 361-364).-1n the urine of a patient who entirely abstained from tea and coffee the three known methyl derivatives of xanthine usually found in urine I-methyl- xanthine heteroxanthine and paraxanthine were absent. Guanine was also absent but xanthine adenine and epiguanine were present. Hypoxanthine was absent and this fact is accounted for by the cir- cumstance that a modified method of isolating the bases was employed which is described in detail in which a change of adenine into hypoxanthine does not take place. The results account for the origin of the methjlated purine derivatives in urine S. B. S.PIIYSIOLOGICAL CHEMISTRY. 167 The Excretion and Detection of Atoxyl in the Urine. GEORG LOCKEMANN and MARTIN PAUCKE (Chem.Zentr. 1908 ii 1542-1543 ; from Deutsch. med. Woch. 1908,34 No. 34).-Gadamer’s statement (Apoth. Zeit. 22 566) that atoxyl is not decomposed by hydrogen sulphide is only correct in a limited degree. If the gas is passed through the heated solution acidified with hydrochloric acid arsenic is precipitated quantitatively. I n the presence of strong hydrochloric acid at Oo hydrogen sulphide also produces a precipitate which is probably p-aminophenylarsenic sulphide NH,-C,H,*AsS or a similar compound. Also in neutral hot solutions hydrogen sulphide causes a precipitate. If the atoxyl compound is warmed with sulphur dioxide until all the latter is driven off hydrogen sulphide then causes a yellow precipitate at the ordinary temperature.Atoxyl preparations are very inconstant in composition j this is not only due t o variations in water of crystallisation but to other com- pounds mixed with the atoxyl. Atoxyl can be detected by Ehrlich and Bertheim’s reaction (Abstr. 1907 i 812) either in water or in urine. I n water 1 mg. in 100 C.C. can be detected ; the delicacy of the test in urine is less. After subcutaneous injection atoxyl is rapidly excreted in the urine almost wholly unchanged. I f the injections are repeated traces are found for a week afterwards ; a small amount cjf cleavage occurs in the body as shown by the presence of “free” arsenic in traces in the urine. Later a certain amount is taken up and bound in the organism and finally excreted with keratin. The Diazo-reaction of N o r m d Urine.R. ENGELAND (Chern. Zmtr. 1908 ii 1273-1274; from Miinch. me&. Woch. 1908 55 1643-1645).-The statement of Penzoldt and Petri (Bed. kZin. Woch 1883; Zeitsch. klin. Med. LSS4) that normal urine gives Xhrlich’s diazo-reaction is confirmed. It is attributed to substances such as histidine which contain an imino-azo-nucleus and the absence of the reaction in many normal urines is attributed to the presence of such substances as creatinine which unite with imino-azo-compounds. In certain pathological conditions the excretion of the last-named substances is increased. ERWIN RUPP (Chern. Zentr. 1908 ii 1536-1537 ; from Bpoth. Zeit. 1908 23 7 14).-A form of apparatus suitable for rapid freezing-point estima- tions with urine. Hydrochloric Acid Content of Gastric Juice in Anchylo- stomiaais with Special Reference to its Relationship toanaemia and Appetite. TANZO YOSHIDA (Chem.Zentr. 1908 ii 1950 ; from Arch. Schvfls.T~openhyg. 1908,12,683-697).-The acidity of the gastric juice in Japanese and also in Chinese varies between 45 and 49 degrees of acidity with 0*09-0.17% HC1. I n anchylostomiasis these figures remain normal; the juice was rarely subchlorhydric and still more rarely hyperchlorhydric. The proportion of free hydrogen chloride decreases when anzemia becomes more intense and the appetite in anchylostomiasis is closely connected with this. W. D. H. W. D. H. A Simple Apparatus f o r the Cryoacopy of Urine. W. D. H. G. B,168 ABSTRACTS OF CHEMICAL PAPERS. Experimental Glydosuria. IV. Cause of the Hyperglyceemia Produced by Asphyxia.JOHN J. R. MACLEOD (Amer. J. Phpiol. 1909,23 278-302).-Hyperglycamia lasts some time after asphyxia- tion. The source of the sugar is the hepatic glycogen for after extirpation of the liver hyperglycamia does not occur. The same is true for the hyperglycaemia produced by curare. The asphyxia1 (and curare) blood acts directly on the liver cells for the usual results take place after the hepatic nerves are cut. The substance in the blood considered to be responsible for the action is carbon dioxide and not loss of oxygen. W. D. H. Toxicology of Nickel Carbonyl. H. W. ARMIT (J. Hygiene 1909 8 565-600).-The lethal dose of nickel varies according to the animal employed and the method of administration. I n the form of nickel carbonyl the conditions for rapid absorption are most favourable and rabbits die after 3-4 mg.per kilo. of body-weight and cats after 8.5 mg. When the ~ R S is breathed nickel probably as hydrated basic carbonate is deposited on the respiratory surface from which it is taken up by the lymph and blood. It is thus carried to the tissues and deposited there especially in the brain and adrenals. The histological appearances produced are figured ; there is endothelial degeneration fatty degeneration of the vessel walls and adrenals and possibly a primary action on the brain cells. Haemorrhages and other secondary results follow. Nickel is excreted by the kidneys and intestine. Iron- carbonyl produces very similar results but the fatal dose is larger ; cobalt occupies an intermediate position in toxicity.No treatment was found to avert death. W. D. H. Chemical Constitu tion and Physiological Activity of Acids. JACQUES LOEB (Biochem. Zeitsch. 1909 15 254-271).-The physio- logical activity was determined by ascertaining the strengths of various acids necessary to produce a fertilisation membrane in the eggs of sea-urchins. A number of eggs were immersed in solutions of the acids of varying strengths in sodium chloride solution isotonic with sect-water for definite intervals then transferred back again t o sea-water and the percentage of eggs which had formed membranes determined in each case. It was found in the case of the fatty monobasic acids that the larger number of carbon atoms they contained the more active were they as membrane producers.The hydroxy- acids were less active than the corresponding unsubstituted acids ; the polgbasic acids were less active than the monobasic. The mineral acids were also less active than organic acids. The conclusion is drawn that the first action of the acids is to penetrate the cell-membranes and this is a function of the undissociated acid as a whole and not of the hydrogen ions. The hydrogen ions appear however to inhibit the formation of the membrane as this takes place only after the eggs are transferred back to sea-water after immersion in the acid s. B. s.PHYSIOLOGICAL CHEMISTRY. 169 Is Phenolphthalein Split in the Body? C. FLEW (Chem. Zentr. 1908 ii 1374 ; from Bull. Sci. Pharmacol. 1908 15 381-384. Compare Abstr. 1908 ii 313).-Various organs of the dog were perfused with a solution of phenolphthalein. The amount was the same after as before perfusion except in the case of the kidney where it was slightly lessened.Influence of the Asymmetric Carbon Atom in Pharmacology. The Action of d- r- and ECamphor on the Chloral-poisoned Frog’s Heart. JUHO HA&L4LAINEN (Chem. Zentv. 1908 ii 1451 ; from Skand. Arch. Physiol. 1908 21 64-79).-The three modifica- tions of camphor have no action on the normal frog’s heart. They however stimulate the heart’s action after this has been lessened by chloral. Theaction of the three kinds of camphor is pretty equal but that of the I-variety is least. W. D. H. W. D. H. Chemical Examination and Physiological Action of Nutmeg. FREDERICK B. POWER and ARTHUB H. SALWAY (Amar.J. Pharm. 1908 80 563-580).-The narcotic action of nutmeg is generally attributed to myristicin but owing to the fact that the action of nutmeg itself is much more pronounced than that of an equivalent quantity of pure myristicin it was considered desirable to make a complete investigation in order to ascertain if other substances are present which contribute to the effect. The essential and expressed oils of nutmeg have already been studied (Trans. 1907 91 2037; 1908 93 1653). An examination of .the 6Lpress-cake” has revealed the presence of the following substances which were not identified in either of the oils dextrose tannic acid colouring matters resins and a very small quantity of ipuranol (Trans. 1908 93 907; Abstr. 1908 ii 725). The results of a physiological investigation have shown that the narcotic property of nutmeg is undoubtedly due to myristicin but have indicated that this substance when associated with the other constituents is in a more favourable condition for absorption than when it is in a pure state.E. G. Absorption Excretion and Destruction of Strophanthine. ROBERT A. HATCHER (Amer. J. Physiol. 1909,23 303-323).-T.he absorption of strophanthine is rapid even from ligatured loops of intestine. Absorption when the drug is given by the mouth (in man and dog) is however comparatively slow and with small doses excretion keeps pace with it so that a large dose has to be given to produce toxic effects. The amount destroyed in the alimentary canal is small It can in the rat be detected subsequently in all the tissues. The oral administration of strophanthine is regarded as therapeutically irrational W. D. H. Influence of Iodothyrin Spermine and Adrenaline on Oxidation Processes and on the Toxicity of the Urine. A. J. JUSCHTSCHENKO (Biochem Zeitsch. 1909 15 365-452).-1n mental diseases the toxicity of the urine varies being sometimes VOL. XCVI. ii. 12170 ABSTRACTS OF CHEMICAL PAPERS. increased sometimes lessened. It is stated that similar variations are produced in animals accompanied by changes in gaseous metabolism by the administration of iodothyrin spermine and adrenaline or by the extirpation partial or complete of the glands which produce these substances. W. D. H. Behaviour of ‘( Bromoglidin ” in the Organism. HEINRICH BORUTTAU (Chem. Zentr. 1908 ii 1742 ; from Deutsch. rned. roc/&. 1908 34 1883-1 881).-The bromine of ‘< bromoglidin ” is secreted in a similar manner to the bromine of potassium bromide except that secretion is increased. The physiological action appears also to be greater than is indicated by the bromine content. J. V. E. Effect of Magnesium on Some of the Toxic Effects of Eserine. DON R. JOSEPH (Amer. J. Physiol. 1909 23 315-225). -Although magnesium salts have no influence on eserine myosis they have a certain value as an antidote in eserine poisoning; thus they abolish the muscular tremor produced by eserine. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9099605157

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

170 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Influence of Aeration on the Formation of Volatile Products in Alcoholic Fermentation. E. KAYSER and A. DEMOLON (Compt. rend. 1909 148 103-105. Compare Abstr. 1907 ii '714; 1908 i 317 j Trillat Abstr. 1908 ii 615).-The authors have compared the action of the champagne yeast No. 3 with that of a yeast (the yeast of bananas No. 221) of a definitely aerobic character on malt extract (containing 15.76% of sugar) with reference to the quantities of volatile acids esters aldehydes and higher alcohols formed. Comparative experiments were made (a) in long-necked flasks completely filled in order to avoid contact with the air ; ( b ) in shallow vessels two-thirds full and exposing a large surface of liquid to the air.A t the end of one month the quantities of sugar decomposed and of yeast volatile acids esters and aldehydes formed by the banana yeast were considerably greater (two to five times) in the shallow vessels than in the flasks whilst the alcohol content was found to be greater in the unexposed liquid. On the other hand similar experiments with the champagne yeast showed that exposure to the air had very slight effect on the amounts of sugar decomposed and yeast formed decreased those of volatile acids and esters to less than half doubled the amount of higher alcohols and enormously increased the proportion of aldehydes. At the end of six months the effect of exposure to air on the action The results are given in tabular form.VEGETABLE PHYSIOLOGY AND AGRICULTURE.171 of the banana yeast is still to increase the amount of sugar decomposed and of yeast formed although to a smaller extent than after one month but to largely decrease the amounts of volatile acids and esters. Only traces of aldehyde are found in either exposed or unexposed liquids. After six months comparison of the exposed with the unexposed liquids fermented with the champagne yeast shows that the weights of yeast aldehydes and higher alcohols are greater and that of esters is less in the former than in the latter. Addition of mercuric chloride to the liquid fermented by the champagne yeast in a shallow vessel for six months reduces the amounts of yeast and aldehydes formed but increases those of esters ethyl alcohol and higher alcohols probably by protecting these from oxidation.E. H. Influence of Inorganic Salts particularly of Stannous Chloride on Fermentation. G. GIMEL (Compt. rend. 1908 147 1334-1 326).-Kayser and Marchand have shown that small traces of manganese favour alcoholic fermentation. The author now finds that the effect of stannous chloride on various species of yeast is even more marked a culture containing one part in 10,000 producing 4% more alcohol than the control. G. B. Denitriflcation. MASANIELLO CINGOLANI (Chem. Zentr. 1908 ii 19 1626; from Stax. sperim. agrar. ital. 1908 41 530-540).-Five grams of fresh freces (from a calf) were placed in 100 C.C. of a 0.3% solution of sodium nitrate and two organisms which cause denitrifica- tion were isolated. Both were cocci and they are termed Bacillus porticensis denitrijcans-a and -p.The latter attacks nitrates reducing them to nitrites but it has no further action; the former reduces nitrites to ammonia and then to free nitrogen but has no action on nitrates. Ammonia is said to be an intermediate product; when ammonium nitrate is used in place of sodium nitrate the reaction is much accelerated. E. J. R. Sewage Purification. W. MAIR (J. ETygiene I909,8,609-654). -An experimental discussion of the methods of sewage purification especially in relation to the part played by bacteria. In the contact beds a considerable proportion of the organic nitrogen disappears as gas as a result of alternate nitrification and denitrification. The amount of nitrate in the effluent is a direct measure of the degree of aeration to which the sewage has been exposed in the percolating beds.If the nitrate disappears from a contact bed it is a sign that the bed is being overworked ; the denitrifying process being allowed to proceed too far. So long as nitrate is present cultures of the Bacillus hyponitrosus have no putrefactive odour. W. D. H. Standardisation of Disinfectao ts. Emulsified Disinfect- ants. HARRIETTE CHICK and CEARLES J. MARTIN (J. Hygiene 1909 8 654-697 698-703. Compare Watson Abstr. 1908 ii 976).- In any method of standardisation it is necessary that the tests be carried out under constant conditions of temperature culture medium 12-2172 AUSTRACTS OF CHEMLCAL PAPERS. number of bacteria per unit volume and duration of observation. A logarithmic relation exists between concentration of the disinfectant and velocity of disinfection.In the case of metallic salts traces of the disinfectant carried over with the test sample must be neutralised by sulphide ; in the case of mercuric chloride an excess of sulphide is necessary to decompose a compound formed between the salt and the substance of the bacterium. Some disinfectants are more efficient against one species of bacterium others against another. In the case of spores metallic salts are most efficient. As a rule virulent species are more difficult to kill than non-virulent ones. I n the process of standardisation it. is therefore necessary to fix on a particular organism in the test. Bacillus typhosus is the best to employ but a non-virulent strain should be selected in order to minimise danger to thoso engaged in the test.The presence of 10% of blood-serum reduces the efficiency of 1% of phenol by about 12%. The effect on emulsified disinfectants is somewhat greater. The presence of finely particulate matter affects the germi- cidal value of emulsified disinfectants containing the higher phenols to a much greater extent than it does solutions of phenol. The removal of an emulsion of the higher phenols by bacteria by finely divided animal charcoal by dust etc. obeys in all cases the same quantitative laws. Finer emulsions are more seriously reduced in value by particulate matter than coarser ones. The removal of an emulsion of higher phenols by bacteria is in the first instance a process of adsorption ; disinfectants of t h i s class possess superior efficiency because owing to this adsorption the bacteria rapidly become surrounded by the disinfectant in much greater concentration than exists throughout the liquid W.D. I€. Degradation of Sugar during the Respiratory Process. P. BOYSEN JENSEN (Ber. Deut. hot. Ges. 1908 26a 666-667).- Alcoholic fermentation is identical with the intramolecular respiration of seeds and the latter process is the starting point for normal respiration. I n alcoholic fermentation dihydroxyacetone is formed as an intermediate product ; if hydroxylamine hydrochloride is added during fermentation the oxime is formed in small quantity and after the end of the fermentation dihydroxyacetone can be isolated as its phenylmethylosazone. Dihydroxyacetone prepared by Fenton and Jackson’s method yields on fermentation alcohol and carbon dioxide.Zymase consists therefore of two separate enzymes dextrase and dilydroxyacetonase. I n a glycerol solution of dextrose the second of these is inhibited so that dihydroxyacetone is the end product. Dihydroxyacetone is also decomposed by oxyditse yielding carbon dioxide and water but not alcohol. The fact that oxydase attacks neither sugar nor alcohol leads to the hypothesis that in the normal respiration of plants dihydroxyacetone is the immediate precursor of the carbon dioxide and water ; in intramolecular respiration that is i n an atmosphere deprived of oxygen it yields carbon dioxide and alcohol. The process of normal respiration can therefore be imitated by adding oxydase toVEGETABLE PEYSIOLOGY AND AGRICULTURE 173 a fermenting dextrose the degradation of the latter then taking place as follows C,H,O -3 OH*CH,*CO*CH,*OH -+ CO + H,O.G. B. The R81e of Zymases in the Respiratory Processes of Seed- plants. s. KOSTYTSCHEFF (Biochem. Zeitsch. 1908 15 164-195).-1t bas been shown by various observers that anaerobic respiration of pea-seeds is in all essential respects identical with the process of typical alcoholic fermentation. Experimeots were carried out to throw further light on the mechanism of the reaction by determining the amount of alcohol and carbon dioxide produced by pea-seeds and wheat embryos in the presence and absence of air and in the presence of sugar and also in the intermediate products formed from the latter by yeast fermentation.It was shown that the assumption that the alcoholic fermentation of seed-plants is independent of the oxygen respiration will not hold in that such powerful excitants of alcoholic fermentation as pea-seeds produce with full aeration no alcohol. Furthermore alcohol does not appear to be a normal intermediate pro- duct of sugar utilisntion for although pea-seeds will when aerated consume slowly the alcohol previously produced in absence of air the consumption is not accompanied by an increasedoutput of carbon dioxide. W heat-seeds and embryos do not possess this capacity for alcohol consumption a t all. On the other hand dextrose causes an increased production of carbon dioxide. Solutions containing the intermediate products of fermentation (produced for example by the action of zymase in the presence of phosphates) cause an even larger carbon dioxide output than sugar itself.The greater part of the primary products of the zymase action appear to be immediately oxidised further without production of alcohol. The presence of the latter substance in certain seeds is to be explained on the assumption that these primary products do not all undergo immediate oxidation; in this case thev are converted into carbon dioxide and alcohol. which latter .I must be regarded as a by-product only of the respiratory processes. S. B. S. Phosphorus and the Formation of Amino-acids in Higher Plants. FRANCESCO SCURTI (Chem. Zent.r*. 1908 ii 16 1370; from Stax. spwirn. agrar. itccl. 1908 41 456-470).-The non-protein nitrogen compounds in plants are made up of the same substances as are found in germinating seeds and in young seedlings.Phosphorus is known to play an important part in protein formation and the author considers that it may function in the formation of amino- acids. E. 5. R Occurrence and R61e of Zinc in Plants. MAURICE JAVILLIER ((??hem. Zentr. 1908 ii 1828; from Bull. Sci. Pharm. 1908 15 559-565).-Besides certain well-defined varieties growing on soils which are rich in zinc most plants contain appreciable quantities of this metal which is especially found in Conifers. The growth of yeast is favoured by small quantities of zinc although the optimum concentration of the metal is greater than in the case of dspergi~~us.174 ABSTRACTS OF CHEMICAL PAPERS.Zinc can also act favourably on the growth of Phanerogams for example cereals. G. B. The Chemical Processes of Ripening. The Ripening of Oranges. Presence of Asparagine and Glutamine in the Juice. FRANCESCO SCURTI and G. DE PLATU (Chern. Zentr. 1908 ii 16 1370; from Staz. specim. ugray. itul. 1908 41 435-455).-The authors draw the following conclusions from their experiments (1) The acidity of oranges is due to citric and malic acids the quantity of which increases in the earlier stages but falls off afterwards. I n this respect oranges resemble other acid fruits. (2) The sugars present are dextrose laevulose and sucrose; the two first steadily increase during ripening whilst the sucrose decreases. There is more lmwlose than dextrose. I n sweet and in bitter oranges there is more reducing sugar than sucrose but not in common Italian oranges.No relation- ship could be discovered betwoen acidity and the amount of sucrose present. (3) The total nitrogenous matter decreases but the loss falls entirely on the proteins precipitated by basic lead acetate and not on the other nitrogen compounds which remain constant in amount. These non-protein compounds consist chiefly of asparagine and glutamine it is significant that these two which are constantly associated with germination and assimilation should also be present during ripening. E. J. R. The First Stages in the Development of Perennial Plants compared with those of Annuals. GUSTAVE A N D R ~ (Compt. rend. 1908 47 14S5-1487).-During the first two years of the life of a perennial plant the root is much more developed relative t o the shoot than is the case in annual plants and contains a larger propor- tion of phosphates than the root of tbe latter. G.B. NICOLAI A. WALJASCHKO and N. KEASOWSRY (J. Bu.ss. Shys. Chem. Soc. 1908 40 1502-1509).-Discussion of previous work on this subject (see Tschirch and Pedersen Abstr. 1898 i 599 ; Hesse Abstr. 1900 i 40; Tschirch and Polacco Abstr. 1900 i 681) and of the results obtained by Krasowsky (see following abstract). Constituents of the Fruit of Rhamnus cathartica. T. H. P. Berries of Rhamnus cathartica and the Methods of Separating the Substances Contained Therein. N. KRASOWSKY (J. Buss. Phys. Chem. SOC. 1908 40 1510-1569. Compare Tschirch and Polacco Abstr. 1900 i 681).-After describing in detail the methods used for extracting the various constituents from the berries and purifying them the author discusses separately each of these con- stituents which 4re as follows. (1) Quercetin apparently identical with that obtained from quer- citrin.(2) Rhamnetin. (3) Xan thorhamnin (compare Tanret and Tanret Abstr. 1900 i lS5) which is hydrolysed by dilute sulphuric acid giving rhamnetin galactose and rhamnose (2 mols.) C,,H,,O + 3H,O = C,,H,07Me + C,H,,O + ZC,H,,O,. The only difference between the product described by Tanret and Tanret (loc. cit.) and that obtainedVEGETABLE PHYSIOLOGY AND AGRICULTURE. L75 by the author is that the former gives golden-yellow crystals whilst the latter separates in faintly yellow crystals. m. p. 254-255' which is a trihydroxymethylant hraquinone and closely resembles frangula-emodin (compare Oesterle Abstr.1900 i 304). (5) Rhamnoxanthin C21H2,0g,H,0 which is reduced to methyl- anthracene by zinc dust in an atmosphere of hydrogen and readily undergoes transformation into emodin when crystallised repeatedly from alcohol. ~etra-cccetylrhamnoxanthin C,,Hl6OYAcq crystallises from acetic acid in microscopic pale yellow needles m. p. 146-149O. Rhamnoxanthin is a glucoside and is resolved into emodin and methyl- pentose on hydrolysis with dilute hydrochloric acid C,,H2,0g + H,O = C1,H1005 + C,H,,?,. (6) Jesterin C26H30013,$H20 m. p. 205 -2 18O which is a glucoside yielding emodinanthranol hexose and pentose on hydrolysis (7) Rhamnocathurtin C21K3,01 which is hydrolysed by alkali giving rhamnoxanthin and an unknown hexose C27H3,Ol + H,O = C21H2009 + C,H,,O and by acid giving emodin rhamnose and hexose thus C2,H,,0 + 2H20 = C15HlOO5 + C,H1205 + C6Hl2O,.(8) Emodin- anthrccnot (ti.ihydroxymethylanthrccnol) (4) Emodin C15HlOO5,=20 C2,$Ta,-,013 + 2H20 = C,,H1,04 + C6H1,06 + G5HloO5. . - C,H2( OH),<~~H)>C,H,MeOII which separates from ethyl acetate in faintly yellow crystals m. p. 280° ; its tetru-acetyl derivative CI5H8O4Ac4 crystallises from alcohol in pale yellow plates m. p. 197". I n alkalino solution emodin- anthranol is oxidised by the oxygen of the air yielding emodin C6Ha(OH)2<CO>C6H,Me*OH co reduction of which by means of t i n and hydrochloric acid yields emodinanthranol. (9) Rhamnonigrin or a mixture of rhamnonigrins which were not characterised.(10) Succinic acid. The berries of Rhamnus cathccrtica contain dextrose in the free state and galactose rhamnose and pentose only in the form of glucosides. T. H. P. Chemistry of the Eigher Fungi. 11. Polyporus ignarius. JULIUS ZELLNER (Monatsh 1908 29 11 71-1 187. Compare Abstr. 1908 ii 216).-The constituents of Polyporus closely resemble those of T~arnete8 suaveolens previously examined (loc. cit.) in accordance with the fact that these closely-related fungi are parasitic on the same host (willow). The ash (with much calcium sulphate) ergosterols fats resins soluble proteins and volatile substances dextrin-like carbo- hydrates (which are abundantly present) and ferments are all very similar. The constituents of the cell wall however are different and unlike Trametes Polyporus contains mannitol and tannins but no m ycose.G. B. A. GORIS and M. MASCR~ (Compt. rend. 1908 147,14SS-1489).-Young spezimens of PsolEaotci campestris contain urea to the extent of 2.75% and Presence of Urea in Certain Higher Fungi. mature ones 4.3% of their dry weight (compare Abstr. 1903 &-567). G. B.176 ABSTRACTS OF CHEMICAL PAPERS. Some Mannas and Related Products. ALFRED EBERT (Chem. Zentr. 1908 ii 1874-1875 ; from Zeitsch. AZZg. Oesterr. Apoth. Ver. 479-481 491-492 503-504 515-516 529 -530). - This gives the proximate composition of a number of Persian and Australian mannas. The figures given below are expressed in percentages of the crude materials except where otherwise stated. ‘‘ Trehala,” derived from the larval cocoons of a beetle living on the stems and flowering heads of Echinops persicus contains moisture 11.1 ash 2.6 trehalose 175 gum (yielding mucic acid on oxidation) 27.1 and tannin and residue 44.5 ; of the residue 71% consists of a starch giving a reddish-brown colour with iodine. “ Terendschabin ” is exuded from the leaves and thorns of A h g i maurcn’um ; it consists of moisture 5.2 ash 9.4 chlorophyll with some guw 0.5 sucrose 42.0 a gum (yielding oxalic acid on oxidation) 20.3 and residue 32.0.“ Bide-khecht,” derived from the leaves of SccZix fragilis contains moisture 4.1 ash 25.4 dextpose 17.5 sucrose 50.1 matter soluble in water 13.3 and insoluble matter 19.2. The sample was adulterated with wheat-flour and gypsum. ‘[ Gueze-elefi,” from Quercus uallonia contains moisture 7.5 ash 5.4 sucrose 53.2 dextrose 19.0 gum (yielding mucic acid on oxidation) 10.3 and insoluble residue 10.0.[‘ Schir-Khist,” the manna from Cotoneaster nummuZaTia contains moisture 15.9 ash 2.2 dextrose 37.5 sucrose 12.9 gum (yielding mucic acid) 24.2 and insoluble residue 9.5. ‘‘ Eucalyptus manna,” from E. Guwnii var. rubida contains moisture 9.7 ash 6.8 melitose 68.5 dextrose 20.9 sucrose 2.1 gum (yielding mucic acid) 3.2 and insoluble residue 4.3. A specimen from E. pulver- dents S. consists of melitose 21.4 laevulose 16.2 sucrose 60.0 and insoluble residue 1 -0. Tabssheer a siliceous deposit from bamboo culms especially Barn- busa stricta R. contains sucrose 4.2 gum (yielding mucic acid) 2.6 and inorganic residue about 90 (compare Ince Abstr.1897 ii 278). 1908 46 427-429 439-440 447-450 459-460 467-470 T. A. H. Mode of Combination of Mineral and Organic Acids in Wine. ANTONIO QUARTAROLI (Bied. Zentr. 1908 37 862; from Staz. sper. agrar. ital. 1906 30 993).-The mineral acids of wine are in the form of salts unless present in very large amounts. Addition of mineral acids can be detected by determining the electrical conductivity which is distinctly increased by adding potassium hydroxide to wine containing neither mineral nor free organic acid. When organic acids have been liberated by addition of mineral acid the conductivity is diminished by adding potassium hydroxide. Addition of 1 gram of sulphuric acid per litre can be detected in this manner. Amounts of Nutrients Utilised by Sugar-beet in the First Year and their Relation to the Amount of Sugar in the Roots. KARL ANDRLfK and JOSEF URBAN (Zeitsch.Zuchrind. Bohm 1909 33 221-240 Compare Abstr. 1908 ii 1066).-For N. B. J M.VEGETABLE PHYSIOLOQY AND AGRICULTURE. 177 a yield of 400 quintals per hectare of roots it was found that the indispensable amounts of phosphoric acid nitrogen and potash were 65.1 139.8 and 168.6 kilos. respectively. The amount of phosphoric acid is thus approximately the mean of the amounts found by Hoffmann (71.4) and by Willfarth (62.0 kilos.) whilst the amount of nitrogen is lower and that of potash higher than those given by Hoffmann and Willfarth ; the yield of sugar in Bohemia was however also higher than the yields obtained in Germany. At present the most favourable relations of the different nutrients are N=2*15 and K,O=2*59 t o 1 part P,O,.When by selection roots are obtained containing higher amounts of sugar it will be necessary to ascertain whether these amounts still hold good. N. H. J. M. Influence of Some Calcium Compounds on the Manurial Value of Ammonium Sulphate and Calcium Cyanamide. ALEXANDER STEBUTT (Bied. Zent?.. 1908 37 805- 806 ; from Fiihling's Landw. Zeit. 1907 56 669).-Pot experiments in which mustard was grown in loam containing 0.09% of calcium carbonate and manured with ammonium sulphate and calcium cyanamide in conjunction with calcium oxide carbonate and sulphate respectively. The conclusion is drawn that under normal conditions the calcium compounds are without effect on the action of the two nitrogenous manures. N.H. J. M. OSCAR LUEW (Chem. Zeit. 1909 33 21-22 Compare Abstr. 1908 ii 775).-Pot experiments with barley in garden soil with mineral manures and with N = 0-75 gram in the form of dicyanodiamide (1 and 2) and as ammonium sulphate (3). A fourth pot mas without nitrogen. The highest amount of dry matter (43.2 grams) was obtained in the pot which had ammonium sulphate. Dicyanodiamide in heated soil gave the next highest amount (31.3 grams) then the pot which had no nitrogen (24.8 grams) and last dicyanodiamide in non-sterilised soil. The conclusion is drawn that dicyanodiamide is directly utilised by plants under sterilised conditions but that in unsterilised soil it is converted by microbes into substances injurious to plants. Is Dicyanodiamide Poisonous to Crops 3 The soil of ( 1 ) was heated a t 100" for one hour.N. H. J. M. Phosphoric Acid with Different Citric Acid Solubility as Manure for Meadows. HANNO SVOBODA (Chem. Zentr. 1908 ii 1893 ; from Zeits. Landw. Versuchswes. Oesterr. 19OS 11 733-774).- Whilst the rapidity of action of phosphate manures depends on a high percentage of phosphoric acid soluble in citric acid the value of the manure depends mainly on the amount of total phosphoric acid. N. H. J. M. The Causes which Determine the Replacement of Potassium of Leucite in Soils. LUIGI BERNARDINI (Chem. Zentr. 1908 ii 15 1285 ; from Stax. sperim. agrar. ital. 1908 41 304-320).-The leucite used contained when dried at 110" SiO 56-89 ; A1,0,+ Fe,O 24.08 ; K20 15.63 ; Na,O 1.77 ; CaO 1.11 ; MgO traces.178 ABSTRACTS OF CHEMICAL PAPERS.The solubility was determined in hydrochloric acid 5% acetic acid water a solution of carbon dioxide in water and in a number of salt solutions including sodium chloride nitrate and sulphate ammonium chloride nitrate sulphate and carbonate calcium chloride nitrate sulphate and dihydrogen phosphate and magnesium chloride nitrate and sulphate. Sodium and ammonium salts caused a good deal of potassium to go into solution ; magnesium and calcium salts on the other hand had only a slight solvent power. The author considers that double decomposition takes place the potassium of the leucite being replaced by sodium or ammonium. Ammonia produced in the soil by bacterial processes would therefore react with leucite forming an in- soluble ammonium leucite whilst at the same time a soluble potassium compound is formed which is available for plants. The ammonia can no longer be washed away by rain but mafstill be nitrified. E. J. R. Humus-Silicic Acid. HJALMAR VON FEILITZEN (Bied. Zentr. 1908 37 793-794 ; from ASvenska Mosskulturforening Tidskr. 1907 ; and Vienee. landw. Zeit. 1907 No. 43).-The manure which is prepared from peat has the following composition water 10.12 ; organic matter 46.13 ; N 1.26 ; K,O 2-64 ; CaO 6.44 ; P,O (a) soluble in boiling 24% HC1 3-33 ; and ( b ) citrate soluble 2.55%. Application of the manure alone (1000 kilos. per hectare) to a poor sandy soil increased the yield of peas but was without effect on oats owing to the deficiency of nitrogen in the soil. When applied in conjunction with other manures humus-silicic acid gave similar results with peas and very slightly increased the yield of oats. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9099605170

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

178 ABSTRACTS OF CHEMICAL PAPERS. An alg t i c a1 Chemistry . Simplified Apparatus for Gas Analysis at a High Tempera- ture. ANTOINE DE SAPORTA (Chem. Zentr. 1908 ii 1377-1378; from Rev. gen. chirn. pure appZ. 1908 11 311-314).-The apparatus consists essentially of a distilling flask a repeatedly bent delivery tube a graduated cylinder and a small trough filled with mercury placed in a larger vessel containing water. I n the delivery tube just before it reaches the graduated cylinder and under the surface of the mercury i s a small hole. If now from whatever cause the evolution of gas ceases mercury ascends into the delivery tube and equilibrium is restored so that absorption can never take place. Quantitative Folded Filter Papers. F. .HART (Chem. Zed. 1908 32 1228).-The aut4hor advocates more general use of folded filter papers for quantitative work where rapid filtration is required ; their use is recommended especially when working with fine quartz- sand and cglloidal precipitates.L. DE K. J. V. E.ANALYTICAL CHEMISTRY. 179 Pressure-equalising Attachment for Desiccatore. EDWIN DOWZARD (Amer. J. Phacrm. 1908 80 558).-The following arrange- ment has been devised in order t o obviate the lifting of the lid of a desiccator caused by the expansion of the air when a hot crucible or basin is placed in it and the subsequent reduction of the pressure or?. cooling. A calcium chloride U-tube is placed in the lower part of the desiccator and carries an arm which passes through a perforated rubber stopper in the side of the desiccator.E. G. Estimation of Halogens in Organic Compounds. C. W. BACON (Chsm. News 1909 99 6 ; J. Amer. Chem. Soc. 1909 31 49-52).-The following details are given for successfully carrying out halogen determinations by Stepanoff’s method (Abstr 1905 i 335) Let w represent the number of grams of halogen compound taken (about 0.2) in a dry Kjeldahl flask; it is warmed under a reflux condenser with 15620 C.C. of at least 98% alcohol if the compound contains chlorine 68w C.C. if it contains bromine or 44w C.C. if i t contains iodine. The addition of sodium must extend over 30 minutes the weight of metal required being 1 9 . 5 ~ grams 8.52~ grams or 5 . 5 ~ grams according as the substance contains chlorine bromine or iodine. When all the sodium is added the solution is gently boiled for an hour allowed to cool to 50-60° diluted freely with water and acidified with nitric acid.A moderate excess of silver nitrate is added and when quite cool the excess of silver nitrate is estimated volumetrically by Volhard’s method. If the halogen involved is chlorine the precipitate should be filtered off; with bromine or iodine this is not necessary ; when copiously diluted with water the presence of alcohol does not interfere with titration. J. V. E. Detection and Estimation of Chlorates. JUAN FAGES VIRGILI (Anal. 3%. Quina. 1908 6 459-476).-Two solutions are recom- mended as a means of detecting chlorates in the absence of certain oxidising agents (enumerated below) the first A a solution of 50 grams of aniline hydrochloride in 1000 C.C. of hydrochloric acid D 1-12; the second B a solution of 50 grams of the same salt in 1000 c c.of hydrochloric acid D 1.14. B is used instead of A when the solution to be tested is dilute so that more of the latter has to be used in the test. This is generally carried out by taking 1 drop to 1 C.C. of the solution (or a small fragment to 1 gram of solid) in a test tube and adding 1 C.C. to 4 C.C. of solution A ; a chlorate produces an intense blue coloration. This is primarily due t o chlorine being liberated and acting on the aniline salt so that a number of oxidising agents (chlorine hypochlorites hypobromites bromates iodates peroxides chromates manganates permanganates vanadates and ferricyanides) also produce it ; but dilute nitric acid solutions of nitrates and nitrites do not give the blue colour so that the test is very useful for detecting chlorates in many special cases for example in nitres explosives urine.By means of it 0.00007 gram of potassium chlorate can readily be detected. In presence of bromides or iodides the reagent does not give an indication with chlorates or other oxidising agents; in such a case the haloids have t o be first removed180 ABSTRACTS OF CHEMICAL PAPERS. by adding silver nitrate in excess and then sodium chloride t o pre- cipitate the excess of silver; the filtered solution is used as jubt stated. I n the absence of oxidising agents the solutions A and B can be used to estimate small quantities of chlorates colorirnetrically. Solution A is used for quantities of 0*0001 to 0 0022 gram per 5 c.c.and B for quantities from 0 0005 to 0.0070. Twenty C.C. of the reagent are then added to 5 C.C. of the solution. For larger quantities of chlorate up to 0.01 gram 40 C.C. of B are added to 10 C.C. of the solution. The colour obtained after twenty minutes is compared with that of a series of solutions containing known quantities of chlorate and differing from one tube to another by 0.0005 gram for quantities between 0 005 and 0.01 gram and by 0.00025 for quantities between 0.002 to 0 005 gram. Another method is to make the colour comparison by means of successive dilution until the shades correspond. The results obtained are very good. W. A. D. Detection of Fluorine in Beer. JULES FLAMAND (Bull. SOC. chirn. Belg. 1908 22 451-453).-0ne litre of beer deprived of carbon dioxide by shaking is rendered alkaline by addition of ammonium carbonate and ammonia a few C.C.of saturated sodium sulphate solution are added and the liquid is heated to boiling. A 10% solution of barium chloride is added and after boiling for ten minutes the precipitate is allowed to settle; the clear liquid is decanted and the deposit is collected on a filter which is then at once placed in a drying oven ; the precipitate need not be washed. When dry it is detached from the filter transferred to a platinum crucible and gently ignited. When cold the crucible is placed in a cold water-batb. A little sulphuric acid is added and the crucible covered with a paraffin-coated glass plate on which some lines have been engraved. The plate must be kept cool by any suitable arrange- ment and the water-bathais then heated to boiling and kept so for an hour.If fluorine is present the usual etching will be obtained. L. DE K. Estimation of ‘gNeutral’’ Sulphur in Urine. LEO HESS (Chem. Zentr. 1908 ii 1290 ; from Berlin klin. Woch. 1903 45 1452-1453).-Five hundred C.C. of urine are mixed with 25-50 C.C. of bydrochloric acid and excess of barium chloride and heated to boil- ing in a flask fitted with a bulb apparatus containing alkaline pyrogallol; the heating is then continued for six hours on the water- bath. After twenty-four hours the liquid is filtered rendered alkaline with sodium hydroxide and saturated with chlorine. After the lapse of a few hours the liquid is acidified with hydrochloric acid and boiled.The barium sulphate thus formed represents the ‘( neutral ” sulphur. L. DE K. Estimation of Sulphuric Acid as Barium Sulphate. ERNST RUPPIN (Chew. Zeit. 1908 33 17-18).-Barium chloride should be added t o the boiling acid solution all at once and in quantity about twice that actually required. The precipitate should then be boiledANALYTICAL CHEMISTRY. 181 four times in succession with acidified water. Better results are however obtained by precipitating the sulphate in presence of sodium hydrogen carbonate (about 0.5 gram to 1 gram of sulphate); the co- precipitated carbonate is then re-dissolved by addition of hydrochloric acid. The barium sulphate thus obtained is after careful washing perfectly pure. L. DE I(. Estimation of Sulphuric Acid in Leather. JOHANNES PAESSLER and ARNOLDI (Chem.Zentr. 1908 ii 1297 ; from Collegium 1908 358-362).-Five grams of the finely-divided sample are placed in a platinum boat and mixed with 5 C.C. of 10% sodium carbonate and 1.5-1*8 grams of cobaltic oxide. If only combined sulphate is to be estimated no sodium carbonate is used. After drying the mixture is heated in a slow current of oxygen; the boat is placed either in a wide combustion tube or else in Schopper’s electric apparatus. L. DE I(. Nitrometer [Volumeter] with Barometric Correction. HERMAN (Bull. SOC. chim. Belg. 1908 22 440-444).-The nitrometer which however is suitable for a more extended application will be readily understood from the figure. The reservoir A is filled with a sufficient quantity of water and the stopcock R is turned in such a manner that the interior of the burette B is in communication both with the outer air and the mixer M.The air-tap r of the gasometer should be open. M which contains the substance and also the reagent needed to liberate the gas is attached to the burette and tho water level is brought to zero by raising the reservoir. Stopcock 22 is then turned so as to shut off the air but to still leave the connexion with the burette. A t this moment the reaction is started bylallowing the con- tents OF M to mix; it is seized by the stem and well shaken. The gas evolved displaces the liquidjin the burette and when the water level shows no further alteration the reservoir is lowered and the levels are restored The barometric correction is made by reducing the pres- sure of the gas evolved t o 760 mm.R is then turned 80 as toclose the upper part of B. If the pressure indicated by the barometer exceeds 7609 the bell jar is raised after closing the air-tap T. The mercury level falls while the volume of gas in the burette is increasing. If the pressure is less than 760 mm. the reverse happens. In either case the pressure is brought to 760 mm. and this will be the same both in the barometer and the burette as both are connected with the reservoir. The182 ABSTRACTS OF CHEMICAL PAPERS. thermometer employed has a scale attached to it for correction for temperature and tension of aqueous vapour but this scale is not shown in the figure. A table is given for correcting the volume of the gas for the temperature of 17" also for Oo and in the dry state.To save calculation the burette is also graduated so as to show the weight in milligrams of the gas. L. DE K. Estimation of Phosphoric Acid as Ammonium Phospho- molybdate. HENRI PELLET (Ann. China. anal. 1908 14 7-ll).- Chesneau's process (Abstr. 1908 ii 427) is recommended for the estimation of phosphorus in iron and steel and for the accurate estimation of very minute quantities of phosihoric acid in general. L DE K. Estimation of Phosphoric Acid in Basic Slags by Weighing the '' Yellow Precipitate." ZYGMUNT ROMA~~SKI (Chem. Zeit. 1909 33 46-47).-Fifteen C.C. of the sulphuric acid solution prepared as usual (= 0.15 gram of the sample) are neutralised with 15% sodium hydroxide solution using phenolphthalein as indicator. Five C.C.of acid mixture (34 C.C. of sulphuric and nitric acid D 1.2 up to one litre) are added and the whole heated to boiling. Fifty C.C. of molybdate solution are added and after remaining overnight the precipitate is collected at the pump on a Neubauer crucible washed with 1% nitric acid then with alcohol and finally with highly volatile light petroleum D 0.7. After drying at 40° it is weighed; multi- plication by 0.03496 gives the amount of phosphoric anhydride. When dealing with citrate-soluble acid 20 C.C. of the solution (=0.2 gram sample) are mixed with thirty. C.C. of the above acid heated to boiling and precipitated with fifty c,c. of molybdate solution. The molybdate solution should be prepared as follows four litres of nitric acid and 1600 grams of ammonium nitrate are placed in a ten-litre flask and the temperature is raised to 20°.Six hundred grams of ammonium molgbdate are dissolved in 2800 C.C. of hot water cooled to 30° and then poured into the acid liquid with constant shaking. When clear the reagent is filtered and ready for use. L. DE K. Estimation of Mineral Constituents in Vegetable Sub- stances. I;. VUAFLART (Bull. Assoc. Chim. sum. dist. 1908 26 448-455).-Phosphoric acid is generally estimated by burning the substance in the presence of calcium oxide but even this does not prevent a loss of the acid particularly in the case of wheat. It is therefore advisable to destroy the organic matters by heating the substance in a Kjeldahl flask with sulphuric acid and a globule of mercury adding afterwards some nitric acid to complete the oxidation ; the phosphoric acid is then estimated by the molybdate process. Potassium may be estimated as usual after destroying the organic matters with sulphuric and nitric acids but equally accurate results are obtained by moistening the substance with sulphuric acid and subsequent ignition.Chlorine will be retained completely in the ash if the substance is mixed previously with calcium oxide (5 2). SulphurANALYTICAL CHEMISTRY. 183 and sulphates may be estimated without loss by boiling the substance with nitric acid expelling the excess of the latter neutralising with sodium carbonate and finally heating the dry mass. Manganese is estimated in the ash by the lead peroxide method. Nitrates are best estimated as nitric oxide in the Schloessing apparatus. The author removes interfering matters by adding to the hoii aqueous extract treble the volume of alcohol.After a few days the solution is filtered and the filtrate concentrated to a few C.C. L. DEK. Estimation of Silvep. FRANZ MAWROW and G. MOLLOW (Zeitsch. anorg. Chem. 1909,61,96-99).-0n the addition of hypophosphorous acid to a boiling solution of silver nitrate heating being continued until the liquid is clear a black precipitate of silver separates immediately becoming grey ; this is collected washed with 96% alcohol until free from acid (water causes it to pass through the paper) dried and weighed as silver. The operation is complete in ten to fifteen minutes and gives accurate results. The presence of organic acids is without influence.Lead is precipitated by hypophosphorous acid as lead hypophos- phite. C. H. D. Estimation of the Hardness of Water. KLUT (Chem. Zentr. 1908 ii 1953 ; from K. Priifi-Alzst. Wassevversorg. dbwmserbeseit. 1908 10 75-85).-From a comparison of methods for estimating the hardness of water it is found that gravimetric methods alone are trustworthy although for rapidly ascertaining the total hardness of a hard water containing much magnesium Clark’s soap method gives good results. The Wartha-Peeifer-Lunge gravimetric method is not so simple or so accurate as the soap method. Carbonate hardness is best determined by Lunge’s method of titration using N/10 acid and methyl-orange as indicator. The qdoption of the terms carbonate hardness instead of b c temporary hardness,” and mineral acid hardness for ‘( permanent hardness,’’ is advocated.J. V. E. Precipitation of Magnesium a,s Ammonium Magnesium Phosphate. ERCOLE RAFFA (Gaxxetta 1908 38 ii 556-566).- The author has made a number of experiments to determine the conditions influencing the precipitation of magnesium as ammonium magnesium phosphate. The amount of precipitate obtained increases with the proportion of ammonia present but never reaches the theoretical quantity if the precipitation is carried out in the cold (compare Neubauer Abstr. 1896 ii 674). The presence of much ammonia or of ammonium chloride is useless to prevent precipitation of magnesium hydroxide. The only effect of excess of ammonia is to diminish the solubility of the ammonium magnesium phosphate an advantage which is often counteracted or greatly diminished by the possible formation of more complex phosphates such as Mg(NH4)4(P0,)2. For the gravimetric estimation of magnesium the following profedure is recommended The precipitant consists of an N/2 solution184 ABSTRACTS OF CHEMICAL PAPERS.of ammonium disodium phosphate obtained by mixing equivalent quantities of ammonia and of the phosphate ; the magnesium solution should contain 0-3-0*5% of magnesium. To 20-25 C.C. of the reagent 10 C.C. of the magnesium solution are rapidly added the mixture being shaken. After depositing the precipitate is filtered off on t o a tared filter or Gooch crucible washed with 2.5% ammonia solution until all the chlorine is removed and converted into pyro- phosphate in the ordinary way.The volumetric estimation of magnesium requires (1) a standard solution of uranyl acetate I C.C. = 0.005 gram P,O = 0.0067 gram PO ; (2) a N/2 ammonium disodium phosphate solution (wide suprcc) titrated at the time of using with the uranyl acetate solution. The magnesium solution should contain 0*3-05% of magnesium and should be perfectly neutral. Into a cylinder having a ground-in stopper and without constriction are placed 40 C.C. of the ammonium disodium phosphate solution and 10 C.C. of the magnesium solution ; the mixture is well shaken allowed t o settle and filtered through a dry filter. An aliquot part of the filtrate is mixed with 1-2 C.C. of acetic acid and the residual phosphate estimated by titration with the uranyl acetate solution.T. H. P. Estimation of Zinc with Ferrocyanide. ERWIN RUPP (Chem. Zeit. 1909 23 3-4).-A solution is prepared containing 4-5% of potassium ferrocyanide. Ten C.C. of this are diluted t o 50 c.c. 6 grams of potassium sodium tartrate are added and then an excess of N/10 iodine. After one hour the liquid is titrated as usual with N/10 sodium thiosulphate. One C.C. of N/10 iodine = 0.0512 gram of ferrocyanogen. When titrating zinc a suitable volume of the neutritlised solution i s added to a judicious excess of the ferrocganide solution diluted to 50-100 c.c. and containing 5 grams of sodium potassium tartrate. After twenty to thirty minutes the excess of ferrocyanogen is titrated as directed. The iodine is without action on the precipitate*formed. It must be remembered however that this precipitate is not zinc ferrocyanide for this in contact with excess of potassium ferro- cyanide rapidly forms a double compound 2K2Zn,(FeCy&.L. DE K. The Use of the Rotating Anode in Electrolytic Separations. MARY E. HOLMES (J. Amer. Chem. Xoc. 1908 30 1865-1874).-The advantage of rotation over stationary electrodes even with low cnrrents is demonstrated. On examining the tables given the following points are noticed. Separation of cadmium from aluminium and magnesium is always possible. The best conditions for the separation of cadmium from chromium are the use of a high current with phosphoric acid as electrolyte ; the separation also succeeds with a !ow current in presence of sulphuric acid. Separation of cadmium from iron is possible with a high current but not with a low one.Separations of cadmium from cobalt and zinc are possible with a low but not with a high current. Separation of cadmilim from nickel succeeds best with a high current. Separation of cadmiumANALYTICAL CHEMISTRY. 185 from manganese succeeds best with a high current but satisfactory results are also obtained with a low current using formic acid as electrolyte. L. DE K. Assay of Lead Sulphides. FELIX JACOBSOHN (Chem. Zentr. 1908 ii 1291 ; from Gummi Zeit. 1908 22 1200).-Commercial lead sulphide often contains sulphate and therefore it is necessary to estimate the true sulphide which is readily done by heating with fuming hydrochloric acid and collecting the hydrogen sulphide evolved in an ammoniacal solution of silver nitrate. Any free sulphur may Detection of Mercury in Organs by means of the Mioroscope. C .LOMBARDO (Chem. Zentr. 1908 ii 1788; from Awh. Farm. sperim. 1908,7,4OO).-The following methods in which the mercury is reduced to the metallic state by means of stannous chloride are stated t o be capable of detecting the presence of one part of mercury in 4,000,000. Five C.C. of the filtered liquid (urine stomach contents etc.) are mixed with 5 C.C. of stannous chloride solution (prepared by dissolving 12 grams of stannous chloride in a mixture of 25 C.C. of hydrochloric acid and 75 C.C. of water)and submitted to centrifugal action for a few minutes. The precipitate is then examined under the microscope. The presence of a small quantity of albumin aids the reaction and practically every mercury salt with the exception of the sulphide may be detected by the test.The second method described consists in placing parts of the organs in either 70% alcohol or 10% formaldehyde solution for about two days then washing them with water and immersing them in the stannous chloride solution ; the pieces are next washed successively i n water alcohol and xylene and embedded in paraffin. Sections are cut and after the removal of the paraffin are examined microscopi- cally; the mercury is seen as small globules. The tests will not detect the presence of mercury in decomposed organs probably owing to the mercury having been converted into the sulphide. Volumetric Estimation of Mercuric Salts. H. MORAWITZ (Zeitach. anorg. Chem. 1908 60 456-458).-The author titrates mercuric chloride by means of '' pure I' N/10 potassium cyanide which has been freed from any carbonate by addition of barium chloride.As indicator and catalyst a saturated solution of p-nitrophenol in N/50 hydrochloric acid is employed of which 10 drops are added. When checking this solution 100 drops are used and the result divided by 10. The number of C.C. of cyanide used are then deducted from those used in the mercury titration. In these circumstances mercuric chloride behaves like a dibitsic acid. Probably other mercuric salts may be converted into ohloride by Estimation of Geria and other Rare Earthe in Rocks. MAX DITTRICH (Ber. 19OS 41 4373-4375. Compare Meyer D.R.-P. 202523 and Hauser Abstr. 1908 ii 987).-The presence of iron be extracted by boiling with a suitable solvent.L. DE E(. W. P. S. means of an alkali chloride. L. DE E. YOL. XCVI. ii. 33186 ABSTRACTS OF CHEMICAL PAPERS. salts affects the precipitation of cerium as cerous oxalate. The best precipitating agent is ammonium oxalate and when iron salts are present it is necessary to use a very large excess of the precipitating reagent. For example with 0-2 gram of cerous sulphate and 15 C.C. of a concentrated solution of ferric salt 200 C.C. of saturated ammonium oxalate are necessary. The precipitate is perfectly white and free from iron compounds and should be washed with dilute ammonium oxalate solution J. J. S. Colloidal Reaction for some Metallic Salts. EDMUND STIASNY (Chem. Zentr. 1908 ii 1296 ; from Collegium 1908 348).-A solution of an aluminium salt even i f containing but 0.01 mg.per c.c. gives a flocculent precipitate when 5 C.C. are boiled with 5 C.C. of tannin solution (1 1000) and 10 C.C. of N-sodium sulphate. Sodium acetate may also be used and acts in the cold. Similar precipitates are obtained with the salts of calcium barium strontium magnesium zinc lead chromium and iron but not so distinctly as in the case of aluminium; manganese however gives a Estimation of Manganese in Pig Iron by the Persulphate Method. H. KUNZE (Stahl u. Eisen 1908 28 1715-1716).-Two grams of pig iron or one gram of spiegel are dissolved in a 500 C.C. graduated flask with 30 C.C. of nitric acid D 1.2. The flask is filled up the graphite allowed to settle and 25 C.C. of the liquid taken. To this are added 10 C.C.of the same nitric acid and 5 C.C. N/10 silver nitrate (for pig iron) or 15-20 C.C. for spiegel. The solution is oxidised with persulphate to convert the manganese into permanganate and titrated in the usual way (compare Rubricius Abstr. 1905 ii 766). good reaction when sodium acetate is used. L. DE K. C. H. D. Influence of Copper on the Titration of Iron by the Zimmermann-Reinhardt Method. R. SCHRODER (Zeitsch. ofentl. Chem. 1908 14 477-492).-A series of experiments to study the influence of copper on the accuracy of the estimation of iron by Zimmermann-Reinhardt's volumetric process (reduction with stannous chloride addition of mercuric chloride and titration with perman- ganate). The presence of copper either slightly increases or decreases the amount of iron found; sometimes there is a compromise.The final conclusion arrived a t is as follows quantities of copper not exceeding 0.01% may be neglected in ordinary analyses of iron ores if the operations are conducted with due speed. But with more copper present and in reference analyses the copper should be first removed. Iron wire should not be used as a means of standardising per- manganate if it is not free from copper and the stannous chloride should be tested for that metal. L. DE K. Molybdates of Nickel and Cobalt. HERMANN GROSSMANN (Bull. SOC. chirn. 1909 [iv] 5 5).-A reply to Pozzi-Escot (Abstr. 1908 ii 1042) pointing out that the latter has confused W. Marckwald with E. Marckwald and that it was to the second of these investigatorsANALYTICAL CHEMISTRY 187 the author attributed correctly the process for the detection of nickel in presence of cobalt referred to in his previous paper (Abstr.1908 ii 230). T. A. H. Volumetric Estimation of Chromium with Potassium Ferricyanide. HERMANN BOLLENBACH and E. LUCHMANN (Zeitsch. anorg. Chem. 1908 60 446-455).-The chromic solution which must be free from metals precipitable by hydrogen sulphide also from cobalt nickel manganese and ferrous salts and other reducing inorganic or organic substances is poured into a freshly prepared solution of 4 to 12 grams of pure potassium ferricganide to which 50 C.C. of 2N-sodium hydroxide have been added. After thorough stirring aqueous barium hydroxide is added until all the chromate formed has precipitated and the precipitate is collected on a double filter and well washed. The filtrate is acidified with dilute hydrochloric acid and titrated with permanganate solution which has been standardised say with pure potassium ferrocyanide. If the permanganate contains exactly 3.546 grams per litre 1 C.C.will represent 0.001947 gram of chromium. Chromates must be reduced by means of sulphurous acid the excess of which is then removed by boiling L. DE K. Reaction of Uranium and Cadmium Salts. P. LEMAIRE (Ann. Chim. anal. 1909 14 6-7).-The reagent consists of a 5% solution of thiosinamine to 100 C.C. of which are added when required 5 C.C. of sodium hydroxide. To 3-4 C.C. of the alkaline reagent are added 2-3 drops of the solution to be tested and the mixture is heated to boiling.Cadmium and uranium are the only metals which yield a yellow precipitate. L. DE K. Eatirnation of Antimony and Tin. EDWARD CAHEN and GILBERT T. MORGAN (Anahpt 1909 34 3-9).-The results are given of a detailed examination of several methods which have been proposed for the estimation of these two metals. Vortmann and Metzl's process (Abstr. 1905 ii 655) was found to be trustworthy for the separation of antimony from tin and for the estimation of the former metal if certain precautions such as the absence of nitric acid or other oxidising agent etc. are observed. The method does not however admit of the estimation of tin by any simple process. It is recommended that the antimony trisulphide obtained should be heated to a temperature of 150-180" in an atmosphere of carbon dioxide before being weighed.The method described by Czerwek (Abstr. 1906 ii 708) gave good results in the case of tin but mas quite untrustworthy for the estimation of antimony. The best method was found to be that of Henz (Abstr. 1904 ii 150). w. P. s. Estimqtion of Tin in Tin-plate. KARL MEYER (Zeitsch. angew. Chem. 1909 22 68-69).-Twenty to fifty grams of the cleansed material are cut up into small pieces and placed in a spacious basin. Sufficient water is added to cover the metal and this is then heated at BOO when 1 to 2.5 grams of sodium peroxide are added. Whenthe effervescence ceases a little another gram of the peroxide is added 13-2188 ABSTRACTS OF CHEMICAL PAPERS. and when the evolution of gas ceases altogether the flame is removed and the undissolved iron is examined for any tin.Should there still be some left more peroxide is added and the whole heated to boiling. Finally the iron is washed with boiling water then with alcohol dried and weighed. Any lead present is also dissolved in the alkaline liquid. If desired the true amount of tin may be estimated in the solution. L. DE K. Organic Analysis with Sodium Peroxide. M. EMANUEL POZZI- ESCOT (Ann. Chim anal. 1909 14 5-6).-A slight modification of Von Koneck’s process. The nickel crucible is fitted with a lid which can be tightly closed by means of a bayonet joint and is fitted with a tube 3 mm. in diameter and 7-8 cm. in height. 0.2 Gram of the substance is carefully mixed with 4-5 grams of sodium peroxide and introduced into the crucible. After fixing on the lid a slight heat is applied with a small flame when very soon the action sets in causing the crucible to become white hot.After cooling for ten minutes the lid is removed and the crucible is placed in a vessel filled with water. The process gives satisfactory results for the estimation of the halogens ; nitrogen is converted into nitrate sulphur into sulphate and phosphorus and arsenic are also retained as phosphate and arsenate. l’he author however cannot recommend the process for the estimation of the carbon. L. DE K. A New Colour Reaction of Petroleum. CHARLES ARRAGON (Chem. Zed. 1908 33 20-21).-Equal volumes of petroleum and nitric acid D 1.4 free from nitrous acid are well shaken for half a minute. Pure American petroleum turns a fine violet whilst the acid layer turns yellow.Austrian Gallician and Russian petroleum turns intensely yellow the acid becoming brown. I n the case of mixtures the whole first turns a pale violet and then suddenly changes to yellow. I n this manner 10% of Austrian oil may be detected in American petroleum. L. DE K. Some Reactions and Properties of Essential Oils. LOUIS DUPARC and ALF. MONNIER ( A d . sci. p?bys. nat. 1908,26,609-639). -This research was undertaken in order to discover a simple method of detecting absinthe and similar liqueurs containing thujone. A modified form of Legal’s reagent is suggested for this purpose. Preliminary experiments on the determination (a) of the quantities of water necessary to just produce turbidity in alcoholic solutions of various essential oils ( b ) of the quantities required to just ensure *‘ complete precipitation ” of oils from such solutions and (c) observa- tions on the opacities of such ‘( completely precipitated ” preparations showed that these methods could not be employed satisfactorily for distinguishing between liqueurs containing thujone and those free from this constituent but containing other oils.Similarly the iodo- metric method devised by Sangk-FerriAre and Cuniasse (Abstr. 1903 ii 247 336 331) for the estimation of essential oils in absinthe was found to give different results even with the same distillate under the same conditions and is therefore untrustworthy.ANALYTICAL CHEMISTRY. 189 Cuniasse's observation (Abstr. 1907 ii 413) that Legal's reagent givee a deep red coloration with oils containing thujone such as those of wormwood and tansy was confirmed.Of the other essential oils and their constituents tried citral is the only one likely to occur in liqueurs which gives a red colour likely to be mistaken for that given by thujone although somewhat similar colours are also given by oils of vervain caraway and rue. Red colorations are also given by rum brandy and other spirits due to the aldehydes they contain. The application of the test has therefore been modified. To 100 C.C. of the liqueur 1 C.C. of aniline and 1 C.C. of syrupy phosphoric acid are added and the mixture heated during. one hour in a reflux qpparatus. The mixture is then distilled and 90 c c. collected. To 10 c c. of this distillate 2 C.C. of zinc sulphate solution (lo%) 0.5 C.C.of sodium nitroprusside solution (lo%) and after cooling 4 C.C. of sodium hydroxide solution (5%) are added. The cooled liquid is acidified with 2-3 C.C. of acetic acid when if thujone is present a gooseberry-red precipitate is formed. Citral gives an orange-red precipitate under similar conditions but this constituent if originally present would be eliminated by the preliminary treatment of the liqueur. The pre- cipitate formed is much more stable than the red colour given by Legal's reagent. If very small quantities of thujone are present a preliminary concentration of the oils in the liqueur is effected by precipitating them with water and extracting with light petroleum which is then removed by careful distillation the residue being dissolved in 60' alcohol.T. A. H. Relation between the Gryoscopic Points of Wines and their Alcoholic Strength. W. MESTREZAT (Ann. Chirn. anal. 1909 14 ll-l4).-The author has found that the alcholic degree of mines may be determined with sufficient accuracy by dividing the cryoscopic points by 0.44. The apparatus resembles a Winkler cryoscope (for milk testing). It is composed of a Violette-tube in which moves by way of a stirrer a platinum wire having a spiral a t its lower end; a thermometer divided to 1/50" occupies the axis of the tube. Twenty-five C.C. of the mine are placed in the apparatus which is then cooled in a mixture of ice and salt l o - 6" or - 7". The thermometer gradually lowers but then suddenly rises up to a fixed point which is the Estimation of the Total Acidity of Wines.OTTORINO CARLETTI (Boll. chim. farm. 1908 4'7 787-788).-When the acidity of a red wine is estimated by titration with sodium hydroxide solution in presence of phenolphthalein the change of colour of the liquid can be easily seen if only the light traversing the solution and not the reflected light as well be observed. For this purpose the author uses a box blackened inside and having a circular hole in the top jusb large enough to admit the beaker used in the titration and another slightly smaller hole in the bottom; the height of the box should be rather less than that of the beaker. A white porcelain plate rotatable about a horizontal axis is so arranged that the maximum of cryoscopic point. L. DE K.190 ABSTRACTS OF CHEMICAL PAPERS.light is reflected into the beaker. For the titration with N/10 sodium hydroxide solution 10 C.C. of wine diluted with a few C.C. of water are taken together with five drops of a 1% alcoholic solution of phenolphthalein. T. H. P. Soma of the Fatty Acids occurring in Butter Fat. R. K. DONS (Zeitsch. Nahr. Gecnussm. 1908 16 705-725).-1n a previous paper (Abstr 1908 ii 238) the author has given a method for the estimation of caprylic [octoic] acid in butter fat and as this method depends on the different solubility of the lower fatty acids in hot water he now gives the results of an investigation on the solubility and volatility of these acids. Capric acid [decoic acid] although by itself slightly soluble in cold water is not extracted by hot water from mixtures containing higher fatty acids ; octoic acid dissolves to a slight extent and when a mixture of fatty acids is shaken with several successive quantities of hot water small amounts of this acid are found in each of the extracts.Hexoic acid is completely extracted from mixtures with higher fatty acids on repeated treatment with hot water and butyric acid is obtained in solution by shaking the fatty acid mixture once with water. The total quantity of octoic acid in a mixture of butter fatty acids may be estimated by the method described previously if about 1250 C.C. of distillate are collected and allowance made for the small quantity of the acid extracted from the fatty acids by the hot water. A method for the estimation of decoic lauric and myristic acids is also suggested ; it is based on the different rates at which these acids distil in a current of steam.Colour Reaction of Oleic Acid. Quick Method of Identify. ing Vegetable Fibre. A. MANEA (Chem. Zentr. 1908 ii 1702 ; from Bul. SOC. Stiente Bucuresti 1908 17 256-257).-Cellulose as indeed all vegetable fibres when mixed with strong sulphuric acid and oleic acid or its esters gives a red coloration when water is added t o the solution so as to cause it to become warm. Stearic palmitic margaric butyric and isobutyric acids do not behave in this manner neither do animal fibres when in presence of concentrated sulphuric acid and oleic acid give this coloration. It is thus possible to use this reaction for discriminating between animal and vegetable fibres and also for identifying oleic acid.Various fractions of crude petroleum more especially that boiling a t 250° give a similar colour reaction when care is taken that the addition of water td the strong sulphuric acid does not greatly increase the temperature. Nature of the Chromophore Group in the Resorcinol Telst for Tartaric Acid. GEORGES DENIG~S (Bull. Xoc. chim. 1909 [iv] 5 19-24).-Results of the application of the resorcinol test (Abstr. 1896 ii 80) to a large number of substances show that the character- istic red to reddish-violet colour is only given by those containing the complex H0.C-C*OH. This group may be present as such as in ethylene glycol or it may be partly or wholly esterified as in P-chlorolactic acid or dibenzoyltartaric acid. In order that the group W. P.S. J. V. E. I 1 IANALYTICAL CHEMISTRY. 191 should behave as a chromophore the spare affinities of the carbon atoms as shown above must be united to (1) hydrogen atoms (ethylene glycol and its derivatives) or (2) carbon itself united t o hydrogen (homologues of ethylene glycol) or (3) a carbinol grouping. The colour produced is most intense when the chromophore is in the near neighbourhood of a carboxyl group as in tartaric tartronic and trihydroxyglutaric acids. These rules are also applicable when . resorcinol is replaced by other polyhydric phenols such as phloro- glucinol. Applied in the following manner the test may be used t o distinguish glyceric tartaric and tartronic acids. Two C.C. of a mixture of 10 C.C. each of sulphuric acid (D 1-84) and acetic acid with 1 C.C.of a 2% solution of resorcinol are heated to boiling and 0.1 C.C. of a solution of the acid (0.005% in water) added. With glyceric acid the liquid acquires immediately a pink tint passing rapidly into gooseberry-red Tartaric acid gives a pomegranate-red appearing more slowly and with a solution one-tenth the above strength the colour is wine-red. With tartronic acid a dead-leaf colour appears slowly. On boiling each of these liquids the red colours of the first two become intensified whilst the colour of the third changes t o wine-red. Substances such as ethylidenelactic acid contain the chromophore but do not give the colour reaction owing to their decomposition by the sulphuric acid used. T. A. H. Separation of Benzoic and Cinnamic Acids.K. SCHERINQA (Phamn. Jeekblad. 1908 45 1535-1536).-A reply to de Jong (A.bstr. 1908 ii 993). The author admits that benzoic acid is formed if the excess of permanganate added is not removed quickly. A solution of benzoic acid in ether may be eva.porated and the residue dried at 40' on a water-bath without any appreciable loss of acid. L. DE I(. Microscopic Analyses of Soluble Crystallisable S ubshnces. [Salicylic Acid. Caffeine.] ANNIBALE FERRARO (Boll. cfiinz. farm. 1908 47 789-790).-1n order t o decide whether a sample of salicylic acid is pure the author evaporates a drop of its ethereal solution on a microscope slide and examines the crystalline residue under the micro- scope similar examination being made of ethereal solutions of salicylic acid mixed with similar powders such as benzoic acid.By such means the approximate proportions of the components in a mixture can be estimated. The purple-red colour obtained by treating caffeine with nitric acid or chlorine and subsequently with ammonia is sometimes not clearly shown by caffeine extracted from coffee by means of chloroform or ether but the caffeine can be rendered evident by evaporating a drop or two of the chloroform or ethereal extract and examining the residue under the microscope; it is however found that the appearance of the prismatic crystals of caffeine varies with the solvent used and with the concentration of the solution from which they are deposited. T. H. P.192 ABSTRACTS OF CHEMICAL PAPERS. Objections to the Use of Potassium Dichromate as a Preservative of Milk 'Destined for AnalyBis.A. MONVOISIN (Compt. vend. 1908 147 1403-1404).-1n addition to the dis- advantages already mentioned by Gr6lot (Abstr. 1907 ii 5 13) there is the further objection that milk containing potassium dichromate always produces a blue coloration with p-phenylenediamine ; hence it is impossible to decide whether the milk has been boiled or whether hydrogen peroxide has been added. G. B. Detection and Estimation of Formaldehyde in Milk. HERBERT S. SHREWSBURY and ARTHUR W. KNAPP (Analyst 1909 34 12-13).-To 5 C.C. of milk contained in a test-tube are added 10 C.C. of concentrated hydrochloric acid containing 0.1% of nitric acid ; the mixture is shaken vigorously and kept for ten minutes in a water- bath a t a temperature of 50'.The tube and its contents are then cooled rapidly to about 15'. A violet coloration denotes the presence of formaldehyde and its intensity indicates the amount which may be estimated by comparison with standard mixtures of milk and formaldehyde treated in the same manner. The acid reagent should be freshly prepared. w. P. s. Estimation of Aldehydes in Oil of Lemon. 'ALEXANDER H. BENNETT (Analyst 1909 34 14-l7).-The method proposed is a modification of that described originally by Walther (Abstr. 1900 ii 173) ; the use of sodium hydrogen carbonate is discontinued owing to the objection that the carbon dioxide evolved carries off hydroxyl- amine. The details of the modified process are as follows. Twenty C.C. of the oil of lemon are mixed with 20 C.C. of N/2-alcoholic hydroxyl- amine hydrochloride solution and to the mixture are added about 8 C.C.of N/1-alcoholic potassium hydroxide solution and 20 C.C. of alcohol. The mixture is boiled gently under a reflux apparatus for thirty minutes and then cooled. The condenser is washed and the contents of the flask are diluted by the addition of about 250 C.C. of water the solution being then rendered neutral to phenolphthalein and titrated with N/%sulphuric acid using methyl-orange as indicator. The number of C.C. of acid required is subtracted from the number used in a blank experiment in which no oil of lemon is present and the difference multiplied by 0.076 to obtain the weight of citral. w. P. s. Estimation of Small Quantities of Impurities in o-Toluidine and o-Nitrotoluene.ARNOLD F. HOLLEMAN (Rec. trav. chim. 1908 27 458-462).-1n addition to an account of work published pre- viously (Abstr 1905 i 272) this paper contains details of the analysis of two samples of commercially '' pure " o-toluidine which were found to contain 0.9% and 4.1% respectively of impurities. The method already described (Zoc. cit.) can be applied to the analysis of o-nitrotoluene after reduction with iron and hydrochloric acid. w. 0. w.ANALYTICAL CHEMISTRY. 193 Estimation of Alkaloids. Bitter Principles and Glucosides with the Zeiss Immersion Refractometer. FRANZ UTZ (Chsm. Zed. 1909 33 47-49). -A preliminary papor. Successful attempts have been made to determine the quantity of some alkaloids from their refraction in the Zeiss instrument. The following have as yet been tried.Cafleine in aqueous solution morphine in methyl alcohol also the hydrochloride in acid and aqueous solutions quinine also the hydrochloride in methyl alcohol and 6rucine in methyl alcohol solution. L. DE K. An Error in the Estimation of Caffeine by Juckenack and Hilger’s Method. K. LENDRICH and RUDOLF MURDFIELD (Zeitsch. Nahr. Genussm. 1908 16 647-658).-Experimental evidence is given that caffeine cannot be extracted completely from a perfectly dry residue such as is obtained in the method described by Juckenack and Hilger (Abstr. 1897 ii 611) by means of carbon tetrachloride. The extraction of the alkaloid is however complete if the residue is moist. It is therefore recommended that the aqueous extract of the coffee should be treated as described by Juckenack and Hilger with aluminium hydroxide and sodium hydrogen carbonate and filtered.The portion of the filtrate taken for the estimation is evaporated mixed with powdered aluminium hydroxtde and sand and while still in a moist condition extracted in a Soxhlet apparatus for about ten hours with carbon tetrachloride. w. P. s. The Caffeine-content of Raw Coffee and a Modiflcation of Juckenack and Hilger’s Method for Estimating Caffeine. RUDOLF HEFELNANN (Zeitsch. ofentl. Chem. 1908 14 448-450).- From 0.864 to 1.669% of caffeine was found in specimens of com- mercial unroasted coffee beans; these results lie very close to the figures (1.00 to 1.75%) given by the German Food Regulations as the limits for the caffeine-content of unroasted coffee. It is also pointed out that cof€ee free from caffeine is now on the market. Juckenack and Hilgsr’s method for the estimation of caffeim (Abstr.1897 ii 611) tends to give too low results unless the residue after extraction with carbon tetrachloride is moistened mixed with magnesium oxide re-dried and subjected to a further extraction with this solvent. w. P. s. The Theobromine-content of Cocoa and a New Method for the Estimation of Theobromine. ADOLF KREUTZ (Zeitsch. Nahr. Genzcssm. 1908 16 579-584).-A portion of the theobromine occurring in cocoa is extracted together with the fat in the process described by the author (Abstr. 1908 ii 641) for the estimation of the latter; cocoa also contains a quantity of theobromine in the form of a glucoside and this portion can be separated only after treating the cocoa with an acid.The method now proposed for the estimation of the total theobromine is ,as follows. From 1-5 t o 2 grams of the cocoa are treated with chloral alcoholate as described (Zoc. cit.) and the residue of fat obtained is after being weighed dissolved in cold carbon tetrachloride ; the fheobromine present in the fat remains194 ABSTRACTS OF CBEMICAL PAPERS. insoluble and is separated by filtration. The solution of the fat in carbon tetrachloride is evaporated and the residue of fat weighed. The difference between the two weighings gives the amount of theobromine. The residue of cocoa obtained in this part of the process is then dried and boiled with 50 C.C. of 4% sulphuric acid for forty-five minutes in a reflux apparatus. The hot solution is next neutralised by the addition of moist barium carbonate and evaporated to dryness; the residue is mixed with sand extracted with chloroform for five hours in a Soxhlet apparatus and the residue of theobromine obtained on evaporating the solvent is weighed.From the results of estimations given it is seen that the two kinds of theobromine cannot be separated from each other quantitatively; the total amount of theobromine found in various cocoas varied from 1.99 to 3.85%. w. P. s. Detection of Morphine. C. REICHARD (Pharm. Zentr-h. 1908 49 951-954).-Morphine may be identified by means of the re- actions given previously by the author (Abstr. 1905 ii 68 ; 1506 ii 637) and also by the blue coloration which is obtained when a neutral morphine solution is mixed with ferric chloride or ferric acetate solution.Titanic acid dissolved in concentrated sulphuric acid gives with morphine a reaction similar toathat obtained with iodic acid. I n every case better reactions are obtained if the morphine is tested in the solid .state and not in solution. It is also pointed out that morphine is partly converted into dehydromorphine in the animal body and that this should be remembered when testing for morphine in cases of suspected poisoning Dehydromorphine may be detected or distinguished from morphine by the shape of its crystals its very slight solubility in dilute acids and by giving a blood-red coloration Estimation of Proteins in Milk treated with Formaldehyde. Direct Estimation of Formaldehyde in Milk.ANGELO AGRESTINI (Chem. Zentr. 1908 ii 1640-1641 ; from Stax. sperim. agyar. ital. 41 520-529).-8 criticism of Denigds' mercury process for the estimation of proteins in milk. I n the case of samples containing formaldehyde the addition of a little 10% hydroxylamine hydrochloride solution is recommended before adding the mercury reagent. The presence of formaldehyde may thus be proved by titrating before and ADOLF JOLLES (Bei.. Deut. phurm. Ges. 1908 18 598-599).-0ne hundred C.C. of the urine are placed in a beaker and if necessary neutralised with acetic acid 5 C.C. of formalin reagent are added and the liquid is heated on the boiling water-bath for thirty minutes. The albumin is then at once collected on a weighed filter dried at l l O o washed first with boiling water then with alcohol and ether again dried at l l O o and weighed.Any co-precipitated mineral matter is allowed for as usual. The reagent is prepared by mixing 50 C.C. of 1% acetic acid 50 C.C. of commercial formaldehyde and 15 grams of sodium chloride. with the formaldehyde reagent mentioned previously. w. P. s. after addition of hydroxylamine hydrochloride. L. DE I(. Estimation of Albumin in Urine. TJ. DE K.ANALYTICAL CHEMISTRY. 195 A New Albuminometer. L. E . WALBUM (Chem. Zentr. 1908 ii 1632 ; from Deutsch. med. Voch. 1908 34 1728-1729).-The prin- ciple of the method consists in the fact that trichloroacetic acid gives a turbidity with weak solutions of albumin. The degree of turbidity is then determined in the author's apparatus which is based on com- parison with a standard milky glass.The results are however only Separation of Caseinogen from Human Milk. RODOLPHE ENGEL (Biochem. Zeitsch. 1908 14 234-S37).-The milk is diluted five-fold and acidified with acetic acid ; the mixture is cooled for two t o three hours with occasional shaking then warmed t o 40' for a few minutes and finally filtered. Phenolphthalein as a Reagent for Blood. M. EMMANUEL POZZI-ESCOT (BUZZ. Soc. chim. Belg. 1908,22 415-416).-It has been stated by Delarde and Benoit (Compt. rend. Xoc. Biol. 1908 64 990) that an alkaline solution of phenolphthalein forms a more delicate test for blood than tincture of guaiacum. The author finds that the reagent obtained by dissolving one gram of phenolphthalein in 50 C.C. of sodium hydroxide solution and decolorising by reduction with excess of zinc dust is re-coloured in the presence of hydrogen peroxide not only by fresh blood but also by extract of malt saliva the ash of blood pus most organic secretions and vegetable extracts certain urines free from blood and by a very large number of metallic salts such as those of cobalt manganese iron and lead.The conclusion is drawn that as a test for blood the reagent is absolutely valueless. approximate. L. DE K. W. D. H. E. H. Clinical Methods for the Detection of the Colouring Matter? of Blood and Some Related Colouring Matters. OTTO SCHUMM (Arch. Pharm. 1909 247 12-27).-A critical r&sum& of the methods available for the detection of blood in urine faeces stomach contents etc. in the course of which the delicacy and best conditions for the application of the absorption spectrum test the guaiacum (compare Abstr.1907 ii 320) aloin benzidine (Abstr. 1907 ii 827) and potassium cyanide tests are discussed as also the haemochromogen and haematoporphyrin tests. Lastly the detection of urobilin in urine and faeces by a modification of the zinc chloride test is dealt with. T. A. H. Reaction of Bile Acids with Rhamnose and &Methylfur- aldehyde. CARL NEUBERG (Biochem. Zeitsch. 1908 14 349-350). -The reaction mentioned by Jolles (Abstr. 1908 ii 998) has been des- cribed previously by Neuberg and Rauchmerger (Abstr. 1905 ii 122). The same reaction is given not merely by bile acids but also by cholesterol and camphor and terpene derivatives. Detection of Urobilin in Urine.EDUARD STRAUSS (Xiinch. med. Woch. 1908 No. 49 reprint).-The urine is acidified with a few C.C. of acetic acid and precipitated with about a fourth the volume of lead acetate ; the filtrate is extracted with amyl alcohol which after this J. J. S.196 ABSTRACTS OF CHEMECAL PAPERS. treatment readily dissolves out the urobilin. characteristic fluorescence with ammonium zinc chloride. The extract gives the S. B. S. Simplification of the Jakoby-Solm’s Ricin Method for the Estimation of Pepsin. XAX EINHORN (Chem. Zentr. 1908 ii 1295 ; from Berlin Win. Woch. 1908 45,1567-1568).-The modified apparatus consists of a vacuum glass vessel with ( 1 stand for twelve calibrated pepsin tubes; it is filled with water at 50-60° and well corked. Each tube is marked 2 3 3.5 c.c.and at its lower end it is graduated in millimetres. Each tube is filled with the 1% ricin solution up t o 2 c.c. the diluted pepsin solutions (gastric juice) are then added up t o 3 c,c. and finally N/10 hydrochloric acid up to 3.5 C.C. The corked tubes are shaken and placed in the vacuum vessel. After thirty minutes those tubes are noted in which the precipitate has quite disappeared and a t the same time the height of the precipitate in the others is noted. Normal gastric juice when diluted 10 to 20 times gives a precipitate disappearing in thirty minutes ; if there is still a precipitate with a ten-fold dilution the pepsin content is insufficient and if it disappears with a forty-fold dilution the amount of pepsin is excessive. L. DE E(. Soil Analysis. C. BLOCH and M. HOFFMANN (Bied. Zentr. 1908 37 721-722; from Mitt. landw. Inst. Univ. Breslau 1907 4 Heft 1-2).-In Thiele’s method of soil sampling (ibid. 3 Heft 2) ten samples are taken with a spade ten times at equal distances for an area of $ hectare. The number of samples is then reduced to ten or 40 per hectare by mixing. The samples were found to yield un- satisfactory results the percentages of nitrogen varying from 0,1450 to 0.1556. . To obtain samples for mineral analysis a spadeful of soil was taken five times a t equal distances (on a surface of 25 square metres) after remov- ing about 5 cm. of surface soil. This was repeated five times and in this manner five average samples obtained. The samples were obtained from four plots which had received each year (1) potassium (2) nitrate (3) no manure and (4) complete manure; the total nitrogen and mineral constituents were determined in each. The potassium results in (4) varied from 0.0169 to 0.0672 and the other results were more or less divergent. The result3 show that whilst it would be incorrect to select con- cordan t results and ignore the others approximately correct results can generally be obtained by this method by calculating the total means and the probable errors. Even then however it mas not always found possible to obtain indications of continuous manuring. $ z N. H. J. 11. -3

ISSN:0368-1769    

DOI:10.1039/CA9099605178

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

197 Organic Chemistry. The Relative Ease of Addition in the Alkylene Group. ARTHUR MICHAEL and ROGER F. BRUNEL (Amer. Chm. J. 1909 41 118-148).-Exceptions to Markownikoff's rule governing the addi- tion of halogen acids to unsaturated hydrocarbons have been indicated by SagtzeE (Annalen 1875 179 296) and Linnemann (Annalen 1872 163 96). In a series of papers (Abstr. 1888 1054 ; 1900 i 321 ; 1904 ii 164; 1906 i 550 551) Michael has developed the view that a general law of addition connecting the course of the process with the structure of the substances can be based on the positivenega- tive " hypothesis. This positive-negative law of addition is supported by the work of Berthelot (Compt. rend. 1862 54 1350) and Butleroff (Annalen 1875 180 246 ; Ber. 1873 6 561) on ethylene propplene and isobutylene whilst the observations of Butleroff (Annalen 1877 189 61 ; Abstr.1880 230) and Kondakoff (Abstr. 1897 i 177) tend to confirm the existence of a maximum additive power in the series deduced theoretically. I n order to determine where this maximum occurs the behaviour of the butylenes /?-methyl-A~-butylene py-dimethyl-Ap-butylene and diisobutylene towards sulphuric acid of different strengths the halogen acids and phosphoric acid has been studied. At 28-29" a mixture of 1.5 parts of sulphuric acid with 1 part of water absorbs isobutylene about twelve times as fast as +-butylene which is absorbed by (5 1) sulphuric acid a t about the same rate as the isobutylene is absorbed by the weaker acid. A t the same tem- perature +-butylene is absorbed almost twice as fast as n-butylene by sulphuric acid of the strength 3.5 1.When isobutyl alcohol is dehydrated by passing its vapour through a Jena combustion tube containing pieces of a graphite crucible heated at 500" analysis of the gas produced by absorption with sulphuric acid shows that it contains 55% of isobutylene and 2.5-3-0% of a gas unabsorbed by bromine whilst if the graphite is replaced by aluminium oxide the evolved gas contains 65-70% of isobutylene and about 1% of hydrogen. i8oButylene is dissolved by sulphuric phosphoric and hydrochloric acids at least three times as fast as p-methyl-As-butylene whilst the latter is absorbed twelve times as rapidly as By-dimethyl- A@-butylene by (2 1) sulphuric acid Although py-dimethyl- A-butylene dissolves readily in sulphuric acid of the strength 4 I diisobutylene is not dissolved but is polymerised by twelve days' contact with this acid.Thus it is found that of all the alkylenes examined isobutylene has the greatest additive power the expected decrease occurring between this hydrocarbon and /3- methyl-AP- butylene. Moreover as predicted by theory the difference in additive power between P-methyl-As- butylene and &-dimethyl- AB-butylene is much greater than that between isobutylene and the former hydrocarbon. E. H. VOL. XCVI. i. P198 ABSTRACTS OF CHEMICAL PAPERS. Comparative Stability of Bromoform Chloroform and Iodoform. WILLIAM OECHSNER DE CONINCK (Rev. gzn. Chim. pure et uppl. 1909 12 81).-Bromoform or chloroform when distilled from lead nitrate alone or from an aqueous alcoholic solution of this salt shows no signs of decomposition.When iodoform is thus treated the following reaction occurs BPb(NO,) + 2CH1 + 0 = 2Pb12 +I2 + 2C0 + H,O + 2H,O. This change takes place with the dry materials but in alcoholic solution at 94O no decomposition is observed. G. T. M. Preparation of Acetylene Di- and Tetra-chloridee from Acetylene a n d Chlorine. J. H. LIDHOLM (D.R.-P. 204516).- The interaction of chlorine and acetylene may be controlled by employing a definite source of light such as a quartz-mercury lamp actuated by a current of 5 amperes and 60-75 volts. A mixture of two volumes of chlorine and one of acetylene when thus illumi- nated reacts quite quietly yielding chiefly acetylene tetrachloride with about 10% of the dichloride. G.T. 1%. Preparation of Trimethylene Chlorobromide and Dibromide. PIERRE BRUYLANTS (Bull. Acad. roy. Belg. 1908 1085-1094).-The cyclopropanecarboxylonitrile required for the preparation of the com- pounds described elsewhere (this vol. i 226) was obtained by treating y-chlorobutyronitrile with dry potassium hydroxide and this compound was prepared by Hepry's method the action of potassium cyanide on trimethylene chlorobromide. The author found the methods described by Reboul (Abstr. 1879 127) and by Lermantoff (Abstr. 1877,59) for the preparation of trimethylene chlorobromide (a-chloro-y- bromopropnne) unsatisfactory ; the following modification OF the pro- cess however gave a satisfactory yield of the product and did not involve the use of sealed tubes.Ally1 chloride is saturated with moist hydrogen bromide at 20-29O in sunlight and the operation repeated until the gas ceases to be abmrbed. Trimethylene dibromide (ay-dibromopropane) is similarly prepared from ally1 bromide and hydrogen bromide a t 30-35'. M. A. W. Preparation of Nitromethane. ANDRE WAHL (Bull. Xoc. chim. 1909 [iv] 5 180-182. Compare Preibisch this Journ. 1874 462 ; Auger Abstr. 1900 i 578 and Steinkopf this vol. i 78).-A solution of 100 grams of monochloroacetic acid in 100 C.C. of water is neutralised with a solution of sodium carbonate (90 grams in 150 C.C. of water) and to this is added 90 grams of sodium nitrite. The solution is warmed gently at first and when the reaction has set in a current of steam is passed through and about 175 to 190 C.C.of distillate is collected. The nitromethane is decanted and that contained in the decantation liquid is recovered by a second distil- lation. The yield is about 50% of the theoretical. T. A. H. Oxidation of Alcohols by Simultaneous Action of Ferrous E. DE STOEKLIN (Compt. rend. Compare this vol. i 196).-The author has Tannate and Hydrogen Peroxide. 1909 148 424-426.ORGANIC CHEMISTRY. 199 studied quantitatively the oxidation of ethyl alcohol by hydrogen peroxide in presence of ferrous tannate and gives tables showing the amount of aldehyde and acetic acid formed when 50% alcohol and also when acetaldehyde is submitted to oxidation in presence of varying amounts of the iron salt. The results lead to the following conclusions (1) the alcohol is first converted into aldehyde (2) the aldehyde undergoes further oxidation to acetic acid (3) a portion of the aldehyde is absorbed by the ferrous tannate (4) part of the aldehyde is probably converted into an aldehyde peroxide (5) the amount of aldehyde and acetic acid formed increases with the weight of iron present.It has been observed that oxidation takes place when other organic compounds are substituted for tannin in these experiments. Methyl ethyl n-propyl and n-butyl alcohols have been oxidised in the same way but isopropyl and isobutyl alcohols the higher alcohols and also polyhydric alcohols such as glycol glycerol and sorbitol resist attack. w. 0. w. Catalytic Action of Goal Brown Goal or Peat in the Aerial Oxidation of Organic Substances.MAX DENNSTEDT and F. HASSLER (D.R.-P. 203848).-The oxidation of many organic substances can be brought about by passing their vapours mixed with air over coal heated at 150-300'. In this way ethyl alcohol is oxidised to acet- aldehyde and acetic acid toluene to benzaldehyde and benzoic acid naphthalene to naphthaquinone and phthalic anhydride anthracene to anthraquinone and borneol or isoborneol to camphor and camphoric acid. Brown coal and peat have a similar effect which appears to be due to the contained iron. Accordingly ferruginous compounds are added when the amount of iron originally present in the coal or peat is only small. G. T. M. Action of Ethyl Mesoxalate on Alkyl Magnesium Halides and the Synthesis of P&Dirnethylpentane-p8-diol. JOSEPH LEMAIRE (Bull.Acud. rag. BeZg. 1909 83-159).-The primary object of the research described was the preparation of pentamethylglycerol OH*CMe(CMe,*OH) and the first method tried was the action of Grignard's reagent on ethyl mesoxalate. The latter was prepared by a modification of the method described by Curtis (Abstr. 1906 i 480). As Wieland (Abstr. 1904 i 596) by the action of dry nitrous anhydride on ay-diphenylpropane-ay-dione has obtained the definite intermediate compound N,O,[CH(COPh),] which is decomposed by dilute sulphuric acid,:giving ay-diphenylpropanetrione COPh*CO*COPh it is suggested that in Curtis's reaction an analogous compound N,O,[CH(CO,Et),] is formed and decomposed by the water contained in the nitrous anhydride. When ethyl mesoxalate (1 mol.) is treated with magnesium methyl bromide (5 mols.) dihydroxytetramethylacetone CO(CMe,*OH) small crystals m.p. 117-118" b. p. 238-240°/ 755 mm. is formed the medial carbonyl group remaining unattacked. The latter observation taken in conjunction with the fact that the medial carbonyl group in triketopentane is also stable towarda Grignard's reagent indicates that this inactivity is due in both case6 P 2200 ABSTRACTS OF CHEMICAL PAPERS. to the negative influence of the neighbouring groups. Dihydrouy- tetramethylacetone does not form a phenylhydrazone or a semicarb- azone and does not combine with hydrogen cyanide. The conclusion is drawn that the activity of the carbonyl group is inhibited by the two adjacent tertiary bydroxyl groups. Moreover since the latter are attacked by phosphorus pentdcbloride and sulphuryl chloride but not by acetyl and benzoyl chlorides the behaviour of the complex :C(OH)*CO*C(OH) seems comparable with that of the carboxyl group.Ethyl magnesium bromide (5 mols.) in ethereal solution acts on etbyl mesoxalate giving a mixture of four substances. The chief product consists of ethyl Aydroxydiethylpyruuate OH*CEt,*CO-CO,Et a greenish-yellow liquid b. p. 230-232' D20 1.037 n 1.44335 which does not solidify a t - 60' and does not react with phenylhydrazine or semicarbazide. The second compound is a pale green liquid C,H,,O b. p. 140-150°/755 mm. having an agreeable odour. The third product is a golden-yellow liquid C71-€loOa b. p. 199-200'/750 mm. which forms a semicarbazone m. p. 142'. The quantity obtained of the fourth substance was insufficient for identification but it seems to be dihydroxytetraetbylacetone.The conclusion is drawn that ethyl magnesium halides are more active towards ethyl mesoxalate than methyl compounds and that the bad yield of dihydroxytetramethyl- acetone when using the latter is due to the formation of ethyl hydroxy dimethy lp yruvate. Magnesium propyl bromide reacts similarly t o the ethyl compound with ethyl mesoxalate. The production of dihydroxytetramethylacetone rendered the pre- paration of PG-dimethylpentane-PG-diol desirable for purposes of comparison. Attempts to prepare this compound by the action of methyl magnesium bromide on acetylacetone ethyl malonate ethyl chloromalonate ethyl acetoacetate ethyl sodioacetoacetate or malonyl chloride were unsuccessful.Ethyl P-chloroisovalerate (1 mol.) prepared in the manner described by Montemartini (Abstr. 1898 i 236) reacts with methyl magnesium bromide (2 mols.) giving (1) a liquid b. p. 126-12S0 with a camphor- like odour which combines readily with bromine and must be either CMe,Cl*CH,*CMe:CH or CMe2:C'H*CMe,C1 and (2) a liquid which is probably a mixture of the above compound and its parent chloro- hydrin CMe,Cl*CH,*CMe,-OH. An attempt to prepare the unsaturated chlorohydrin having the second of the above two formulae by the action of hydrogen chloride on Grignard's tetramethylallyl alcohol CMe2:CH*CMe,-OH gave a mixture of /36-dimethyl-AflY-pentadiene CMe,:C:CMe and a dipolymeride of the latter a liquid C14H24? b. p. 215'/755 mm. D20 0.8533 nD 1.4838 which combines with 3 molecules of bromine and probably has the constitution CMe,:CMe-CMe:CMe*CMe:CMe,.Since the latter hydrocarbon probably results from the condensation of 2 molecules of 6-chloro-PG- dime t h y 1-Ab-pentene CMe,Cl*CH CMe with elimination of hydrogen chloride whilst the unsaturated chlorohydrin obtained by the action of methyl magnesium bromide on ethyl /3-chloroisovalerate does not lose hydrogen chloride even whenORGANIC CHEMISTRY. 201 treated with dilute alkali it probably has the first of the above formula?. When hobutylene chlorohydrin OH*CMe,*CR,Cl reacts with potassium cyanide the product consists OF P-hydroxyisovaleronitrite OH*CMe;CH,*CN a colourless viscous liquid b. p. 130-132"/30 mm. 210-21p/756 mm. m. p. - 12" D20 0.96762 nD 1.42911 with an unpleasant odour which unlike its a-isomeride can be distilled with- out decomposition.This nitrile reacts with ncetyl chloride or acetic anhydride forming the acetate OAc*CMe,*CH,=CN a mobile liquid b. p. 115-120°/35 mm. 198-200°/758 mm. D18 0,9951 n D 1.4193 and with phosphorus pentachloride giving partly a chloro-derivative and partly the unsaturated nitrile CMe,:CH.CN identical with that obtained by the dehydration of u-hydroxyisovaleronitrile. The formation of an acetate differentiates the P- hydroxyisovalero- nitrile from the analogous tert.-butanol which gives not an acetate but a chloride and shows that the cyanogen group influences the tertiary hydroxyl even when separated from it by a methylene group. P-Hydroxyisovaleronitrile reacts with methyl magnesium bromide giving a mixture of mesityl oxide and diacetone alcohol ; it is readily hydrolysed with potassium hydroxide giving P-hydroxyisovaleric acid but the ester of the latter can only be obtained pure by the action of ethyl iodide on the silver salt.Ethyl P-hydroxyisovalerate when treated with Grignard's reagent gives PG-dimethylpentane-@-diol but owing to the difficulty in preparing the ester its use was abandoned in favour of the following method. Diacetone alcohol OH*CMe;CH,-COMe (1 mol.) prepared as described by Heintz (Annalen 1875 178 342) reacts with magnesium methyl bromide (2 mols.) giving PG-dirnethylpentane-/36-diol OH=CMe,*CH2*CRle,*OH a viscous liquid b. p. 113'/35 mm. DZo 0.9206 wD 1.4375 already prepared by Franke (Abstr.1907 i 171 816). This diol when distilled at atmospheric pressure is pxrtly dehydrated giving PG-dimethy 1- Aa-pent en e- 6-01 OH = CMe,*CH,*CMe CH a reaction entirely analogous to that undergone by the chlorohydrin but differ- ing from the dehydration of diacetone alcohol and p-hydroxy&wvalero- nitrile. The conclusion is drawn that the influence of a C(0H) group is different from that of a carbonyl or cyano-group on an adjacent methylene group. P6-Dimethylpentane-PG-diol is only very slightly oxidised to dihydroxytetramethylacetone by t wenty-four hours' contact with dilute potassium permanganate solution. Two series of reactions are suggested for the preparation of penta- methylglycerol one starting from y-chloro-P-butanone the other from a-hy droxy -a-meth ylpropionitrile.E. H. Preparation of Chlorohydrin from Glycerol and Sulphur Chloride. DEUTSCHE SPRENGSTOFF AKTIEN-GESELLSCHAFT (D. R.-P. 201230).-Although dichlorohydrin is the product of the action of sulphur chloride on glycerol at loo" it has now been found possible to obtain chiefly chlorohydrin by operating with the calculated amount of the chloride at 25" and then at 50-70". In this way 85-95% of the glycerol is converted into the monochloro-derivative,202 ABSTRACTS OF CHEMICAL PAPERS. only about 1-2% of the dichloro-compound being produced. The chief product is purified by distillation under reduced pressure. G. T. M. Halogen Ethers. A. KARVONEN (Ber. 1909 42 687-692).- According to Palomna (Diss. Helsingfors 1908) the reactivity of the halogen in haloid derivatives of aliphatic ethers varies with the position of the halogen atom with respect t o oxygen.Preliminary oxperiments show that tripropylamine does not react with ethyl P-iodoethyl ether at 100'. Methyl P-iodoethyl ether CH,*O*CH,*CH,I is obtained by the action of methyl alcohol on ethylene iodide at loo3 and may be obtained pure by distilling several times over solid sodium hydroxide. It has a sweet odour and b. p. 137*S0/750 mm. and Dt5 1.8322. It does not turn brown when exposed to diffused light for several months and its aqueous or alcoholic solution yields a precipitate with silver nitrate. Ethyl P-iodoethyl ether (Baumstark Ber. 1874 7 11 72 ; Henry Abstr. 1885 882; Demole Ber. 1876 9 743) is best purified by distillation over solid sodium hydroxide.It has b. p. 154*9-155*2O/ 761 mm. and Di5 1.6698. P-lodoetrbgl pvopyl etheT CH,Et*O*CH,*CH,I has b. p. 175-175*3"/ 750 mm. and Di5 1.5379. J. J. S. Preparation and Physical Properties of as-Tetrachloroethyl Ether. FRED NEHER and WILLIAM FOSTER (J. Amer. Chem. Soc. 1909 31 410-412).-A modification of Henry's method (Abstr. 1871 255) for the preparation of tetrachloroethyl ether is described by means of which the compound can be obtained in a yield of 55-'74% of the theoretical. as-Tetrachloroethyl ether boils at 189-4'/749*1 mm. (corr.) or 79'/16 mm. and has Di8 1.4225. CCl,*CHCl*OEt E. G. as-Dichlorovinyl Ethyl Ether its Preparation from Tetrachloroethyl Ether and its Physical Properties. FRED NEHEB and WILLIAM FOSTER (J. Amer. Chem. Xoc.1909 31 41 2-414).-as-Dichlorovinyl ethyl ether CCl,:CH*OEt (Godefroy Abstr. 1886 607) can be obtained in a yield of 80-907( of the theoretical by the action of zinc on an alcoholic solution of as-tetra- chloroethyl ether at a temperature below 40'. A t higher tempera- tures the product contains a varying amount of dichloroacetal. as-Dichlorovinyl ethyl ether boils at 144-2O/765.3 mm. (corr.) and has Di8 1.2096 and Di0 1.3081. E. G. Difluoroethyl Bromide and Tetrafluorodiethyl Hydrogen Phosphate. FRI~DJ~RIC SWARTS (Bull. Acad. roy. Belg. 1909 60-65). -When difluoroethyl alcohol (1 gram-molecule) is acted on by bromine (1 gram-atom) in the presence of excess of phosphorus about 25% of the alcohol is recovered unchanged another 25% is transformed intoORGANIC CHEMISTRY.203 difliioroetbyl bromide whilst the remainder is converted into a syrupy liquid b. p. 253-255' the analysis and vapour density of which prove it to be dzj?uoroethyl phosphate PO( 0C2H3F2j8. The teaction producing this substance might be represented by either of the two equations (1) P + 516r + 4C2H3F2*OH = (C2H,F2),P0 + C2H3F,Br + 4HBr ; (2) 5 P + 25Br + 20C,H3Fz*OH = 4(C2H3F2),P0 + 8C2H3F2Br f 17HBr + H,PO,. The amount of hydrogen bromide found experi- mentally is in favour of the former equation. The difluoroethyl bromide formed is identical with that obtained from tribromoethane (Abstr. 19OS i 752). Difluoroethyl phosphate is saponified by ammonia giving ammonium detrafEuorodieth?jZ phosphate NH4P04(C2H,F2) which forms beautiful white crystalline spangles and is converted by baryta into the barium salt.The salts of silver and lead are both soluble in water but the rnercwous salt forms a white crystalline precipitate insoluble in nitric acid. Tetrafluorodiethyl hydrogen phosphate is remarkably stable towards both acids and alkalis. Heating with excess of nitric acid on a water-bath for thirty-six hours is required in order to obtain the phosphate reaction with ammonium molybdate. New Method of Extracting a Phosphated Compound (Phytin) from Plants. ANGELO CONTARDI (Atti R. Accao?. Limei 1909 [v] 18 i 64-67).-The author gives the following method for extracting from rice bran the phytin obtained from different sources by several investigators (compare Suzuki and Yoshimura Abstr. 1908 ii 124). The finely-ground rice bran is treated with twice its weight of 0*2-0*3% hydrochloric acid and the liquid separated by pressing heated below its boiling point and neutralised by means of recently- calcined magnesium oxide.The precipitate formed after washing several times with hot water by decantation is dissolved in hydro- chloric acid and the solution filtered decolorised with animal charcoal and neutralised with magnesium oxide. After re-dissolving and again precipitating the calcio-magnesium derivative of phptin is obtained. 'The composition of this compound corresponds with that of the calcio- magnesium derivative of the compound O[CH2*O*P(OH)2]2 described by Posternak (Abstr. 1903 ii 607 679 680). The phytin separated in the above manner behaves like an ordinary ester but is not so readily hydrolysed by alkalis as the latter.DAVID R. KELLOGG (J. Amer. Chern. Soc. 1909,31,403-405).-1t is well known that ester hydrolysis in the presence of a strong acid is greatly accelerated by the addition of a neutral salt of the acid. Experiments have now been carried out with the object of ascertaining the effect of neutral salts on the rate of hydrolysis in the absence of acids. Ethyl acetate mas heated in sealed tubes with water with potassium chloride solutions of 1% lo% and 20% strength and with a saturated solution of this salt. The results show that the 1% solution produces a considerable acceleration the 10% solution a much larger acceleration whilst the 20% solution has but little effect and a saturated solution exerts a strong inhibiting influence E H. T.H. P. Effect of Neutral Salts on Hydrolysis by Water. E. G.204 ABSTRACTS OF CHEMICAL PAPERS. [Preperation of Salts of Iodated Fatty Acids.] FARBEN- FABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 202353. Compare Abstr. 1908 i 122 123 310).-Manganous iodobehenate a white amorphous mass is obtained by adding an aqueous solution of manganous chloride to potassium iodobehenate in alcoholic solution. The corresponding. manganic ferrous and ferric salts are prepared similarly. Q. T. M. [Iodination of the Higher Fatty Acids and Esters.] J. D. RIEDEL (D.R.-P. 202790).-Ethyl oleate dissolved in alcohol is treated with iodine and mercuric oxide and after twenty-four hours freed from iodine with potassium iodide and thiosulphate. The final residue after distilling off the solvent contains 15-26% of iodine.Elaeostearic Acid. RIKO MAJIMA (Ber. 1909 42 674-6SO).- The composition C,,H,,O ascribed by Kametaka (Trans. 1903 83 1042) to the solid acid m. p. 48-49' b. p. 235'/12 mm. in carbon dioxide isolated from oil of Elaococca Vernicia and regarded by Cloez as elaeomargaric acid C,?H,,O and by Maquenne as elzeostearic acid C,,H,,O (Abstr. 1903 I 62) has been confirmed by the author who has prepared a dioxonide C,,H,,O a yellow amorphous semi- solid substance. The products of its decomposition by water include valeraldehyde (thiosemicarbazone m.. p. 6S0) valeric acid (anilide m. p. 60°) azelaic acid and its semialdehyde (semicarbazone m. p. 165O). Consequently elaeostearic acid must have its double linkings between the fifth and the sixth and the ninth and the tenth carbon atoms.Succinaldehyde succinic acid and its semialdehyde cannot be detected although the aqueous solution of the decomposition products Preparation of Ethyl Glyoxylate by the Reduction of Ethyl Oxalate. FARBENFABBIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 201 895).-Ethyl oxalate when reduced with sodium amalgam and absolute alcohol yields ethyl glyoxalate a 30-40% yield of which is obtained in the form of an alcoholate after precipitating the sodium as sodium oxalate and distilling the filtrate from this salt under reduced pressure. The ester itself is obtained by treating the alcoholate with phosphoric oxide. G. T. M. Syntheses by means of Mixed Organo-metallic Compounds of Zinc. Preparation of Ketonic Acids and Diketones.EDMOND BLAISE and A. KGHLER (Compt. rend. 1909 148 489-491. Compare Abstr. 1907 i 749; 19Q8 i 248).-The acid esters of the succinic and glutaric series of dibasic acids are readily prepared by the action of acetic anhydride on the acid anhydride. I n the case of the higher homologues i t is necessary t o mix the normal ester with an alcoholic solution of sodium ethoxide and add the calculated amount of water. Conversion of the acid esters into the corresponding chlorides is best effected by means of thionyl chloride. The following ketonic acids have been prepared by the action of mixed organo- metaallic zinc compounds on the chlorides so obtained eketo-octoic acid COMe*[CH,],*CO,H m. p. 31-32' ; c-ketononoic acid C,H,,O m. p. G. 3'.M. contains B substance which responds to the pyrrole test. c. s.ORGANIC CHEMISTRY. 205 52O; ~-ketodecoic mid C1,Hl,03 m. p. 42'; Bkatoundecoic acid CltH,,O m. p. 64' ; 8-keto-octoic acid C,H,,03 m. p. 53O. f h e corresponding symmetrical diketones are obtained in good yield when the dichlorides of the dibasic acids are treated with the organo- metallic zinc compounds. The reaction however is not available in the succinic and glutaric series since in this instance lactones are obtained. The following diketones are mentioned undecane-yi-dione COEtfCH,],*COEt m. p. 68' ; decane-pi-dione Cl0H~,O2 m. p. 64O ; dodecane-ym5one C12H2202 m. p. 7 2 O ; zmdecam-~K-dzo. w. 0. w. Halogen Derivatives of y-Hydroxycrotonic Acid. ROBERT LESPIEAU and VIGUIER (Compt. rend.1909 148 41 9-422. Compare Abstr. 1908 i 125).-The authors describe further experiments with a,!3-dibromo-y-hydroxy-Aa-butenoic acid which favour the view that this compound belongs to the maleiq rather than to the fumaric series. The acid differs from Tonnies' lactone in yielding a potaseiurn salt OH*CH2*C13r:CBr*C02K,H20. It appears therefore that this lactone CBr-CO to which Hill ascribed the constitution I I >O (Abstr. 1894 i CBr*CH 319) is not a simple derivative of the acid. The acid however under- goes conversion into the lactone when its aqueous solution is saturated with hydrogen chloride. Hydrogen bromide converts y-hydroxytetrolic acid into a mixture of a-bromo-y-hydroxy-Aa-butenoic acid OH* CH,*CH C Br CO,H m. p. qH-CO 158-160° and Hill's lactone I >O (Zoc.cit.). Rromine con- CBr*CH verts the latter into Hill's dibromolactone. The bromo-acid probably belongs to the fumaric series. Iodine and potassium iodide convert y-hydroxytetrolic acid into a-p- di-iodo-y-hy&roxy-Aa- butenoic acid OH*CH,*CI:CI* CO,H m. p. 173-1 '75' (decomp.). Hydrogen bromide converts this into a lactone m. p. 143-145' which has not yet been obtained pure. w. 0. w. Action of Oxalic Acid on Ferric Hydroxide. FRANK K. CAMERON and WILLIAM 0. ROBINSON (J. Physical Chem. 1909 13 157-158).-The solubility of ferric hydroxide in solutions of oxdic acid of varying strengths has been determined at 25'. The results show that the solubility of the hydroxide is directly proportional to the concentration of the acid and that no definite basic ferric oxalate is formed from solution a t 25'.In all solutions more iron is present than is equivalent to the oxalic acid present but the solutions have an acid reaction. G. S. Conversion of Active a-Bromopropionic Acid into Active Methylsuccinic Acid. EMIL FISCHER and ERICH FLATAU (Bnrutkn 1909 365 13-20).-The authors have attempted to increase the number of direct syntheses of optically active substances by replace- ment of some atom or group attached to the asymmetric carbon atom of an active compound. For this purpose the synthesis of an active206 ABSTRACTS OF CHEMICAL PAPERS. methylsuccinic acid from ethyl sodiocyanoacetate and ethyl I-a-bromo- propionate was selected and Bone and Sprankling's method (Trans. 1899 75 839) was used. In the condensation care was taken to keep the temperature as low as possible (below 35') in order to avoid racemisation.The ethyl cyanomethylsuccinate bad b. p. 119-153"/10 mm. and a - 17.6' in a 100 mm. tube. It was hydrolysed to propane-aap-tricarboxylic acid by shaking with fuming hydrochloric acid a t the ordinary temperature and the acid isolated as the insoluble barium salt. The acid was crystallised from a mixture of ether and benzene; i t had m. p. 150' (decomp.) and [a]? - 33%' in aqueous or - 57.8' in sodium hydroxide solution. The acid was decomposed by heating the aqueous solution at looo for four hours a laevorotntory methylsuccinic acid was obtained but the rotation varied considerably with different specimens and was always below the value obtained by Ladenburg (Abstr. 1895 i 449).The possibility of the Walden inversion occurring during the syntbesis is mentioned. J. J. S. Chemical Treatment of Bile. Separation of the Bile Acids. MAURICE PIETTRE (Compt. rend. 1909 148 372-374).-After extrac- tion with ether the bile is desiccated powdered and extracted with boiling methyl alcohol. After filtration the boiling solution is pre- cipitated drop by drcp with barium rnethoxide (compare Etard and Vila this vol. i 124) which carries down the pigments. As soon as the solution becomes alkaline the precipitation is stopped and the excess of barium is removed by carbon dioxide; the bile salts can now be readily omained from the clear colourless solution. The barium methoxide precipitate after acidification and washing is extracted with chloroform and yields bilirubin.G . B. Chloralic Acids. MAURICE HANRIOT (Compt. rend. 1909 148 487-489. Compare Abstr. 1893 i 247 ; 1894 i 105 ; 1895 i 321 ; 1896 i 519).-The compounds of chloral with certain sugars which the author has termed chloraloses undergo oxidation when treated with potassium permanganate and sulphuric acid or with nitric acid giving acids to which the following constitution is ascribed QH*CH(OH)-O*yH-CCi O<CH--- C(OH)*CO,H. I n the case of mannochloralose r? lactone was obtained onoxidation. a-Glucochloralic acid c7H706c1 forms slender needles m. p. 21 2 O . P-Glucochloralic m i d C,H70,C1,,2H,0 occurs as efflorescent rhombic tablets and forms a sparingly soluble sodium salt. The lactone C7H,0,C13 obtained by the action oE acetyl chloride or zinc chloride on the acid has m.p. 185". ~ - G a ~ a c l o c h ~ o r a ~ i c acid C,H706Cl m. p. 3 0 7 O forms a Enctons C7H,O,CI3 m. p. 130'. Mannocldoralic Zactone c,H706c13 is sparingly soluble in water and has m. p. 242O; it dis- solves in aqueous ammonia forming the ammonium salt of the unstable acid. a-Arabinochloralic acid C,H,O,CI forms needlep m. p. 320" j the P-acid is identical with P-galactochloralic acid,ORGAXIC CHEMISTRY. 207 P-Xylochloralic acid is identical with /I-glucochloralic acid. w. 0. w. Action of Nitric Anhydride on Mucic Acid. A. CRUM BROWN and G. E. GIBSON (Proc. Roy. Soc. Edin. 1908,23 96-97).-Mucic acid and nitric anhydride both previously cooled in ice were mixed together and left in a vacuum over sodium hydroxide; on extracting with ether in a Soxhlet tube and evaporating at the ordinary tempera- ture with a vacuum pump colourless needles were obtained which on exposure to air or in a vacuum soon changed to a white powder.The analyses of t h i s substance although discordant correspond with a tetranitrate. In the air the white solid soon begins to decompose with evolution of nitric acid and oxides of nitrogen ; on heating it decom- poses violently. P. H. The Reduction Products of Sulphurous Acid and their Double Compounds with Aldehydes. CHEMISCHE FABBIK VON HEYDEN (D.R.-P. 202825 202826 and 202827).-The double sodium salt H0.C H2-O*SONa,H0*CH2*S02*ONa is produced by passing sulphur dioxide into a mixture of zinc dust and aqueous formalde- hyde until the metal has dissolved and then treating the solution with sodium carbonate.A sparingly soluble benzaldehyde zinc hypo- sulphite can be similarly obtained. When half the proportions of aldehyde and sulphurous acid are employed salts of the type HO*CHR-O*SO=Zn*OH are formed ; these have twice as much reducing action on indigotin as the foregoing double salts. Sodium formaldehyde sulphoxylate HO*CH,*O*SONa is obtained in stable well defined crystals by evaporating its solutions under greatly reduced pressure and separating the product from the liquid without allowing it to cool. G. T. M. Bromo-ketones. J. PASTUREAU (Bull. SOC. chim. 1909 [iv] 5 226-227. Compare Abstr. 1905 i 572; 1907 i 113 185).-A description of bromo-derivatives of homologues of acetone obtained as already described (Zoc.cit. ) from the ketone peroxides. Diethyl ketone peroxide yields the tribromo-derivative CHMeBr*CO* CHBr* CH2Br b. p. 142O/100 mm. D 2.003 which on hydrolysis with potassium car- bonate gives the keto-alcohol OH*CHMe*CO*CH(OH)*CH2*OH. The latter reduces strongly in the cold and gives a phenylosazone m. p. Methyl propyl ketone peroxide under the same conditions yields the tetrahomo-derivative CHMeB r*CH,*CO*CBr m. p. 5 7 O which separates from boiling alcohol in co lourless rhombohedra and hexagonal prisms. On hydrolysis with potas sium carbonate i t yields the lactone co-co ba,. CHMe>O of which the corresponding hydroxy-acid has only been obtained in the form of the lead salt by hydrolysiog the tetrabromo-derivative with litharge in a closed vessel.1 80- 18 1 O. T. A. H.208 ABSTRACTS OF CHEMICAL PAPERS. Oxidation of Ketones and Diketones by Hydrogen Peroxide in Presence of Acid. J. PASTUREAU (Bull. Soc. chim. 1909 [iv] 5 327-229. Compare Baeyer and Villiger Abstr. 1900 i 133 ; Pastureau Abstr. 1905 i 572 and 1907 i 113 185).-The author has shown already that aliphatic ketones yield on treatment with hydrogen peroxide in presence of dilute sulphuric acid the correspond- ing ketone peroxides and hydroxy-ketones acetone furnishing acetone peroxide and acetol (acetyl-carbinol). I n the present paper this reaction is applied to other products of this class. Diethyl ketone peroxide D 1.038 is a liquid insoluble in water (compare Baeyer and Villiger Zoc. cit.) and with it is formed popion y Zmethylcarbinol COEt CHMe.OH which with pbeny 1 h y d razi ne yields acetylpropionyl pbeny losazone m. p. 136'. Methyl propyl ketone peroxide D 1.006 is formed along with the keto-alcohol CH,Ac*CHMe*OH. Acetophenone yields only hydroxy- acetophenone OH*CH,*COPh and benzoic acid. The diketones which contain a carbonyl group between two open- chain radicles y-ield peroxides but not those in which the two carbonyl groups are contiguous with closed-chain radicles. These peroxides are highly polymerised vitreous solids which are not volatile in steam but have properties akin to those of the Feroxides of the simple ketones (Zoc. cit.). Acetylucetone peroxide (C5Hlo04)n is formed along with R keto-alcohol which condenses with phenylhydrazine to form a pyrazole and gives a red coloration with ferric chloride.Benzoyl- acetone peroxide (C,,,H,,O,)~ is obtained together with benzoic acid. Dibenzovlmethane and benzil furnish each 2 mols. of benzoic acid whilst bLnzoin is decomposed yielding a little benzoic acid. T. A. H. Preparation of Diacetyldioxime [Dimethylglyoxime]. HEIN- RICH BILTZ (Zeitsch. anal. Chem. 1909 48 164-165. Compare Tschugaeff Abstr. 1905 ii 613).-Fifty grams of methyl ethyl ketone are dissolved in 100 grams of ether the solution is cooled in ice and eighty-two grams of amyl nitrite are added drop by drop while a current of hydrogen chloride is being passed. After a few bours 150 C.C. of iced water and 50 C.C. of 33% aqueous sodium hydroxide are added and after thorough shaking the alkaline solution is drawn off and the ether j s shaken a few times with dilute sodium hydroxide solution.The alkaline solutions are united and shaken with a little ether and then evaporated on the water-bath to remove the dissolved ether. When cold the solution is carefully neutralised with dilute sulphuric acid and a solution of 50 grams of hydroxylamine hydrochloride in 75 C.C. of water is added. After remaining over- night the crystalline mass is collected using suction and then purified by recrystallisation ; the yield amounts t o 45-50 grams. L. DE K. Simple Notation for Indicating the Configuration of the Sugars and Allied Substances. THOMAS S. PATTERSON (Chem. News 1909 99 124-126).-The empirical names of the compounds are retained. Attention is confined to the -OH groups on the right-ORGANIC CHEMISTRY.209 hand side of the formula in which the most highly oxidised end of the chain is always placed uppermost and the asymmetric carbon atoms are numbered from below upwards. Thus on the right-hand side of the formula for d-arabinose CHO hydroxyl groups are found on the first and second carbon atoms and the symbol d-arabinose (1 2) is HO*b3*H applied. Similarly we have d-glucose (1 2 4) and H.&.OH I-ribose (0) there being no hydroxyl group on the H.bI.OH right-hand side. For substances having the same group at either end of the molecule two different symbols are possible; thus d-sorbitol is written (';:$. In d-idosaccharic acid (2 4) the two symbols are identical. For 'inactive substances for example dulcitol !:'$ the second symbol is entirely different from the first.eH,*OH E. F. A. Behaviour of Oellobiose and its Osone towazds Certain Enzymes. EMIL FISCHER and GBZA ZEMPLEN (Arcwlen 1909 365 1-6).-The disaccharide cellobiose (Skraup a'nd Konig Abstr. 1901 i 370; 1902 i 135) is readily hydrolysed by emulsin but is not affected by the extract of dry Frohberg yeast or yet by the enzymes of Aspergillus rziger or kephir lactase. Cellobiososone obtained from the osazone is a syrup which sets to a vitreous mass and in its behaviour towards enzymes resembles cello- biose. The behaviour of the disaccharide is similar to that of geatio- biose (Abstr. 1902 i 744) isomeltose (Abstr. 1896 i 119) and to a certain extent milk sugar. In all these compounds it is probable that . the two molecules of dextrose are united in the same manner and that in maltose the condensation is of a different type.J. J. S. Colloidal Properties of Starch in Relation to its Chemical Constitution. EUG~NE FOUARD (Compt. rend. 1909,148,502-505. Compare this vol. i 13).-When potassium hydroxide is added in increasing quantities to a perfectly clear starch solution (filtered through collodion) the rotatory power of the latter diminishes at first rapidly then more slowly and finally it approaches asymptotically to the rotatory power for a maltose solution. The change is reversible so that the rotation increases again on neutralisation ; there is a definite rotation for every degree of alkalinity. The rotatory power of the part remaining dissolved when a starch solution gradually gelatinises diminishes while gelatinisation proceeds and the final portions to be gelatinised have a rotation also approaching asymptotically to that of pure maltose.Starch is therefore to be regarded as being simply a condensation product of maltose of varying degrees of complexity. G. B. Course of the Oxidation and Hydrolysis of Starch and its Constituents by Hydrogen Peroxide. Z. GATIN GRUZEWSKA (Conapt. rend. 1909 148 578-580 j.-Hydrogen peroxide hydrolyses starch and at the same time oxidises it the final products being maltose and oxalic acid. The constituents of starch amylopectin and amylose are acted on in different mays by hydrogen peroxide (as they210 ABSTRACTS OF CHEMICAL PAPERS are by diastase). I n the case of both constituents dextrins are formed as intermediate products In the case of amylopectin the attack on the micellae appears to be simultaneous in that of amylose successive.G. B. Cellulose Hydrates. HERMANN OST and F. WESTHOFF (Chem. Zeit. 1909 33 197. Compare Abstr. 1907 i 390).-The name cellulose hydrate has been used by Cross and Bevan (Trans. 1895,67 433) to designate substances which contain besides hygroscopic water also water more firmly retained such as is present in mercerised cellulose the composition of which is given as ZC,H,,O,,H,O. The hydrocelluloses are substances which in the dry state contain water in chemical combination ; they have the composition (CBK1005)R,H20 and it has been shown by Schwalbe (Abstr. 1907 i 390) that cellulose hydrate is quite different from hydrocellulose. The present paper records a careful comparison of dried cellulose cellulose hydrate and hydrocellulose and from the results of the estimation of water driven off at 110-130'and from analyses the conclusion is drawn that mercerised cellulose contains more hygro- scopic water than hydrocellulose ; further that the so-called cellulose hydrates (mercerised cellulose etc.) when freed from water by drying at 120-125' have the same composition as ordinary cellulose namely (C&4oO&- Hydrocellulose on the other hand when in the anhydrous state has the composition represented by the formulae C00H102051 C3,H620,1 etc.analogous to the hydrolytic decomposition products of starch. J. V. E. Putrefaction of Glutamic and Aspartic Acids. L. BORCHARDT (i%dsch. physiol. Chem. 1909 59 96-100).-During putrefaction glutamic acid yields butyric acid as a result of de-amidation and evolution of carbon dioxide. Aspartic acid also loses NH and is con- verted into succinic acid and finally by loss of carbon dioxide into propionic acid.Volatile bases other than ammonia were not detected. W. D. H. Preparation of' Alkyl Dialkylarnino-aaa-trichloro-p-hydroxg- ethoxyisobutyrate. LES ETABLISSEMENTS POULENC FR~RES and EBNST FOURNEAU (D.R.-P. 203643)-Esters having pronounced saporific properties with low toxicity are produced by condensing anhydrous chloral with the a1 k y 1 dime t h ylamino hy droxyiso but yra t es. Ethyl dimethykamino-aaa-trichloro-P-h ydroxyet~~oxyisobutyrate CCl,*CH( OH)*O*CMe( CH,*NMe,)*CO,Et rectangular prisms m. p. 66-67' b. p. 140-142'/22 mm.hydro- chloride needles m. p. 18 1-1 82O and propyl dimethyZalrLino-aaa-trichloro- 6-hydroxyethoxyisobutyrate transparent crystals m. p. 65O were thus obtained. These esters when exposed to moist air undergo hydrolysis to the acid CCl,*CH(OH)-O*CMe(CH:,*NMe,)~CO,H. Aminohydroxy-acids. 11. Amino-derivatives of a-Hydroxy- isobutyric Acid. ERNEST FOUBNEAU (Bull. Soc. chim. 1909 [iv] 5 229-241. Compare Abstr. 1907 i 622).-Much of the work now G. T. M.ORGANIC CHEMlSTRY. 211 recorded has been published previously (Abstr. 1908 i 937) and in this paper fuller experimental details are given and a number of additional derivatives described. The starting point of the investiga- tion was P-chloro-a-hydroxyisobutyronitrile b. p. 103-104°/16 mm. which was converted into the corresponding acid,:of which the ethyl ester b.p. 197'/765 mm. or 106"/30 mm. propyl ester b. p. 217'/765 mm. or 106-1073/16 mm. and umyl ester b. p. 241-242'/765 mm. or 115-116°/12 mm. were prepared. The acid on treatment with ammonia solution in a closed vessel yields P-amino-a-hydroxyiso- butyric acid which is crystalline decomposes a t 281° and yields a crystalline hydrochloride and sulphute. The ethyl ester (loc. cit.) furnishes an isovaleryl derivative b. p. 194-196"/21 mm. a urethane OH*CXe(CH,-NH*CO,Et)*CO,Et b. p. 164-1 65'/16 mm. (which with alcoholic ammonia gives the corresponding amide OH*CMe(CH,*NR°C02Et)*CO*NH m. p. 1 2 5 O silky needles) and a propylurethnne derivative b. p. 184'/3O mm. The ethyl ester condenses with potassium isocyanate and on treating the proauct with hydrochloric acid 5-hydrozy-5-kthyl- dih ydrourucil N H<Co Co'CMe(ONFI$>~~2 crpstallising in colourless tablets from boiling water is obtained.The propyl and amyl esters of P-amino-a-hydroxyisobutyric acid were also prepared ; their urethanes are colourless syrupy liquids which are soluble in water and have b. p. 167-168'/14 mm. and 173- 174*/12 mm. respectively. I n preparing ethyl p-methylamino-a-hgdroxyisobutyrate (loc. cit. ) by esterifying the acid in the usual manner some ethyl methylaminobis- hydroxyisobutyrate NMe[CK,*CMe(OH)*CO,Etl b. p. 180°/1 7 mm. is obtained as a thick oily liquid soluble in water. The methylamide of p-methylamino-a-hydroxyisobutyric acid b. p. 157'/31 mm. is obtained by the action of methylamine on the original ethyl chlorohydroxyim butyrate in presence of alcohol or benzene.p-Dimethylamino-a-hydroxyisobutyric acid m. p. 174" crystallises in bulky transparent tablets and possesses a sweetish slightly nauseous taste; the benxoyl derivative m. p. 182O crystallises in spangles and the umide m. p. 102' in needles. The ethyl ester (Zoc. cit.) yields the following acyl derivatives vaZeryl b. p. 143-145O/20 mm. liquid ; bromovalery2 hydrochlwide m. p. 142' colourless prisms ; bromohexoyl hydrochlwide m. p. 134" quadrangular tablets ; p-nitro- benxoyl hydrochloride m. p. 196O,. yellow prisms. The propyl ester (loc. cit.) furnishes a valeryl derivative b. p. 148-150°/16 mm. a liquid having a feeble odour of smoked fish ; its hydrobromide m. p. 120° is crystalline possesses a burning taste and is employed in medicine under the name '( quietol." T.A. H. Derivatives of Oximinocyanoacetic Acid. MAX CONRAD and ABNOLD SCHULZE (Ber. 1909 42 735-'742).-Ethyl oximinocyano- acetate is readily obtained in 87% yield by treating a cold mixture of ethyl cyanoacetate and aqueous sodium nitrite with glacial acetic acid and decomposing the resulting yellow crystalline sodium derivative212 ABSTRACTS OF CHEMICAL PAPERS. with hydrochloric acid. D 1.22 into ethyl forrnylaminomalonamate CH0.N H*CH( CO,Et)*CO*NH m. p. 142O the constitution of which is proved by its conversion by concentrated ammonium hydroxide into formylaminomalonamide (this vol. i 21 3). Ethyl oximinocyanoacetate is readily oxidised by potassium permanganate t o ethyl nitrocyanoacetate of which the G ~ ~ w T and the potussium derivatives are described.Oximinocyano- acetamide (deoxyfulminuric acid) is readily obtained by treating an aqueous solution of cyanoacetamide and sodium nitrite at 0" with glacial acetic acid and decomposing the resulting sodium derivative with the calculated quantity of hydrochloric acid ; by reduction by zinc and formic acid it yields formylaminomalonamide whilst oxidation by potassium permanganate leads to the formation of nitro- cyanoacetamide (fulminuric acid) the potassium salt of which is also obtained by the action of concentrated ammonium hydroxide on the potassium derivative of ethyl nitrocyanoacetate. Cyanoacetylcarbamide obtained by heating carbamide cyanoacetic acid and acetic anhydride at 60" for three hours reacts with sodium nitrite in hot water to form yellow crystals of the sodium derivative of oximinocyanoacetylcarbamide C411,0,N,Na,H20 which develops an intense violet coloration with ferrous sulphate and sodium hydroxide. Oximinocyanoacetylcarbamide CN*C( NOH) CO*NH* CO*NH m.p. 220' (decomp.) is oxidised by potassium permanganate to the potassium derivative of nitrocyanoacetylcarbamide. Cyanoacetylzcrethane CN*CH,*CO*NH-CO,Et m. p. 167-168' prepared from urethane cyanoacetic acid and acetic anhydride yields in a similar manner oxirninocyccnoacet$urethane CN*C( :NOH)*CO*NH*CO,Et m. p. 201' (decomp.) which also gives a violet coloration with ferrous Action of Hydrazine on Ethyl Mesoxalate. RICHARD S. CURTISS ALFRED R. KOCH and E. J. BARTELLS (J.Amer. Chew. Xoc. 1909 31 416-421).-1n earlier papers (Curtiss Abstr. 1906 i 339 ; Curtiss and Tarnowski Abstr. 1908 i 760) the action of ammonia and hydrazine on esters of mesoxalic acid has been described. When ethyl dihydroxymalonate is treated with an aqueous solution of hydrazine hydrate or carbonate ethyl hydraxinobistartrorate N H,*N[ C( C0,E t),*OH Igr m. p. 5 8 O is produced which forms colourless rhombohedra1 crystals and has a bitter taste. It isstable in theair but if left i n a desiccator or carefully heated water is eliminated and an oily substance is formed. The compound reduces silver nitrate and platinic chloride to the metallic state and is decomposed by nitrous acid with production of nitrogen ethyl dihydroxyma€onate and small quantities of a compound m.p. 253O. Phosphorus pentachloride reacts with ethyl hydrazino- bistartronate with evolution of hydrogen chloride thus proving the presence of hydroxyl groups. When the compound is warmed with mercuric oxide nitrogen and ethyl dihydroxymalonate are produced. It is changed by zinc dust and formic acid sulphate and sodium hydroxide. c. s.ORUANIC CHEMISTRY. 213 By the action of benzaldehyde on the h ydrazine compound benzalazine is formed and by the action of benzoyl chloride or benzoic anhydride a dibenxoyZhlydrazine m. p. 241' (corr.) is produced. When hydrazine hydrate solution is added to an alcoholic solution of ethyl mesoxalate a compound C,H,,0,N2 m. p. 125-1 30' (decomp.) is obtained which crystallises in colourless needles. E. G. Reduction of the Esters of d-Alanine and of dl-Phenyl- alanine.EMIL FISCHER and TOKUHEI KAMETAKA (AnnaZen 1909,365 7-1 2. Compare Fischer Abstr. 1908 i 323 ; Neuberg ibid. 322). -A 17% yield cif d-a-aminopropionacetat! NH,*CHMe*CH(OEt) is obtained when the d-alanine ethyl ester is reduced with sodium amalgam in slightly acid solution and the resulting amino -aldehyde treated with an alcoholic solution of hydrogen chloride a t 0". It is a colourless liquid b. p. 55-56'/11 mm. has Dm 0.902,and nD 1.41955. The solution in hydrochloric acid has [a]; + 14.5'. The picrate C,,H,,O?N crystallises from benzene in yellow prisms m. p. 86' (corr.) after sintering at 82'. The normal oxalate C16HaeOsN2 separates as colourless plates when ethereal solutions of the components are mixed ; it has m.p. 176' (corr. decomp.). The acetal can be readily h ydrolysed but the hydrochlcride of the amino-aldehyde has not been obtained in a crystalline form. dl-a-Amino-P-phenylpropionacetul CH2Ph*CYH(NH,)*CH(OEt) has b. p. 103-105°(corr.)/0~25 mm. or 163.5°/11 mm. D20 0.995 nD 1.49383. It is practically insoluble in water and does not reduce Fehling's solution. The picrate CI9Hz4O9N4 cry&allises from benzene in small yellow prisms or plates m. p. 106-107° (corr.). J. J. S. Malonamide Derivatives. . MAX CONRAD and ARNOLD SCHULZE (Ber. 1909,42 729-'735).-0nly one of the methylene hydrogen atoms of malonamide can be replaced by an alkyl group by treatment with sodium alkyl oxide and an alkyl halide. Metbylmalonamide CHMe(CO*NH,) bas m. p. 212O and etiiylntalonumide m.p. 212-214'. o-Nitrobenzylma!onamide NO2-C,B4*CH2*CH(CO.NH,!2 m. p. 234O (decomp.) is obtained from malonamide sodium ethoxide and a cold alcoholic solution of o-nitrobenzyl chloride. The interaction of oximinomalonamide formic acid D 1 *22 and zinc dust on the water-bath leads to the formation of formylaminomdon- amide HCO*NH*CH(CO.NH,) m. p. 2 0 6 O (decomp.) darkening at 195-200'. Methyl fomnylamanomulonute CHO*NH-CH(C02Me)2 m. p. 8 5 O b. p. 250' (decomp.) prepared in a similar manner from methyl oximinomalonate is converted into the preceding compound by an excess of concentrated ammonium hydroxide. Ethyl formylamino- malonate has m. p. 48'. The reduction of oximinomalonic esters by zinc dust and 80% acetic acid yields glycine. MaZornyZdiurethane CH,(CO*NH*CO,Et) obtained by heating malonic acid urethane and acetic anhydride for five hours on the water-bath has m. p.124O yields ammonium barbiturate urethane and malon- amide by treatment with ammonia and by beating with a solution of sodium nitrite and decomposing the cold product with the calculated amount of hydrochloric acid forms nitrosomalon yldiurethams CgH1307NS VOL. XCVI. i. 421 4 ABSTRACTS OF CHEMICAL PAPERS. m. p. 203-204' which gives a colourless solution with sodium hydroxide a yellow solution with ammonium hydroxide and in aqueous solution yields a deep blue precipitate by careful treatment with sodium hydroxide and ferrous sulphate. 0. s. Action of Semicarbazide on Chloroaldehydes. ANDRB KLING (Compt. rend. 1909 148 568-570).-Chloral hydrate or chloral alcoholate reacts readily with semicarbazide in aqueous solution forming chEoval hydvate semicarbaxide CCI,*CH(OH)*NH-NH*CO*NH2 an unstable crystalline substance decomposing a t 90'.When boiled with water or alcohol it loses hydrogen chloride and forms the semi- carbazone of glyoxylic acid. When an alcoholic solution of dichloroacetaldehyde and semi- carbazide is alllowed to evaporate in a vacuum dichloroucetaldehyde sem~curbazide C,H,OCI,N remains as a crystalline mass m. p. 155-156' (decomp.). On boiling with water it is transformed into glyoxalsemicarbazone. Chloroacetaldehyde hydrate forms a semicurbaxone CH,Cl-CH:N*NH* CO *NH m. p. 134-135O (decomp.). w. 0. w. Desmotropy and Merotropy. VI. Constitution of Cyanic Acid. ARTHUR MICHAEL and HAROLD HIBBERT (Annalen 1909 364 129-146.Compare this vol. i 91).-The authors have endeavoured to determine the constitution of cyanic acid by investigating the action of tertiary amines on the substance in the state of vapour and also in solution. The problem is complex on account of the ease of conversion into cyamelide and the fact that not only do the primary and secondary amines react in solution to give the corresponding salts but also the tertiary amines trimethylamine triethylamine and tripropylamine. The salt is mixed in many cases with cyamelide the amount of the latter varying with the nature of the solvent. Triisoamylamine however does not give rise to salt formation in any solvent the precipitate consisting exclusively of cyamelide ; the same result is obtained by passing the vapour into the amine at - loo.Since i t is possible to prepare the salt indirectly and it proves to be stable under the conditions just mentioned the conclusion is drawn that cyanic acid in the state of vapour and in solution is really carbonimide C0:NH. The main support of the latter argument lies in the fact that triisoamylamine combines with the weakest acidic substances such as phenols to give stable salts and its power of enolisation is practically non-existent. The salt formation in the case of the other tertiary amines is explained as follows When a molecule of an amine NR comes into the sphere of action of a molecule of carbonimide O:C:NH there is in every case a tendency towards salt formation. This expresses itself in a primary attraction of the positive nitrogen of the amine for the negative oxygen of the carbonimide in consequence of which the positive character of the former undergoes a considerable alteration.AsORGANIC CHEMISTRY. 215 a result it has a greater affinity for a positive element for example hydrogen which if pronounced enough results in the migration to it of the hydrogen of the carbonimide as indicated thus If the character of the nitrogen of the amine is rendered strongly positive through the introduction of certain radicles for example igoamyl then in spite of the influencing of the negative oxygen atom it has not the necessary affinity for hydrogen to enable it to separate the latter from the nitrogen of the carbonimide. Triisoamylamine for this reason does not yield a salt but the large amount of free.chemica1 energy in the molecule makes itself felt in the conversion of tho carbonimide into cyamelide.From this point of view salt formation does not presuppose the primary change -HNCO -+ NCOH but represents the phenomenon of merotropieation that is the formation of a salt directly from a merotropic substance. The influence of various solvents on the transformation of cyanates into the corresponding carbamides has also been investigated. It is found that there is no simple relation between the specific inductive capacity of the solvent and the rate of conversion (compare Michael and Hibbert Abstr. 1908 ii 465). Alkylammonium cyanates have not been obtained hitherto in a pure state ; they may be readily prepared however by adding the amine to an ethereal solution of cyanic acid at -loo except in the case of tripropy lamine triisobutylamine and triisoamylamine.The salts of primary and secondary amines change into the corresponding substituted carbamides at the ordinary temperature ; the rate of change depends largely on the nature of the amine. The following salts were prepared in the manner just described and analysed ; they are white crystalline substances and melt in sealed capillary tubes at the temperatures given. isoAmy1ammoniu.m cyanate m. p. 49-51' ; diethylammoniurn cyanate m. p. about 30-32O ; diisobutylammonium cyanate m. p. 53-54'; piperidine cyanate softens a t 35-37'; trimethylammonium cyanate and triethylammonium cyanate. Propyl- ammonium cyanate and benxylammonium cyanate are obtained as white precipitates by adding the amine to a solution of cyanic acid in chloro- form.Z7riisoamylammonium cyanate is obtained as a thick oil by adding water t o the alcoholic solution of the salt formed by shaking a solution of triisoamylalvmonium chloride in methyl alcohol with silver cyanate a t - 10". 0C:NH \ J NR W. H. G . Fulminic Acid. 11. Two New Methods of Preparation of Fulminic Acid. HEINRICH WIELAND (Ber. 1909 42 820-S22. Compare Abstr. 1907 i 196).-(1) Silver fulminate is formed by treating potassium aminomethylnitrosolate with nitric acid in the presence of silver nitrate. The aminomethy lnitrosolic acid is undoubtedly decomposed thus OH*C(NH,):N*OH-+H,O + N + C:N*OH. (2) Methenylamino-oxime when treated with nitric acid yields fulminic acid which in the presence of silver nitrate is obtained as its silver salt. Nitrous oxide undoubtedly derived from ammonium ! I 2216 ABSTRACTS OF CHEMICAL PAPERS.nitrate formed during the reaction is evolved ; the methenylarnino- cxime is decomposed thus CH(NH,) NOOH-+NH + C:N*OH. W. H. G. Nitroacetonitrile. IV. WILHELM STEINKOPF (Ber. 1909 42 617-621).-The constitution of this compound was fully established (Abstr. 19G8 i 327) but experiments to hydrolyse the nitrile to amide were unsuccessful. It is already known that trichloroaceto- nitrile may be hydroljsed to the corresponding amide (Abstr 1907 i 488) and the hydrolysis of the nitroacetonitrile D15 1.36 may be accom- plished by passing dry hydrogen chloride through an ethereal solution of nitrile (1 mol.) and methyl alcohol (1 mol.) cooled by a freezing mixtui e NO,*CH,*CN + MeOH + HCl-+[NO;CH,.C(OMe):NH,HCl] jNO,*CH,*CO*NH + MeCl.The yield is 40% and the compound YO prepared has m. p. 106-107°; it is however identical with nitro- acetamide piepared by other methods (compare Abstr. 1905 i 122 m. p. 101-102°; Ratz Abstr. 1904 i 858 m. p. 98-99'). This method is recommended as the best method for preparing it. Diclzloronitroacetonitrile NO,*CCI ,*CN prepared by the action of chlorine on a n ice-cold aqueous solution of ammonium acinitroaceto- nitrile is a colourless heavy oil b. p. 39'/21 mm. It decomposes when b3iled under atmospheric pressure is apt to explode if impure under these conditions and the vapour excites tears. When an ice-cold solution of ammonium nitroacetonitrile is treated with a concentrated aqueous solution of sodium nitrite cyanomethyz- lnitrolic acid CN.C(:KOH)*NO is formed as a viscous oil solidifying to a mass of hygroscopic crystal?.It is unstable and forms unstable red ammonium and carmine-red silver salts. W. R. Nitrile Oxides. 11. HEINRICH WIELAND (Ber. 1909 42 803-816. Compare Abstr. 1907 i 527).-It has been shown previously (Abstr. 1907 i 196) that methylnitrolic acid when warmed with dilute nitric acid decomposes into fulminic and nitrous acids. It is now found that an aqueous solution of methylnitrolic acid when evaporated on a water-bath leaves a residue of carbamide; in this case nitrous acid is eliminated and the CNOH residue changes into cyanic acid Fhich then passes into carbamide.It seemtd probable that the substance first formed in these reactions was formonitrile oxide hich then underwent transformation into cyanic acid or fulminic acid. The isolation of formonitrile oxide although not in the unimo!ecular form has shown the correctness of this assumption. When an aqueous solution of methylnitrolic acid is treated with the theoretical quantity of a 16% solution of sodium carbonate at very low temperatures a n orange-red solution is obtained which almost immediately becomes colourless and deposits a subbtance having the empirical composition CHON. This compound has the properties of the hypothetical formonitrile oxide; thus it yields salts of cyanic acid with alkalis car bamide with ammonia phenylcai bamide with aniline formic acid and hydroxylamine with acids formic acid and am- monia when reduccd with zinc dust and acetic acid hydrogen cyanide when aluminium amalgam is employed as the reducing agent andORGANIC CHEMISTRY.217 formhydroxamic acid when treated with water at the ordinary tem- perature. The physical properties of the substance and its close similarity to trioxymethylene cyamelide and cyanuric acid suggest the constitution represented by CH.0 CPh-’ formula I. It is proposed to -NA& N/\N/ name the substance tr$uZmin ; *<H(-jl ICH O<PhCI lCPh it is obtained as a colourless \/ I \/ I powder and is almost as explos- Tribenzonitrile oxide (formula (1.) (11.1 11) is prepared from phenylnitrolic acid in the same way as trifulmin. It is a colourless crystalline substance m.p. l25-13O0 (decomp.) and is not so explosive as trifulmin. I n its chemical behaviour it is similar to bonzonitrile oxide (compare Abstr. 1907 i 527); thus it is converted by cold alcoholic hydrochloric acid into oxoazoxime hydrochloride to the extent of SO% whilst the remainder is de- composed into benzoic acid and hpdroxylamine. It is converted by aniline into diphenylcarbamide and when heated in toluene or xylene passes quantitatively into phenylcarbimide. I t is suggested that a nitrile oxide is Formed as an intermediate product in Hofmann’s reaction thus R*C(ONa):N*Br -+ NaBr + -+ 0:C:N.R. Similarly in Curtius’ azoimide N-’ ive as silver fulminate. N-0 W. H. G. Nitrile Oxides. 111. The Salts of Greul and Hantesch’s Leuconitrolic Acid.HEINRICH WIELAND (Ber. 1909,42 81 6-820. Compare preceding abstract).-Ethylnitrolic acid like the correspond- ing methyl compound is decomposed by an aqueous solution of sodium carbonate yielding triacetonitrile oxide C6H903N3 obtained as a brittle vitreous mass decomposing at about 95’; it is very similar to trifulmin in its chemical properties. The remainder of the paper contains confirmation of the work of Graul and Hantzsch (Abstr. 1899 i 187). It is pointed out that the leuco-salts behave as mixtures of triaTetonitrile oxide with a nitrite ; thus aniline hydrychloride in aqueous solution is at once diazotised by potassium leuconitrolate ; the latter when heated in xylene yields methyl carbimide and when treated with aniline yields s-phenyl- methylcurbamide. It is definitely shown however that the leuco- salts are not mixtures ; moreover they have the unimolecular formula C,H,ON,M and it is suggested that they have the constitution CMe-N-0.“(OK)’ W. H. G. Hydroxide and Salts of Mercuriethylenediamine. LEONE PESCI (Gaazetto 1909 30 i 143-147).-Salts of mercuriethylene- diamine Hg:C,H,(NH,) are prepared by the action of ethylene- diamine on mercury salts by boiling ethylenediamine salts with yellow mercuric oxide or by double decomposition of the acetate. They are /o\218 ABSTRACTS OF CHEMICAL PAPERS. decomposed by hydrogen sulphide mineral acids potassium iodide or sodium thiosulphate. Mercuriethylenadiumine hydroxide C,H4Hg(NH,=OH),,3*5H20 pre- pared from the sulphate and barium hydroxide forms a white amorphous powder decornp.128’) soluble in water decomposed %y light. The chloride crystallises from boiling water decomp. 160’ ; the sulphate forms an insoluble precipitate of microscopic rectangular tablets containing H,O. A preparation known as eubzamina con- taining 43% Hg appears to contain molecular proportions of this sulphate and of ethylenediamine. The nitrate forms microscopic anhydrous granules insoluble in water ; the acetate is also anhydrous and forms microscopic hexagonal scales m. p. 1 9 5 O . Synthesis of a-Hydroxymercuri-fatty Acids. 11. Methyl Hydroxymercurimethylrnalonate and its Product of Hydrolysis a-Hydroxymercuripropionic Anhydride. WALTER SCHOELLER and WALTER SCHRAUTH (Ber. 1909 42 777-785. Compare Abstr. 1908 i 617).-Whereas methyl mercuridimalonate is formed remarkably easily (Zoc.cit.) alkyl-substituted malonates react sluggishly with mercuric oxide. Methyl a-hyd?*oxymercurimethJ- mazonate OH-Hg*CMe(CO,Me) results when the ester (la mols.) is shaken with precipitated mercuric oxide (1 mol.) and water for four days at 37O in the dark. Admixed mercuric oxide is removed by careful washing of the product with 1% acetic acid; it decomposes at 235O and the ester is regenerated by boiling with a halogen acid N-Sodium hydroxide yields a 4 ydroxymercuripropionic anhydride C. H. D. CHMe Hg<o->CO in 97% yield ; ammonium sulphide causes blackening a reaction which appears t o be a characteristic of a-hydroxymercuri-fatty acids ; P-acids do not give this reaction. The blue copper salt Hg2C,HI,0,Cu mas analysed ; the cuZcium Zead and mercury salts are white; the silves.yellowish-white. Towards mineral acids it behaves similarly to its lower homologue (Zoc. cit.). Sodium a-hydroxymercuripropionate is poisonous (( organotrop ” ; the P-hydroxy-salt is on the other hand a disinfectant ‘( parasitotrop.” Hydroxymercuripropionic anhydride can be obtained in 93% yield from mercury acetamide and methyl methylmalon&e in the presence of alkali. The acetamide formed initially from the condensation of mercury acetamide and methyl methylmalonate is soluble in water whereas that from methyl malonate is not and as these regenerate the ester with hydrochloric acid advantage is taken of these facts for the purification of commercial malonic esters. W. R. So-called Pure A1:3-Dihydrobensene and its Molecular Re- fraction.CARL D. HARRIES and HANS VON SPLAWA-NEYMAN (Ber. 1909 42 693-698).-According to Zelinsky and Gorsky (Abstr. 1908 i 619) A1:3-cyclohexadiene exhibits no optical exaltation although it contains conjugate double linkings. Briihl (ibid. ii 1002) has already questioned the constitution of this compound and the authors bring forward evidence which indicates that the productORGANIC CHEMISTRY. 219 obtained by Crossley’s (Trans. 1906 85 1403) or Zelinsky’s (Zoc. cit.) method is a mixture o€ A1‘3-cycZohexadiene and cyclohexene. This evidence is based on the fact that the ozonide of the hydro- carbon when decomposed with acetic acid yields adipindialdehyde as well as succindialdehyde and from the former cydopentenaldehyde (Baeyer and Liebig Abstr. 1898,-i 638) was readily isolated.J. J. S. Sodium Derivative of Indene. RUDOLF WEISSUERBER (Ber. 1909 42 569-572) ; GESELLSCHAFT FOR TEERVERWERTUNU (D.R.-P. 205645. Compare A bstr. 1908 i 873).-Many unsuccessful attempts have been made to obtain the potassium derivative of indene (compare Thiele Abstr. 1901 i 182 ; Kraemer ibid. 535). It is now found that the sodium derivative C,H4<CHNa>CH may be prepared by heating indene with sodamide at 110-115° by treating indene and sodium a t 120-130° with ammonia or by heating indene with sodium a t 140-150°; it is obtained as a brown amorphous mass having the appearance of colophony. The formation of the sodium derivative of indene furnishes a ready means of obtaining this hydro- carbon in a state of purity from the so-called “heavy benzene,” b.p. 175-185’ obtained from coal-tar. This fraction is treated in the manner just described the unattacked hydrocarbon removed by distillation under reduced pressure and the sodium indene decomposed with water. W. H. G. Indene in Coal Tar. ADOLF SPILKER and ALFREDOMBBOWSKY (Ber. 1909 42 572-573. Compare Kraemer and Spilker Abstr. 1891 205).-Pure indene obtained from coal-tar by the method described in the preceding abstract has b. p. 182.2-1S2*4°/761 mm. (cow.) Di 1.0002 n’,” 1.5’773 f. p. - 2’. Indene dibromide contrary to the statement of Kraemer and Spilker (Zoc. cit.) is a stable substance crystallising in colourless thick prisms xu. p. 315-32-5O. CH W. H. G. Photochemical Reactions of the White and Yellow Diphenyl- octatetrenes.HANS STOBBE (Ber. 1909 42 565-568. Compare Abstr. 1908 ii 339).-From the method of formation it is probable that the white at9-diphenyl-Aaw-octatetrene of Fichter and Hirsch (Abstr. 1901 i 594) and the yellow aO-diphenyl-hauc~-octatetrene of Fittig and Batt (Abstr. 1904 i 744) are stereoisomerides in which case it should be possible to convert one into the other by the action of light. It is found that both substances in the presence of air and under the influence of light undergo oxidation yielding resinous products containing benzaldehyde and benzoic acid. I n the absence of oxygen however only one substance is acted on namely the yellow variety which passes into the white isomeride. W. H. G. Photochemical Reactions. IV. Thermodynamic Theory of Photochemical Processes.FRITZ WEIGERT (Ber. 1909 42 850-862. Compare Abstr. 1908 ii 914).-The photopolymerisation of anthracene to dianthracene has been further studied. The pro- portionality previously found between the amount of light energy220 ABSTRACTS OF CHEMICAL PAPERS. used chemically and the total energy absorbed by the anthracene is confirmed. From experiments made in the dark at 8 5 O and 1 0 5 O the conclusion is drawn that the equilibrium 2C,,H,0 C,,H is altered in favour of the dianthracene a t the higher temperature and the tbermal value of the polymerisation is calculated as - 20,000 cal. The relation between the equilibrium constant in the dark and temperature is expressed by the equation logH= - 4330/T+ 10.27 which has been tested by experiments at different temperatures in toluene solution and also in benzene and xylene.The high value of 43% has been experimentally found to represent that proportion of the energy absorbed by the anthracene which is used chemically. When a platinum wire heated electrically is made to glow (tempera- ture about 900') in a boiling solution of anthracene in ether or light petroleum which contains solid anthracene a crust is formed on the wire. This in part consists of dianthracene. E. F. A. Preparation of Aniline and its Homologues. AKTI ENGESELL- SCHAFT FCR ANILIN FABRIKATION (D.R.-P. 20495 l).-The halogen of chlorobenzene can be replaced by ammonia by heatiog the halogenated hydrocarbon with ammonia in presence of copper salts. Chlorobenzene (200 parts) 25% aqueous ammonia (600 parts) and copper sulphate (25 parts) when heated at 180-290° for twenty hours yield 80% of the calculated amount of aniline.CX. T. M. Preparation of Sulphanilic Acid. AKTIENGESELLSCHAFT FUR ANILIN FABRIKATION (D.R.-P. 205150).-Sulphanilic acid in an SO% yield can be obtained by heating chlorobcnzene-p-sulphonic acid with aqueous ammonia and copper chloride at 170° for twelve hours. G. T. M. Action of Calcium Hypochlorite on m-Nitroaniline. WILHELM KORNER and ANGELO CONTARDI (Atti R. Accad. Lincei 1909 [v] 18 i 93-103. Compare Abstr. 1908 i 523).-By the action of calcium hypochlorite in such quantity as to contain 1B mols. of active chlorine on 1 mol. of ua nitroaniline in glacial acetic acid at 40-60° allowing the solution to remain for twelve hours a reddish-brown pro- duct is obtained when ice-water is added and a further brownish- yellow precipitate is obtained on partial neutralisation of the filtrate.The first product consists mainly of 2 6-dic?doro-3-nitroaniZine long needles m. p. 110.89 The acetyl derivative forms glistening crystals m. p. 128.6'. Together with this is the 2 4 6 trichloro- 3-nitroaniline m. p. 102.5' the acetyl derivative has m. p. 194-195O and also 2 4-dichloro-3-nitroaniline m. p 97.5' acetyl derivative hag m. p. 128.9'. 1 he second fraction contains chiefly 4-chloro-3 nitroaniline m. p. 97.6"; acetyl derivative m. p. 150". No trace of 4 :6-dichloro- 3-nitroaniline could be detected. C. H. D. [Preparation of the Alkali Derivatives of Aromatic Primary and Secondary Amines.] BASLER CHEMISCHE FABRIK (D.R -P.205493)-The aromatic amines do not react readily with the alkaliORGANIC CHEMISTRY. 221 metals but it bas now been found that when a mixture of alkali metal and an alkali hydroxide is employed the reaction proceeds smoothly. A mixture of metallic sodium and potassium hydroxide heated to 200-260° was employed and a t these temperatures aniline o-toluidine and methylaniline merj readily absorbed forming mixtures of their sodium and pota3sium derivatives which were thus obtained as crystalline dark brown very reactive products regenerating the base on treatment with water. G. T. M. Mercury Double Salts of Tetrahydronaphthylamines. OSKAR GROHMANN and ARJEN BROUWER (Annalen 1909 365 50-52. Compare B.imber ger A bs tr. 1 888 6 00 9 60).-ac-P-Tetrahyd ro- naphthylamine hydrochloride combines with mercuric chloride in two proportions. The one compound C,oH,1~NH2,HC1,2HgC12 crystal- lises from water in long glistening prisms m. p. 241.5-242'; the other 2(C,,H,~NH,,HCI),HgC12 crystallises in colourless plates m. p. 221-%22 and is only formed in the presence of an excess of hydrochloric acid. When crystallived from water it yields the less fusible compound. ar-a-Tetrahydronaphthylamine yields the compound C,,Hl,*NH,,HC~,HgC1 m. p. 179-180' ; also a compound 2(C,oH,,*NH2,HCI),HgC12 which crystallises in doubly refracting plates m. p. 217*5-219O and a third compound C,,H,,*NH,,HC1,2 HgCI which forms colourless prismatic needles m. p. 192.5-1 93.5'. J. J. S. Preparation of 2-p-Nitrosoanilinonaphthalene-6 Sdisul- phonic Acid.BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 205414). -When treated with alcoholic or concentrated aqueous hydro- chloric acid the nitrosoamines of the 2-ary1am;nonaphthalenes are converted into nitroso-derivatives containing the nitroso-group in the contiguous a-position of the naphthalene nucleus. When the nitros- amine of 2-anilinonaphthalene-6 8-disulphonic acid is thus treated the nitroso-group migrates into the phenyl ring in the para-position to the aminic nitrogen forming 2-p-nitrosoanilinonaphthalcne-6 8- dieulphonic acid NO,*C,H,*NH.C,,B,(S~~H)~ reddish-brown needles readily soluble in water. G. T. M. The Compounds which Cause the Red Colour in Phenol. HARRY D. GIBBS (Philippine J. Sci. 1908 A 3 361).-Phanol which had become red by exposure to sunlight at a temperature of 30° was treated with a small quantity of sulphurous acid and distilled in steam; the residue in the distillation flask after filtration from a very small amount of red precipitate was extracted with ether and found to contain considerable quantities of catechol and quinone. The red colour is attributed to the solution in phenol of quinone and the highly-coloured condensation product phenoquinone.The presence of oxygen was proved to be necessary for the production of the red colour since no coloration was produced in moist phenol contained in sealed tubes filled with carbon dioxide on exposure to222 ABSTRACTS OF CHEMICAL PAPERS. sunlight. This fact moreover appears to shorn that water and carbon dioxide do not react in the presence of sunlight to form hydrogen peroxide and oxygen as assumed by von Baeyer since the presence of oxygen in these experiments would have been revealed by the production of a red colour.Preparation of p-Aminophenol and its N-Alkyl Derivatives. AKTIEN~ESELLSCHAFT FUR ANILIN FABRIKATION (D.R.-P. 20541 5).- By heating p-chlorophenol a t 135-140' with ammonia or primary base8 (such as methylamine) in the presence of copper salts (copper sulphate for example) p-aminophenol p-methylaminophenol and similar compounds are readily obtained in excellent yield. p-Ethyl acmirwphnol white Deedles m. p. looo which is thus obtained gives an oily nitroso-compound. Behaviour of 3-Nitro-p-cresol towards Sulphuric Acid GUSTAV SCHULTZ and OSKAR Low (Ber.1909 42 577-578).-The compound obtained by the action of fuming sulphuric acid on %nitro- p-cresol previously thought to have the formula C7H,0 (Schultz Abstr. 1907 i 1030) has now been found t o be identical with acetyl- acrylic acid and is formed as follows P. H. G. T. M. The reaction takes place according to the equation 2C7H70,N + 7H,SO,-= 2C5H,0 + (INH,),SO,% 4H,O + 6S02 + 4C0,. J. c. c. Intramolecular Transformations of Acylated Compounds. KARL AUWERS (Annulen 1909 364,147-182).-The results obtained in this investigation together with those published previously on the intramolecular transformations of acylated phenols containicg amino- and imino-groups (compare Auwers Abstr. 1904 i 581 736 1051 ; Auwers and Bondy ibid. 1053 ; Auwers and Burger ibid.1054 ; Auwers and Dannehl Abstr. 1908 i 458) are discussed in detail and the following conclusions drawn (1) In ordinary circumstances an acyl group migrates spontaneously from the oxygen to the nitrogen no matter whether this be the first second or third member of a side- chain in the ortho-position provided the acid character of the acyl group and the basic character of the nitrogen group are sufficiently pronounced. (2) The migration of the acyl group is rendered more difficult by greatly diminishing the basic character of the amino- or imino-group ; in many cases a rearrangement is totally prevented. (3) The migration of the acyl group is similarly affected by reducing the acidic character of the acid radicle but up to the present no case has been observed where the migration has been completely checked. (4) The nitrogen group is able to attract both heavy and light acid radicles provided its basic character is sufficiently pronounced.The relative weight of the acyl group is however a determinative factor in the intramolecular transformation when the compound is a neutral substance or only slightly basic; as a rule in such cases the ease with which the acyl group migrates diminishes greatly with an increase in the weight of the group.ORGANIC CHEMISTHY. 223 [With KARL M u ~ ~ ~ ~ . ] - p - T o l y l methyl ether and chloroacetyl chloride react in equivalent proportions in the presence of aluminium chloride yielding 3-chloroacetyl-p-cresol and 3 5-dichloroacetyl-pcresol (compare Fries and Finck this vol. i 42).3 5-Diacetyl-p-cresoZ CiiHi203 is obtained when 3 mols. of chloroacetyl chloride are employed ; it crystallises in slender needles and long compact prisms m. p. 82-83O. 3-Cbloroacety1-p-creso1 when reduced with zinc dust and acetic acid yields 3-acetyl-p-cresol long glistening colourless prisms m. p. 50" (compare Auwers and Betteridge Abstr. 1900 ii 262) and when heated with benzoyl chloride yields the benxoah C,,H1,03C1 long glistening prisms m. p. 92'. The latter substance when heated with aniline or p-toluidine dissolved in toluene yields C H- CMe YH CH-C(OH) Co CO* CH,*NPh B z N-benzoyZ-3-phsnyZgZycyl-p-cresol I I 9 pearly scales m. p. 172*5" and N-benzoyZ-3-p-'tolpk$ycyZ-p-cr&oZ C,,H2,03N silvery leaflets m. p. 193.5"; the oxime of the former C29H2003N2 forms flat compact needles m.p. 157- 158'. 3-PhenyZgZycyZ-p-crcsot C,,Hi,02N obtained by boiling 3-chloroacetyl-p-cresol with an alcoholic solution of aniline crystallises in small slightly yellow needles m. p. 82-83' ; i t yields the N-benzoyl derivative m. p. 173*5" even when benzoylated in pyridine. [With Huao D A N N E H L . ] - ~ ~ ~ ~ the acetate of dibromo-p-hydroxy- benzyl bromide is heated with pnitrophenylhydrazine under pressure at loo" it yields the a-N-acetate of dibromo-p-hydroxybenzyl-p-nitro- phenylhydrazim 0H8[.C6H,Br2*CH2*NAc*NH-C,H,*N02 a chocolate- brown crystalline substance m. p 258-259' (decomp.) ; the same compound is obtained by condensing 8-acetyl-p-nitrophenylhydrazide with dibromo-phydroxybenzyl bromide. [With FRITZ EISENLOHR.]-T~~ phenyhwethnne of 3-nit~o-p-c~eso~.NO,-C,H,Me*O*CO*NHPh is obtained by heating the nitrocresol with phenylcarbimide under pressure at 120-130" ; it forms pale yellow crystals m.. p. 102O and when reduced with zinc dust and acetic acid yields O-carbanilido-3-amino-p-creso1 C,,HI,0,N2 white crystals m. p. 169" ,and N-carbaniZido-3-ccrnino-p-cresol C,,Hl,0,N2 ; the latter substance may also be prepared by the action of phenylcarbimide on 3-amino-p-cresol or by treating the 0-derivative with hot glacial acetic acid ; it crystallises in slender silky needles m. p. 158-159'. [With W. HrRTand KARL M u ~ ~ ~ ~ . ] - 3 - ~ e n x e n e a z o - p - t o l y l propionah Cl6Hl,O,N2 obtained by the action of propionyl chloride on 3-benzene- azo-.p-cresol forms small bright red needles m.p. 48-49' and is reduced by sodium amalgam to the corresponding hydraxo-derivative C16Hl,0,N2 a green powder m. p. 100" (decornp.). p Z'oluerceazo-p-toll propionate C17HI8O2N2 can only be obtained by heating the azo-phenol with propionic anhydride ; it crystallises in dark red leaflets m. p. 6 2 O and when reduced yields the corresponding hydrazo-derivative C17H2,02N2 obtained as colourless leaflets m. p. 105'. Both of the preceding hydrazo-compounds are definitely shown to be 0-propionates. Dibromo-opropioitoxybenzy2 bromide C10H902Br3 forms white felted needles m. p. 89' and when acted on by phenylhydrazine yields224 ABSTRACTS OF CHEMICAL PAPERS. the a - N -propionyl- 3 5 - dibvomo - 2 - iLydroxybanzylp~nyZ~ydrazine OH*C,H,Br,*CH,*N(COEt)*NHPh pearly leaflets m.p. 164' ; the same compound is obtained by the action of s-propionylphenyl- hydrazine on dibromo-o-hgdraxyl benzyl bromide. Di bromo-o-propion- oxybenzyl bromide wben treated with s-acetylphenylhydrazine yields the o-propionate of a-N-acetyZdibsomo-o-hydroxybenayZphenyZ~~~razine C,8H,,0,N2Br cryetallising in glistening leaflets m. p. 188-189O. The. substance is not affected by boiling with glacial acetic acid. W. H. G. 0 rgs t dlog r aphy of p - D it h y m olylamioe Dime t h y 1 Ether. A. FERSMANN (Zeitsch. Kryst. Min. 1909 46 219 ; from Bull. SOC. Nat. MOBCOU 1906 Nos. 1 and 2 133-138).-The crystals are rhombic [a b c = 1,152 1 0.6851 (compare Decker and Solonina Abstr. 1905 i 197). L. J. S. Beparation of 0- and p-Phenolsulphonic Acids. JULIUS OBERMILLER (D.R.-P.202 168).-A solution of 0- and p-phenol- sulphonic acids is treated with barium carbonate and evaporated until granular aggregates of barium o-phenolsulphonate separate accompanied by needles of the para-salt. The latter is dissolved by the cautious addition of water and the less soluble ortho-salt thus separated. The mo:her liquor is treated with magnesium sulphate and evaporated until magnesium p-phenolsulphonate separates. The final mother liquor contains a little of tho meta-isomeride and more of the ortho-salt. When the free acids are converted into magnesium salts and their solutions evaporated the major portion of the para-salt separates first. Further addition of magnesia t o the mother liquor leads to separation of the dimaguesium salt of the ortho-acid.G. T. M. Preparation of p-Aminophenol-2 sulphonic Acid. AKTIEN- GESELLSCHAFT FUR ANILIN FABRIKATION (D. ft.-P. 202566).-p-A mino- phenol-2-sulphonic acid is prepared by heating 4-cblorophenol-2- sulphonic acid with aqueous ammonia and copper chloride at 165O. G. T. M. New Salts of Guaiacolsulphonic Acid. ACHILLE TAGLrAvINr (Boll. chim. farm. 1909 48 6 -9).-Potassium guaiacolsulphonate is used as a drug; salts have now been prepared with antipyretic and analgesic bases. OEt*C,H,*NH* C0.CH2*NH,,0Me*C6H3( OH)*SO,H prepared by adding an ethereal solution of the base t o a concentrated alcoholic solution of the acid forms small crystals m. p. 183O. p- Phe netid yZg1yc yl guainco Isulphonnate Euquinine guaiacoZsuZphonate CO,E t -C2,1H?302N2 OMe*C,H,( OH) *SO,H prepared by mixing hot solutions of basic euquinine sulpbate and barium guaiacolsulphonate forms a powder m.p. 84O. p - Phenet idine guaiacolsutphonate ~Et*C,H,*NH,,~Me*C,H,(OH)=SO,~,ORGANIC CHEMISTRY. 225 prepared similarly to the first salt mentioned forma microscopic crystals m. p. 186-18s'. Preparation of Salts of Carbonatoguaiacol-mono- and -di- sulphonic Acids. ALFRED EINHOBN (D.R.-P. 203754).-It has been found that carbonyl chloride will condense with alkali guaiacol- sulphonates in alkaline solution giving derivatives in which the carbonyl group becomes attached to two phc nolic oxygens. C. H. D. Potassium car bonatodig uaiacoldisulphot ate CO[OC,H,(OMe)oS03E(] needles from water is produced by passing carbonyl chloride into an alkaline solution of potassium guaiacolsulphonat e (thiocol).Potassium carbonatodiguaiacolsul phonate C,H,(OMe)*O*CO*O-C,H,(OMe) * S03K is similarly obtained from a mixture of guaiacol and its sulphonate. G. T. M. 2- Hydroxystilbene. STANISLAUS VON KOSTANECKI and JOSEF TAMBOR (Ber. 1909,42 S25-S27).-2-Hydroxystilbene prepared from 2-methoxystilbene by heating with alcoholic potassium hydroxide at 160° crystallises in colourless needles m. p. 147O which dissolve in dilute sodium hydroxide with a green fluorescence ; 2-acetoxystilbene forms colourless needles m. p. 54-55'. 2-Acetosystilbene dibromide OAc-C,H,*CHBr*CHPhBr prepared by the addition of bromine in carbon disulphide solution separates in long glistening needles m. p. 150'. When heated with sodium ethoxide it is conrerted into the 1 -phenplcoumarone C,H,<$i>CPh m.p. 120-1 21° described by Stoermer (Abstr. 1904 i 181). 2-Stilbenyloxyacetic acid CHPh CH*C,H,* O=C H,.CO,H crystallises in long needles m. p. 136'; the dibromide forms colourless needles m. p. lSSo (decornp.). Ethylene di-2-stilbenyl ether C,H,(O*C,H,*CH:CHPh) formed by the action of ethylene bromide on an alcoholic solution of sodium-o- h ydroxystilbene crystallises in colourless needles m. p. 1 10'. E. F. A. Preparation of Anthranol and its Derivatives from the Corresponding Anthraquinones by Reduction with Metals and Acid. FARBENFABRIEEN VORM. FRIEDR. BAYER CE Co. (D.R.-P. 201 542).-Anthranol is readily obtained by adding copper or aluminium powder to a solution of anthraquinone in concentrated sulphuric acid at 30-40° and pouring the decolorised solution into water ; it is recrystallised from glacial acetic acid containing a trace of aluminium and a little hydrochloric acid.a-Aminoanthranol can be similarly prepared from a-aminoan thra- quinone by reduction with aluminium bronze in cold concentrated sulphuric acid. G. T. M. ERNESTO PUXEDDU (Gazzetta 1909,39 i 131-137). -Whilst isoeugenol and similar compounds containing the ally1 group readily polymerise the isomerides containing the propenyl group do not yield polymerides. isoEugeno1 is best etherified by treatment Diisoeugenol.226 ABSTRACTS OF CHEMICAL PAPERS. with sodium hydroxide and ethyl sulphate; the ethyl ether forms brilliant scales m. p. 64' (compare Eykmaa Abstr. 1890 748). The molecular weight in acetic acid solution is normal.Dry hydrogen chloride in ethereal solution converts it i n to a polymeride crystallising from aqueous alcohol in white prisms m. p. 130'. The polymeride obtained by Wassermann (Abstr. 1879 790) had a lower m. p. and was insoluble in ether whereas the new compound dissolves readily in ether Diisoeugenol is best prepared by heating an alcoholic solution of isoeugenol with fuming hydrochloric acid on the water-bath. It forms white needles m. p. 1 SOo. Ethyl sulphate or iodide converts its sodium derivative into an ethyl ether identical with that obtained by the direct polymerisation of isoeugenol ethyl ether. The nature of the isomerism of the two diethyl ethers is not yet certain. The products of bromination and oxidation are under investigation.C . H. D. LUIGI FRANCESCONI and ERNESTO PUXEDDU (Gaxaettcc 1909,39 i 202-21 1). -Although compounds in which the side-chain contains a pair of doubly-linked carbon atoms one of which is directly joined to the benzene ring generally polymerise there are great differences in the readiness with which polymerisation takes place in related compounds. The authors have studied the influence of constitution in the case of eugenol and isoeugenol and their ethers and of safrole and isosafrole. Diisoeugenol is obtained when light acts on an alcoholic solution of isoeugenol in presence of hydrochloric acid or by the action of hydrogen chloride on the dry ethereal solution (compare Puxeddu preceding abstract). The product is in all cases identical with that obtained by Tiemann (Abstr.1892 45) by the hydrolysis of the acetpl derivative. Eugenol and safrole do not polymerise when treated by either method. isoSzlfrole yields a viscous product. Diisoeugenol dimethyl ether crystallises from aqueous alcohol in long whiteneedles m. p. 106". Bromine reacts with diisoeugenol in chloroform solution yielding a dibromo-derivative m. p. 16S0 which on analysis did not give figures corresponding with any simple formula. Bromine converts diisoeugenol dimethyl ether in ethereal solution into a nLonobs.omo-derivative C,,H2,0,Br crystallising from alcohol m. p. 125O. It is insoluble in water dilute acids or aqueous alkalis. Polymerisation of Aromatic Ethylenic Compounds. C. H. I). Cyclic Trimethylene Compounds of the Type RHC<bH,.CH2 PIERRE BRUYLANTS (BUZZ. Acad. roy. Belg. 1908 1011-1084).-The author has prepared a series of compounds containing the cycbpropyl group and has recorded in a series of tables the relations obtaining between the boiling points and densities of these compounds and the corresponding isopropyl and ally1 derivatives The cornpounds examined include (1) ketones of the type R*CO*C!H<?H2 obtained by CH,'ORGANIC CHEMISTRY. 227 the action of organomagnesium derivatives on ethylenoacetonitrile (cyclopropanecarboxylonitrile) NC*CH< I - (2) the secondary alco- hols OH*CHR*CH<yH2 prepared from the ketones by reduction j CH CH ' CH CH2 (3) the tertiary alcohols OH*CRR*CH< I prepared by applying CH the Grignard reaction to the ketones; (4) t*he chlorides bromides iodides and acetates of the tertiary alcohols; (5) the ethers and unsaturated hydrocarbons obtained from these salts.(Perkin Trans. 1885 835 ; Lipp Abstr. 1889 843) prepared by the action of magnesium methyl bromide on cyclopropanecarboxylonitrite has b. p. 114'/772 mm. cycloPropyl ethyl ketone COEt*CH< I b. p. 132-133' (corr.)/ 767 mm. D20 0.9152 n? 1.42931 on reduction with sodium and alcohol yields cyclopropylethylcarbinol OH*CHEt*CH< I ' b .p. 140"/767 mm. DT0 0.8901 1-4326; theacetate has b. p. 159'/765 mm. DZo 0.8175 cjcloPropyl isopropyl ketone COPrp*CK< I 2 b. p. 139-141"/769 mm. D2O 0.9006 n2,o 1.42731 yields on reduction cyclopropylisopropylcurbinol OH*CHPrp*C'H<yH2 b. p. 15 1-1 52.1 769 mm. nD 1.43643; the acetate bas b.p. 171-173'. cycZoPropyldimeth ylcarbinol OK*CMe,*CH<~H2 (Zelinsky Abstr. 1901 i 661 ; 1902 i 70) prepared by the action of magnesium methyl bromide on ethyl cyclopropaaecarboxylate has b. p. 124'/776 mm. D20 0.9335 nz 1.43232 ; the chloride has b. p. 132-133* D20 0.9441 ; the bromide has b. p. 152-153O/766 mm. D20 1.218 ; the iodide has b. p. 113-114'/55 mm. D20 1.338; the ucetnte has b. p. 159-1609 D20 C'H c=2 cycZoPropy1 methyl ketone COMe*CH< I CH CH2 CH ( 3 3 2 CH CH CH2 CH2 0.91 67. The unsaturated hydrocarbon P-cydopropyZpopyZene CH, CMe-CH<bHo CH2 b. p. 77'/758 mm. D20 0,7375 ng 1.45037 i i obtained advantageously by the action of dry potassium hydroxide on the preceding bromide at 170" ; it is also produced by the action of alcoholic potassium hydroxide on the chloride bromide or iodide or by the direct dehydration of the alcohol by means of phosphoric oxide and combines with bromine t o form the tribromo-derivative CH,Br=CMeBr*CBr<yH2 1-Ethoxy- CHo* 1 -isopropylcyclopropune ?H2>CPrs.0Et b.p. 140-1 45',DZ0 0.82493 CH ng 1.42481 is formed togetLer with the preceding hydrocarbon when cyclopropyldimethylcarbinol is heated with alcohol at 1 OO' or by the action of alcoholic potassium hydroxide on its bromide chloride or228 ABSTRACTS OF CHEMICAL PAPERS. iodide ; it reacts with hydrobromic acid to form l-broino-l-isopropyl- cyclopropane,~H2>CPIaEr b. p. 174' or 108-1 10°/55 mm. D20 1 *1597 which is isomeric with the bromide of the original alcohol. CH2 - cy clo Prop y ldiet h$cccrbinol OH* CEt,*CH<yH2 has b. p.1 5 8- 1 5 9'1 CH 759 mm. D20 0.9055 wg 1.44638 ; the chloride ha b. p. 160-166' D20 0 9407; the bromide has b. p. 186-187O/756 mm. D20 1.1479 ; the iodide has b. p. 152'/55 mm. D20 1-3357; when the bromide is heated with alcoholic potassium hydroxide a mixture of the et'hylenic hydro- carbon CHMe:CEt*CH<yHZ y-cyclopropyZ-A~-umylene and the tthw CH CHEt2*C(OEt)<gE2 (P-eth yl-h-eth yleno-a ethozybutune) is produced ; the hydrocarbon has b. Ip. 129-130° D2O 0.7644 ng 1.45841 and the ether has b. p. 176-27S0 D20 0.81 30. cycloPropylmetl~yZeth?lZcai.binoZ OH*CMeEt*CH<yH2 has b. p. 141-142'/761 mm. D2O 0.90119 n 1.44135 ; the ch2oride has b. p. 150-153O D20 0.9391; the bromide has b. p. 167-168'/766 mm. D20 1.1938; the iodide has b. p.128-130°/55 mm. D20 1.3499. The ethy lenic hydrocarbon CHMe C hie* CH<FH2 (P-cyclopropyl-AP -but yl- em) is obtained from the preceding bromide by the action of potassium hydroxide at 170° and has b. p. 107-109°/764 mm. D2O 0,7743 74g 1.44476. M. A. W. CH2 CH2 Action of' Sodium and Amy1 Alcohol on Cholesterol. G. G. WILENKO and SIGMUND MOTYLEWSKI (BUZZ. Acad. Sci. Cmcow 1908 837-841. Compare Diels and Abderhalden Abstr. 1906 i 272; Neuberg ibid. 356 ; Windaus ibid. 1907 i 610).-1n addition to dihydrocholesterol two new products have been obtained by reducing cholesterol with sodium and boiling amyl alcohol. One of these resembles coprosterol and is termed 1-coprostei.ol. Of the three compounds it is the one most readily soluble in ethyl alcohol and crystallises in long needles m.p. 86-87'. It has [a] - 14.3" and gives most of the colour reactions characteristic of ordinary coprosterol. The third product termed y-cholesterol C,7H,,0? is sparingly soluble in ethyl alcohol and crystallises in glistening rhombic plates m. p.. 135-137'. Some specimens were dextro- rotatory others inactive. It yields an acetate m. p. 100-102° but does not form an additive compound with bromine. The best yields of y-cholesterol are obtained when the reduction is carried out at 110-1 15'. Higher temperatures favour the formation of I-coprosterol. J. J. S. Phytosterol from Rape Seed Oil. ADOLF WINDAUS and A. WELSCH (Ber. 1909 42 612-616. Cornpare Windaus and Hautb Abstr. 1907 i 129 92l).-The phytosterol from rape seed oil likeORGANIC CHEMISTRY.229 phytosterols from other sources is a mixture of a stigmasterol and a sitosterol which may be separated by the action of bromine on the mixture of acetyl derivatives. The stigmasterol yields a compound C30H4802Br4 analogous to stigmasteryl acetate tetrabromide. This is termed hassicasteryz acetate tetrabromide and crystallises from a mixture of chloroform and alcohol in well-developed rhombic plates which decompose a t 209'. Brassicmsteryl acetate C30H4s02? obtained by the action of zinc dust and acetic acid on the tetrabromide crystallises from alcohol in thin six-sided plates m. p. 157-158O. When hydrolysed with alcoholic potash it yields brassicasterol C,,H,,O,H,O which also crystallises from alcohol in six-sided plates m. p. 148'. It loses the water of hydration a t loo' and has .[u] -64'25' in chloroform and -63'31' in ether; the propionate C,,H,,O has m.p. 132' and yields a tetrabromide which decomposes at 206'. The b w t a crystallises from alcohol in long glistening needles m. p. 167'. Tho sitosterol can be obtained from the mother liquors of the stigmasterol tetrabromide in the form of its dibromide. The sitosterol has m. p. 142' and [u]g - 34'20' in ether. The acetate has m. p. 134' ; propionate 116'; cinnamate 151° and benzoate 143'. J. J. S. Preparation of Crystalline Salte of o-Dihydroxyphenyl- ethanolmethylamine. FARBWERKE VORM. MEISTEB LUCIUS dt BBUNINGI (D.R.-P. 202169. Compare Abstr. 1908 i 418).- 0- Rihydroxyphn ylethanolmeth y Zamine hydrochloride colourless crystals m. p. 157' was prepared by adding alcoholic hydrochloric acid to synthetically prepared o-dihydroxyphenylethanolmethylamine moistened with absolute alcohol. Q.T. M. Crystallography of 2-MethglcycZohexyl Benzoate. MISS E. D. REVUTZKY (Zeitsch. Kryst. Mi.n. 1909 46 218; from Bull. Xoc. Nut. Moscou 1906 Nos. 1 and 2 139-141).-The crystals are rhombic [U b c = 0.9460. 1 0.781 11. Preparation of Acyl Derivatives of the Esters of the Arninohydroxy-acids. LES ~TABLISSEMENTS POULENC FRPEES (D.E.-P. 202167. Compare Abstr. 1908 i 937).-The acylation of the alkyl esters of the aminohydroxy-acids must be effected in the absence of strong alkalis in order to avoid hydrolysis of the ester group. NMe,*CH,*CMe(OBz)*C02Et was obtained in the form of its hydyochZoride,'needles m. p. 137O by mixing cold benzene solutions of benzoyl chloride and ethyl dimethyl- aminohydroxyisobutyrate; the base is a syrup b.p. 210'/42 mm. The methyl and arnyl esters are prepared similarly; their hydrochlorides melt at 149-150' and 134' respectively ; the corresponding bases boil a t 220'/75 mm. and 213'/27 mm. The patent contains descriptions of six other similar esters. G. T. M. JULIUS VON BFLAUN (Bcr. 1909 42 839-846).-The opening of the piperidine L. J. S. Et h y Z /3-dimeth y Zarnino-a-benzo yloxyiso but yrate Synthesis of Inactive Lysine from Piperidine. VOL. XCVL i. r230 ABSTRACTS OF CHEMICAL PAPERS. ring by means of phosphorus chloride has been made use of for the synthesis of cadaverine pimelic acid and e-leucine (Abstr. 1904 i 918 970 1019; 1907 i 524). Amongst the products of this reaction are two namely ephenoxghexonitrile C,H,O*[C E€,],*CN and benzoyl-c-leucinenitrile COPh*NH-[CH,l,.CN which contain the skeleton of lysin.The corresponding phenoxyhexoic acid forms a compound C,H,Br*O*[CH,];CHBr*C02H m. p. 105" in which the a-bromine atom can be replaced by NH bat the elimination of the brominated phenyl group by bromine could not be carried out. On the other hand e-benzoylaminohexoic acid can be brominated in the a-position the bromine replaced by NH and the benzoyl group eliminated giving inactive lysine. eBenxoyZamhohexoic acid COPh*NH*[CH,lj*CO,H is obtained on hydrolysing the nitrile with potassium hydroxide under special precautions in long colourless needles m. p. 79'. It decomposes when distilled even in a vacuum forming benzoic acid and the elactam NH*[CH,I5*CO.When brominated in presence of phosphorus a con- siderable excess of bromine is required. Apparently the imide bromide complex C,H5*CBr:NX is formed at the same time as the a-carbon is brominated but the complex is destroyed on adding water. a- Bromo-r-be~naoy Za~~nohexoic acid COPh =NH [ CH,] 4* CHBr CO,H forms a mass of colourless needles m. p. 166'. It reacts with aqueous ammonia at O' forming a-ccmino-c-benxoylccminoh~ic acid m. p. 268O when heated quickly m. p. 263' when slowly heated. The monobenzoyllysine described by Fischer and Weigert (Bey. 1902 35 3772) was probably mainly the a-benzoyl compound NH,* [ CH,],*CH( NH* COPh)*CO,H. Inactive lysine obtained by heating benzoyllysine with excess of hydrochloric acid for several hours under pressure at 1 15O is in all respects identical with the product obtained by Fischer and Weigert I I (ZOC.cit.). Characteristic is the hydantoin compound COPh*NHfCH,]4*CH<NH. CO-NPh b0 . By the action of phenylcarbimide on c-benzoyllysine the hydantoic acid COPh*NH*[CH,],*CH(NH*CO*NHPh)*CO,H is first formed as a grey mass This is warmed with concentrated hydrochloric acid and converted into the hydantoin crystallising in matted needles m. p. 156O. E. F. A. Preparation of o-Nitrobenzonitrile and o-Nitrobenzamide. KALLE & Co. (D.R.-P. 204477).-When o-nitrobenzaldoxime is warmed with dilute aqueous sodium carbonate for nine hours it yields o-nitrobenzamide together with a small amount of o-nitro- benzoic acid. When heated with a weak solution of potassium cyanide for nine hours this oxime furnishes o-nitrobenzonitrile with small.quantities of o-nitrobenzamide and o-nitrobenzoic acid. G. T. M. Preparation of 2-Nitro-4-aminobenzoic Acid. FARBWEREE YORM. MEISTER LUCIUS & BR~~NING (D.R.-P. 204884).-2-Nitro-4-cc~~~o-ORGANIC CHEMISTRY. 231 bsnxoic acid yellowish-brown crystals m. p. 234-2350 has now been obtained by reducing 2 4-dinitrobenzoic acid with sodium sulphide at 90° in the absence of alkalis. Oxidation Products of 6-Nitro-1 3-dirnethylbenzene-4~d- phonic Acid. WILLIAM J. EARSLAKE and P. A. BOND (J A m . Chsm. ~ o c . 1909,31,405-410).-Potassium 6-nitro-1 3-xylene-4-sulphonab has been prepared by a modification of Claus and Schmidt's method (Abstr. 1886 708). When this salt is oxidised with cold alkaline solution of potassium permanganate the following three products are obtained.The corresponding barium barium hydvogen and silver salts are described. By the action of phosphorus pentachloride on the potassium salt a mixture of two chlorides is obtained which melt at 133" and 93'; i t is probable that the compound of higher m. p. is the symmetrical chloride N02*C6H2Me<~~2~l whilst the other is the unsymmetrical chloride N02*C,H,Me<~~~>0. The potassium hyckogen and d v e r salts are also described. The acid crystallises in prismatic plates. The chloride m. p. 90" (corr.) when treated with concentrated ammonia yields a compound m. p. 274O which is probably the diamide. G. T. M. (1) Potassium 4-nitro-2-suZpho-6-tolwte.(2) Potassium 6-nitro-4-suJpho-3-toluate. (3) Potaaaiurn dihydrogen 6-nitro-4-szc2phoisophthcczaccte N02-C,H,(C0,H),-S0,K 2H,O. The acid chloride is obtained in two forms one m. p. 147O crystal- lising in needles and the other an oily liquid; when treated with ammonia the former gives a compound m. p. 277O and the latter a compound crystallising in coarse needles. Methyl Salicylate. 11. Solubility in Water at 30'. HARRY D. GIBBS (PhiZ+pine J. Xci. 1908 A 3 357-359. Compare Abstr. 1908 ii 906).-The solubilities ofpethyl salicylate a t 30' in water and N/10 sulphuric acid are shown to be 0.014 and 0.077 gram in 100 grams of solvent respectively. Slight improvements are described in the colorimetric method for determining methyl salicylate (loc. cit.). P. H. Preparation of o-Alkylthiolbenzoic Acids and their Alkyl Esters.FAIZBWERKE VORM. MEISTER LUCIUS & BR~JNING (D.R.-P. 203882).-MethyZ o-mthylthiolbenxoic acid SMe*C,H,*CO,Me colour- less needles m. p. 66-67O obtained by adding methyl sulphate to thiosalicylic acid dissolved in aqueous sodium hydroxide is hydroly sed into o-methylthiolbenxoic acid m. p. 168-170° this acid being also produced from thiosalicylic acid and sodium methyl sulphate in aqueous sodium hydroxide. Ethyl o-ethylthwlbenxoate SEt-C',H,*CO,Et crystals m. p. 27-28' b. p. 152-153O/lO mm. is obtained by treating sodium thiosalicylate with ethyl sulphate; the use of sodium ethyl sulphate in this reaction leads to o-ethylthiolbenxoic acid yellow crystals m. p. 134-1 359 E. G. GI. T. M. r 2232 ABSTRACTS OF CHEMICAL PAPERS.Preparation of Alkylthiosalicylic [o-Alkylthiolbenzoic] Acids. FARBWERKE V O ~ M . MEISTER LUCIUS & BRUNING (D.R.-P. 203388).- The o-alkylthiolbenzoic acids can be produc'ed in one operation from the o-aminobenzoic acids by diazotising the latter neutralising the diazo-solution and then treating with sodium sulphide and sodium methyl sulphate gradually heating to 60' or 70". o-Methylthiol- benzoic and ethylthiolbenzoic acids m. p. 168-169' and 134-135' respectively were obtained in this way. G . T. M. Ethyl a-Dinitrophenylacetoacetate and Related Compounds. I. WALTHER BORSCHE (Ber. 1909 42 601-612. Compare Heckmann Abstr. 1884 178).-A 75% yield of ethyl a-2 4-dinitro- phenylacetoacetate can be obtained by heating an ethereal solution of chloro-(or bromo-)2 4-dinitrobenzene with a suspension of ethyl sodio-acetoacetate in ether for one hour on the water-bath.The corresponding methyl ester C,H,( NO,) *CH Ac*CO,Me cr y stallises from methyl alcohol in compact yellow needles m. p. 114" and is not so readily soluble as the ethyl ester. The ester forms a stable sodium derivative when it,s ethereal solution is treated with sodium or sodium ethoxide but it has not been found possible to replace the sodium by alkyl groups. a-Alkylated acetoacetic esters do not condense with chloro-2 4-dinitrobenzene. Dry ammonia reacts with an ethereal solution of the ester yielding acetamide and ethyl 2 4-dinitrophenylacetate. Phenylhydrazine reacts in a similar manner yielding ethyl 2 4-dinitrophenylacetate and 8-acetylphenylhydrazine ; with a hot ethereal or alcoholic solution of aniline 2 4-dinitrophenyZacetan~lide C6H3(N0,);CH;CO*NHPh m.p. 181° is formed. Benzoyl chloride reacts with the sodium derivative of the dinitro- ester yielding the 0-benxoyl derivative C,H,(NO,),*C( CO,Et):CMe-O* COPh which crystallises from boiling alcohol in rhombic yellow plates m. p. 142-143'. When hydrolysed it yields benzoic acid and dinitro- phenylacetone. It has not been found possible to transform this 0-benzoyl into an isomeric C-benzoyl derivative. 2 4-Binitrophenylucetone C,K,(NO2),*CH,*CO*CH3 is readily obtained by hydrolysing the original ester with concentrated sulphuric acid and crystallises from dilute alcohol in brilliant pale yellow needles m. p. 75". The ketone dissolves in dilute alkali hydroxides yielding blood-red solutions from which the ketone cannot be recovered.It does not react with aniline even in the presence of formic acid and with an alcoholic solution of p-nitrosodimethyl- aniline in the presence of sodium hydrogen carbonate yields a small amount of a dark green crystalline compound probably the p-dimethyl- aminoanil of 2 4-dinitrobenzaldehyde (Abstr. 1902 i 682). C,H,( N02)?*CH,*CMe N,HPh crystallises from hot alcohol in orange-red needles m. p. 124-125O. The ketone reacts with benzoyl chloride in the presence of pyridine yielding a-2 4-dinitrophenyl-Aa-propene-,8-ol benzoate C,H,(NO,),*CH CMe*O*COPh 2 4-Dinitrophn ylacetonephen ylh ydrcmone,ORGANIC CHEMISTRY. 233 which crystallises from dilute alcohol in pale yellow needles m.p. 9 09 An alcoholic solution of the ketone reacts with a solution oft diaxobenzene chloride and sodium acetate yielding the a-phnyl- h ydrctxone of a-2 4-dinitrophen yl- a p-propundione C6H3( NO,),. CAc N,HPh which crystallises from a mixture of alcohol and ethyl acetate in brilliant orange-red needles m. p. 201-202' (decomp.). With phenylhy drazone it yields the bisphenylhydrazone C2,Hl8O,N6 in the form of glistening black needles which decompose at 206'. Sodium hydroxide produces a black coloration with an alcoholic solution of the monohydrazone but this gradually changes to a pale red colour and the addition of water precipitates a compozlnd C,,H,,O,N which crystallises from a mixture of chloroform and alcohol in pale green glistening prisms m.p. 183-184'. This compound is probably 6-nitro-3-acetyl-l-phenylisoirtdaxole No2*C,H3<gh>N (compare Meyer Abstr. 1889 516). Ethyl a- 2 4-dinitrophen y l benxo y lace t ate c6 H ,(NO,),*CH( CO,Et)*COPh is obtained by the action of an alcoholic solution of bromo-2 4-dinitro- benzene (1 mol.) on ethyl sodiobenzoylacetate (2 mols.). It forms a yellow oil and when hydrolysed with concentrated sulphuric acid yields o-2 4-dinitrophenylacetophenone C6H3(N02),*CH,*COPh which crystallises from a mixture of chloroform and alcohol in slender colourless needles m. p. 136-137'. The ketone reacts with stannous chloride solution yielding 6-amino-2-phenylindoZe NH C,H3<:E>CP h m. p. 240". The base readily turns dark-coloured on exposure to the air ; the hydrochloride forms colourless plates which turn green on exposure to the air.J. J. S. Action of Free Hydroxylamine on Lactones. LUIGI FRANCESCONI and GUIDO CUSMANG (Gaxxetta 1909 30 i lS9-202).- Whilst santonin reacts with 3 mols. of hydroxylamine one of which unites with the lactone group desmotroposantonin which contains the same lactone grouping but no ethylenic linkings is not attacked by hydroxylamine (compare Abstr. 1908 j 272). Phthalide is indifferent towards hydroxylamine whilst cournarin which contains a double link- ing in the P-position with respect to the carbonyl takes up 2 mols. oft the base. Although Tiemann found (Abstr. 1886 880) that coumarin did not react with hydroxdamine the combination readily takes place if a methyl-alcoholic solution of the free base is used and the reacting substances are allowed to remain together for six days.The product is a mixture of dihydroxykuminohydrocoumarin C,H,,O,N white crystals m. p. 130-1 31' and arninohydrocournaric [aminomeldotic] acid C,H,,O,N m. p. 208'. Low temperature and high concentration favour the formation of the former compound which at higher tempera- tures reacts with more hydroxylamine nitrogen being eliminated C,H,,O,N + NH,OH = CgH,,03N + N + 2H,O. The reaction with coumarin has been studied in detail.234 ABSTRACTS OF CHEMICAL PAPERS. Dihyhoxylaminohydrocoumarin dissolves slowly inwater t o a neutral solution reduces Fehling’s solution and gives an intense reddish-violet coloration with ferric chloride. It probably contains the lmtone ring.*,I O-- $!(OH)*NH*OH. It is CH(NH*OHkCH and has the constitution C,H4< readily hydrolysed by dilute acids. Acetone flormHwith it a condensa- tion product CI2Hl3O3 crystallising from alcohol in transparent rectangular tablets. This product does not reduce Fehling’s solution until after hydrolysis. On attempting to methylate with methyl sulphate the alkali causes the removal of hydroxylamine from the carbonyl group and methyl- hgdr oxy Zamino?~ydrocoumurin 0H.B Me is obtained in large clear prisms m. p. 167-168O. The methyl derivative does not reduce Fehling’s solution or give a coloration with ferric chloride. dminohydrocoumaric acid probably has the constitution c6H4<EH.CJ32*(!J. OH ; H,N- b it does not reduce Fehling’s solution. Preparation of Substituted o-Carboxyphenylthioglycollic Acids.FARBWERKE VORM. MEISTER LUCIUS & BRUNINQ (D.R.-P. 202243).-The homologues of anthranilic acid when diazotised and treated successively with a C02H /\S.CH,*CO,H metallic sulphide and sodium chloroacetate are converted into the corresponding o-carboxyphenyl- thioglycollic acids in one operation. 6-Carbox~-3-methylphenylthiolcccetic ucid (annexed formula) is thus produced from homoanthranilic acid. Exception to the General Method for Preparation of Aldehydes by means of Glycidic Acids. RENB POINTET (Compt. rend. 1909 148 417-41 9).-The following substituted glycidic acids prepared by condensing ethyl cbloroacetate with ketones of Lhe type R*CO*R do not lose carbon dioxide when heated and are therefore not available for the preparation of the corresponding aldehydes of the type CHRR’*CHO by Darzen’s method (Abstr.1905 i 117). C. H. D. 0 0% G. T. M. . _ CPh CH*CO,H ’ Diphnylglycidic acid O< I m. p. 146O. The ethyl ester Phenyl-p-tolylgl~cid~c ucid O<?Ph’C6H4Me m. p. 134’. The ethyl has m. p. 47’ and b. p. 202-204O/12 mm. CH* CO,R ester has b. p. 225O/’1S mm. 1 FPh*C6H4’0Me m. p. 110”. The O<CH*CO,H P~enyl-p-anisylglycidic acid Y ethyl ester has b. p. 240°/20 mm.ORUANIC CHEMISTRY. 235 When heated this acid loses carbon manoxide and forms pbnyEp an&yhcet& acid OMe*C,H,*CHPh*CO,H m. p. looo. w. 0. w. Attempts to Synthesise Chromenol and ita Derivatives. S. CZAPLICEI STANISLAUS VON KOSTANECEI and VICTOR LAMPE (Bey. 1909 42 827-838).-Since the direct addition of hydrogen cyanide to salicylaldehyde methyl ether does not give satisfactory results to prepare o-hydroxyphenylacetic acid the sodium hydrogen sulphite compound of the aldehyde is converted into o-methoxymandelonitrile OMe*C,H,*CH(OH)*CN and this is heated with eight times its weight of hydrogen iodide.If a smaller proportion is taken o-methoxy- phenylacetic acid m. p. 1 2 4 O described by Pschorr (Abstr. 1900 i 232) is obtained. The hydroxyphenylacetic acid so obtained formR colourlese glistening prisms m. p. 1 4 7 O ; the lactone isocoumaranone has m. p. 28.5O. It reacts with ethylbromoscetic acid in preaence of sodium forming ethyl 2-phenyyleneacetic-glycoZZate CO,H*CH,* C6H,*O-CE3[,*C0,Et which was converted directly into o-phenyleneacetic-glycollic acid by heating with alcoholic potassium hydroxide. This forms colourless needles m.p. 158-159O and shows no coloration with ferric chloride ; the diethy2 ester separates in colourless needles m. p. 48-49'. p- and m-Hydroxypheny Iacetic acids may be prepared in a similar manner but the yield is much less satisfactory. p-Methoxymandelonitrile m. p. 63' (Tiemann and Kohler Abstr. 1882,57) is obtained by the action of potassium cyanide on the sodium hydrogen sulphite compound of anisaldehyde and is converted into p-hydroxyphenylacetic acid when boiled with hgdriodic acid. m- Hethnxymandelonitrile is obtained as a yellow oil from m-methoxy- benzaldehyde in a similar manner and is converted by hydrogen iodide into m-hydroxyphenylacetic acid m. p. 129O (Salkowski Abstr. 1884 1 176).The lactone of o-hydroxyphenylacetic acid and ethyl a-bromophenyl- acetate interact in presence of sodium in alcoholic solution forming the ethyl ester of o-phenyleneacetic-mandelic acid CO,H* CH2*C6H,*OoCHPh C02H. The mid is obtained as a thick oil which crystallises in short wide needles m. p. 178'. The disthyl ester forms short wide needles m. p. 61'. 2-Methoxystilbene-a-carboxyEic acid OMegC6H4*C(CO,H):CHPh is obtained in colourless short needles m. p. 145-146O. It is reduced by sodium amalgam to 2-methoxydibenzyl-a-carboxylic acid OMe* C,H,* CH( CO,H)*CH,Ph which separates in thick prisms united in masses m. p. 93-94O. When heated with hydriodic acid benzyylisocoumaranm is obtained as an oil which crystallises "from alcohol in colourless plates m.p. 61O. This lactone is converted into 2-hyd~oxydibenzyZ-a- carboxylic acid when Iheated with alcoholic potassium hydroxide but this passes back into the lactone when recrystallised from water.236 ABSTRACTS OF CEEEMICAL PAPERS. 2 3' 4'-TTimethoxystiIbene-a-carboxylic acid prepared by the inter- action of veratraldehyde on 2-methoxyphenylacetic acid crystallises in colourless needles m. p. 185-186'. 2 3' 4'-17rimethoxydibenxyl- a-curboxglic acid forms granular crystals m. p. 125-126'. 2-~y~roxystilbene-a-carboxylic mid prepared by the interaction of o-hydroxyphenylacetic acid arid benzaldehyde crystallises in long colourless plates m. p. 155'. ~~nzylideneisocoumaranone formed at the same time as the above separates in yellow prisms or concentrically-grouped needles.The crystals are coloured orange by concentrated sulphuric acid. Benzylideneisocoumaranone is the chromogen of a new class of dyes which contain the same complex chromophore (CO*C:C) as the o*y:CH- and are therefore termed isooxindogenides. oxindogenides <- The three isomeric methoxy-2-hydroxysti1bene-a-carboxylic acids have been prepared in a similar manner. They all yield sodium salts sparingly soluble in cold sodium hydroxide and are converted into the corresponding lactones when melted. The 2'-methoxy-compound crystallises in needles from benzene or plates from dilute alcohol m. p. 152' ; the 3'-methoxy-derivative forms thick crystals m. p. 148' ; the .l'-methoxy-acid yields broad needles m. p 140'. 2'-ddethox~benz~Z~en~~socoumccrcclzon~ forms broad prismatic yellow needles m.p. 126-127' ; the 3'-isomeride forms yellow prisms m. p. 118-119'; the 4'4actone separates in yellow needles m. p. 132'. co 3' 4'- DimethoxybenzyZideneisocoumarons ,& forms orange-yellow prismatic needles m. p. 99-1 00'. hydrolysis of the above lactone crystallises in needles m. p. 187'. 2-Hydroxy-3' 4'-dimethoxyatiZbene-a-carboxylic &d prepared by a- Curboxy-2 -atilbenyloxyacetic acid CO,H* CH,.O*C,H,*C( C0,H) CHPh formed by the interaction of hydroxystilbenecarboxylic acid and ethyl bromoacetate crystallism in plates m. p. 204-205'. a-Carboxy-2- diber~xyloxymetic acid C0,H*CH2*O*C6H;CH( CO,H)* CH,Ph separates in rosettes of colourless needles m. p. 165'. It 1s obtained either by reduction of the foregoing compound or by the interaction of ethyl- bromoacetate or 2 -hydroxydi benzyl-a-carboxylic acid.E. F. A. Condensation of Mesoxalic Esters with Aromatic Eydro- carbons. ALFRED GUYOT and G. ESTEVA (Compt. Tend. 1909 148 564-566. Compare this vol. i 158).-When a mesoxalic ester is treated with an aromatic hydrocarbon in presence of concentrated sulphuric acid condensation occurs with formation of a substituted tartronic ester of the type OH*CPh(CO,R),. A portion of this ester undergoes condensation with a second molecule of the hydrocarbon,ORGANIC CHEMISTRY. 237 giving a substituted malonic ester of the type CPb,(CO,R),. The two esters are separated by distillation in a vacuum. The following compounds have been prepared in this way Methyl phenyltartronate OH-CPh(C0,Me)2 silky needles m.p. 67" b. p. 165'/11 mm. The ethyl ester occurs as a crystalline mass m. p. 2 8 O b. p. 1 70°/10 mm. C6H,Me*C(OH)( C0,Me)2 m. p. 72' b. p. 175'/11 mm. The ethyl ester forms prisms m. p. 41" b. p. 1 80°/9 ' mm. Methyl ditolylmalonate C(CGH,Me),(C02Me) needles m. p. 126.5". Methyl o-xylyltartronate C,€3,Me,*O(OH)(C02Me)2 needles m. p. 94*6' b. p. 18S0/11 mm. The ethyl ester forms a crystalline mass m. p. 35' b. p. 193'/13 mm. m. p. 135'. Ethyl phenyl- tolylmalonate C,H,Me*CPh(CO,Et) has m. p. 55.5'. These compounds are also obtained when ethyl oximinomalonate is substituted for ethyl mesoxalate in the above preparation ; the yields Compounds from Lichens. XVII. Substances Present in Lobulated,Lichens (Peltigeracem). WILHELM ZOPF (AnnuZen 1909 364 273-313.Compare Abstr. 1907 i 218).-Twelve members of the family Peltigera have been investigated and a hitherto unknown derivative of orcinol named peltigerin has been isolated to the extent of 2 to 3% from eight of them namely P. aphthosa P. malucea P . horizontalis P. venosa P. polydact yla P. scabrosa P. propagulgera and P. lepidophora. Peltigerin is not present in P. prcetextata P. canina P. rufescens P . spuria Nephroma arcticum N. antarcticum N. resupinaturn N. lavigatum N. parile Solorina crocm or 8. saccata. Peltigerin C,,H200 or c,6H,6oG crystallises from acetone or ether in thin colourless leaflets with a silvery lustre and from glacial acetic acid in long slender curved needles; it sinters at about 160' and changes into a turbid liquid at 170-180' which becomes trans- parent at about 220'.When peltigerin is heated carefully it yields a sublimate consisting of peltiyeric acid C,,H 204 and peltigronic d. The former acid crystallisea in large compact plates and prisms m. p. about 127O; it is coloured red by calcium hypochlorite and gives a violet coloration with ferric chloride. Peltigronic acid crystallises in rosettes of long needles m. p. 144-145O (decomp.). Zeorin has been detected in P. malacea P . horizontalis P. propa- gulifera N. arcticum N. antarcticurn N. lcevigatum and N. parile. It is not present in the other representatives of these genera which have been investigated. d-Usnic acid was isolated from Nephroma arcticum and N. antarcticum. Mannitol has hitherto been obtained from only two lichens; it has now been separated from 2'.malacea P. horizontalis P. aphthosa P. polydactyla P. cunina 2. rufescens P . spuria P. prcetextata Methyl p-tolyltartronate The ethyl ester forms prisms m. p. 93.5O. Methyl dixylylmalonate The ethyl ester forms prisms m. p. 67'. C(C6H3Me2)2(C02Me)29 * however are poor. w. 0. w.238 ABSTRACTS OF CHEMICAL PAPERS. Nsphroma resupinaturn N. kavigatum N. parile Solorina crocea and 8. seccata. A c S q namely one from each have been isolated from P. smbo8a P. polydnctyla P . venosa P. horizontalis and Xolorina saccata; they become red when treated with calcium hypochlorite but have not been investigated further owing to the small quantities obtained. Peltigera malacea contains an acid which crystallises in small white needles m. p. 220".P. aphthosa contains two acids both of which are turned red by calcium hypochlorite ; one crystallises in slender needles softens at 120° m. p. 125-130'; the other crystallises in small aggregates of slender needles sinters at 200° m. p. about 220'. In addition to soloric acid (compare Zopf Abstr. 1895 i 297) Solorina crocea contains an acidic substance which it is proposed to designate solorinin ; it crystallises in small thin colourless leaflets begins to decompose a t about 170" and forms a reddish-brown liquid at 230O. Peltigera canina contains a neutral substance caminin crystallising in colouriess rhombic plates. Two indifferent substances have been isolated from P. polydactyla namely polydactylin crystallising in silky white needles m. p. about 1 78-180° and peltidactylin which crystallises in glistening colour- less rectangular plates m.p. about 237-240O. Nephrin was detected in Nephroma arcticum and N . lcevigaturn but not in N. resupinaturn or N. antarcticum (compare Hesse Abstr. 1898 i 679). W. H. G. The Oxidation of Organic Compounds by means of the Cornpounds of Nitric Acid with Aldehydes or Ketones. ALEXIS A. SHUKOFF (D.R.-P. 206695).-The aldehydes and ketones readily form nitrates when added t o concentrated nitric acid the pro- duct usually crystallising out. Benzaldehyde nitrate m. p. - lo is obtained by adding the aldehyde to fuming nitric acid and cooling to - 10". Camphor nitrate m. p. 180" produced by adding 152 parts of camphor t o 70 parts of fuming nitric acid separates on cooling with ice. These substances are convenient oxidising agents for organic compounds which may be dissolved in these very fusible nitrates and left to oxidise at the ordinary temperature.Antbracene dissolves in benzaldehyde nitrate on gently warming and anthraquinone separates forthwith. Borneo1 and ieoborneol are similarly oxidised to camphor. Q. T. M. Condensation of Aminohydroxy-acids with Aromatic Alde- hydes. ERNESTO PUXEDDU (G'axxetta 1909 39 i 121-131. Com- pare Abstr. 1908 i 286).-In continuation of former work on the influence of substituents on the condensation of aminohydroxy-acids with aldehydes it has been found that 0- and p-nitrobenzaldehyde readily condense with 5-amino-0- or -m-cresotic acid. Unlike salicyl- aldehyde p-hydroxybenzaldehyde does not condense with either acid.Anisaldehyde ptolualdehyde and catechualdehyde are also without action whilst vanillaldehyde condenses with 5-amino-o-cresotic acid,ORGANIC CHEMISTRY. 239 although slowly but not with its meta-isomeride. In the latter we the methyl group is in the ortho-position relatively to the nitrogen atom. The products are coloured crystalline substances insoluble in water and in most organic solvents except alcohol and acetic acid. They are acid in character. The compound from 5-amino-m-cresotic acid and p-nitrobenzaldehyde forms a hydrochloride m. p 96'. Their constitution is under investigation. 0. H. D. Constituents of Ethereal Oils Further Decomposition of Eksantalal ; Enolisation of Aldehyde8 by Conversion into the Corresponding Unsaturated Esters ; enol-Phenylmet- aldehyde-monoacetate.FRIEDRICH W. SEMMLEB (Ber. 1909 42 584-591).-In the work on essential oils it haR been frequently noticed that although secondary alcohols give good yields of ketones when oxidised with an acetic acid solution of chromic anhydride only poor yields of aldehydes can be obtained from primary alcohols under similar conditions appreciable amounts of less volatile products being formed a t the same time. This is now shown to be due to the enolising action of the acetic acid and the formation of an acetate of the unsaturated alcohol. These acetates are termed monoacetates in order to distinguish between them and the diacyl derivatives to which aldehydes give rise; the prefix enol is also used in order to indicate that they are derived from the enolic form of the aldehyde R*CH,*CH:O -+ R*CH:CH*OH -+ R*CH:CH*OAc.It is only aldehydes which contain hydrogen attached to the a-carbon atom which can react in this manner. enol-PhenyZacetal~e~~de monoacetate (plienylvinyl ace fate) CHPh:CH*c)Ac is readily formed when the aldehyde is boiled For an hour with twice its weight of acetic anhydride; it has b. p. 119-121°/10 mm. D20 1.065 nD 2.5483. When reduced it yields phenylethyl alcohol and ethyl alcohol and when oxidised with ozone the products are benzaldehyde and benzoic acid. Hydrolysis with dilute mineral acids at 100-1 loo yields phenylacetaldehyde and acetic acid. Phenylacet- aldehyde has b. p. 85-86O/10 mm. D20 1.0252 and 12 1.53191. Heptrtldehyde citral citronella] and various other aldehydes react in a similar manner.The formation of these esters of the enolised aldehydes affords the basis of a simple method by means of which the aldehyde group CHO can be removed and an aldehyde or ketone containing one less carbon atom obtained. The readiness with which aldehydes form acetates must be borne in mind when estimating the amount of alcohol present in an essential oil. Tricyclic enol-eksantalal mmoucetate CioH,, CH*OAc has b. p. 132-135O/lO mm. D20 1.023 and n 1.4881 and is laevorotatory. It is usually accompanied by a small amount of a diucetate C,,H,,O which has a higher b. p. When reduced the monoacetate yields eksantalol C11H180 and when oxidised with ozone in benzene solution yields tricyclic nor- eksccntulm CloH140 which has b. p. 101-102°/10 mm.D20 0.988,240 ABSTRACTS OF CHEMICAL PAPERS. and n 1.485. It yields a semicarbazone C,,,H,,:N*NH*CO=NH m. p. 2 1 6 O and an oxime C,OH,,:N*OH b. p. 142-144O/10 mm The behaviour of eksantalnl indicates that it contains a hydrogen atom attached to the carbon atom which is in the a-position with respect to the aldehyde group. Constitution of Dichloropiperonal. GEORGE BARGER (Ber. 1909 42 763-765. Compare Trans. 1908 93 563 735).-Polemical. A reply to Pauly (this vol. i 165). Preparation of 5-Alkyloxy-2-acetylphenyl Mercaptan. FARBWERKE VORM. METSTER LUCIUS & BR~NING (D.R.-P. 202632).- When treated with acetyl chloride in the presence of aluminium chloride the 3-alkyloxyphenyl mercaptans give rise to diacetyl derivatives (I) from which the alkyloxyacetylphenyl mercaptans (11) are produced by warming with dilute mineral acid COCH COCH /\S*CO*CH I -+ n - S H v 0- Alk (1.1 (II.) 5-Methoxy-2-acetyZphenyZ mercaptun colourless plates m.p. 94-96' and 5-ethoxy-2-acetylphenyZ msrcaptan colourless crystals m. p. 68O which are thus produced yield sulphur colouring matters on oxidation. G. T. M. J. J. S . W. R. I I \/ O-Alk Organic Syntheses by means of Sunlight. EMMANUEL PAT ERN^ (Atti R. Accad. Zincei 1909 [v] 18 i 104-105*).-A solution of benzophenone in amylene exposed to sunlight deposits in a few days large crystals of a compound m. p. logo which may be converted into a hydrocarbon containing 18 atoms of carbon ; it therefore probably has the amylene chain attached to the carbonyl carbon the oxygen forming a bridge.Oxidation regenerates benzophenone. Aceto- phenone and amylene yield a liquid compound? boiling at 235-237'. The compound from benzaldehyde and amylene boils a t 239-23 lo. Octane and decane react with benzophenone in sunlight being partly converted into benzopinacone and unsaturated hydrocarbons the latter then reacting with benzophenone to form compounds analogous to that from amylene. Some of these compounds are found by analysis and cryoscopic measurements to be formed from 1 mol. of benzophenone and 1 mol. of unsaturated hydrocarbon but their properties are similar to those of the resins which may also have a simple constitution. Benzene does not react with benzophenone whilst its homologues undergo complex reactions. With ethylbenzene the principal product is a crystalline compound m.p. 88-89O which has the properties of a tertiary alcohol and yields a hydrocurbom m. p. 124-126' and a resin. Certain alcohols ethers and esters react in similar manner to the hydrocarbons. C. H. D. * and Gazxetta 1909 31 i 237-250.ORGANIC CHEMISTRY. 241 Crystallography of Nitrodesmotroposantonin and P-Naph- thy1 Propyl Ketone. ABISTIDE ROSATI (Atti R. Accad. Lincei 1909 [v] 18 i 129-1 32).-Nitrodesmotroposantonin (Bargellini and Daconto Abstr. 1908 i 819) forms rhombic crystals a b c = 0.4133 1 2.2646. It is dextrorotatory in solution. P-Naphthyl propyl ketone forms triclinic crystals sometimes several centimetres in length a b c = 0,6774 1 0.6029 a = 94'31' p = 140'35' y = 90'27'. 9-Formylfluorene. I. WILEELM WISLICENUS and NABTIN WALDMULLER (Bey. 1909 42 785-789.Compare Wislicenus and Densch Abstr. 1902 i 29 1).-9-Formylfluorene obtained by the condensation of fluorene and ethyl formate using dry potassium ethoxide as the condensing agent exists in two tautomeric forms. a-FormyZfluorene ~6H4>C:CH*OH is a yellow viscid oil b. p. 196-197'/14 mm. 193-193.5'/12 mm. which slowly changes into a solid transparent yellow resinous mass. Mo1.-wt. determinations of the latter substance show that it is himolecular formylfluorene (C14HloO)2 ; it yields the unimolecular variety when distilled under reduced pressure. a-Formylfluorene when treated with phenyl- carbimide yields the additive product C,,K,:CH* O*CO*NHPh which crystallises in colourless needles m. p. 145-146O ; the benzoate C,,H,:CH*OBz forms small slender colourless needles m.p. 158-159' ; the acetate Cl,H8:CH-OAc crystallises in small colourless plates m. p. 132-134'. P-RormylJEuorene yeH4>CH*CH0 obtained by treating a solution of the a-modification in aqueous alkali with dilute sulphuric acid crystallises in colourless glistening leaflets ; it turns yellow and sinters at 70° and is completely converted into the a-form at about 90'. The phenyylhgdraxor C2,H1,N2 crystallises in almost colourless leaflets m. p. 1 2 6 4 2 7 ' ; the anilino-derivative C2,H1,N forms small glistening yellow needles m. p. 155'. THEODOR ZINCKE and F. SCHWABE (Ber. 1909 42 797-802).-The statement of Meyer and Desamari (Abstr. 1908 i 658) that tribromoresoquinone is a tribromo-m-benzoquinone is refuted ; it is either a derivative of p-dibenzoquinone or o-dibenzo- quinone although the latter is very improbable.This statement is supported by (1) mo1.-wt. determinations ; (2) reduction of the substance to tetrabromodiresorcinol ; (3) conversion of the reduction product by bromine and water at the ordinary temperature into tribromoresoquinone and by chlorine under similar conditions into a chlorodibromoresoquinone. Dichlorotribromoresorcinol when heated loses bromine and passes into dichlorobromoresoquinone (compare Benedikt Abstr. 1879 O/-\=/-\O O/-\Br 55,464,717). It is very probable \=/ \=/ \=/ that the latter substance is Br 5.) analogous with tribromoreso- quinone and has the formula (I) C. H. D. C6H4 c6H4 W. H. G. Tribromoresoquinone. C1,O 0 c1 c1,o BrH HBr (1.1242 ABSTRACTS OF CHEMICAL PAPERS.whilst the substance from which it is prepared is a ketochloride having the constitution (11). ~h~orod~b~omo~esoqu~norte obtained by the action of chlorine on 0 a solution of tetrabromodiresorcinol in dilute acetic Br/\CIBr acid crystsllises in nodules of small yellow needles 11 lo m. p. 212O (decomp.). It is reduced to dichlorodibromo- H\/ diresorcinol C,,H,Cl,Br,O crystallising in long slender needles m. p. 271O; the same substance H j K O is apparently produced by the reduction of dichloro- Brll IClBr bromoresoquinone. W. H. G. 0 v Preparation of Anthraquinone-a@-sulphonic Acids. R. WEDEKIND & Co. (D.R.-P. 202398).-The P-anthraquinone mono- and di-sulphonic acids undergo sulphonation with fuming sulphuric acid in the presence of mercury or mercuric salts and give rise to new polysulphonic acids containing sulphonic groups in a-positions.Anthra- quinone-3-sulphonic acid sulphonated at 160' with fuming acid (40% SO,) and a small amount of mercuric sulphate furnishes chiefly anthraquinone-1 6- and -1 7-disulphonic acids. These acids are also obtained by starting with anthraquinone itself and sulphonating as before in the presence of mercuric sulphate employed in a coarse granular form. G. T. M. Preparation of Halogenated Anthraquinones. FARBENFAB- RIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 205913. Compare follow- ing Abstract).-The replacement of the sulphonic group by halogen in the anthraquinonedisulphonic acids may be eEected in two stages by employing moderate amounts of halogenating agent.Potassium 1-chloroanthraquinm-5-sulphonate pale yellow needles is obtained by treating sodium anthraquinonedieulphonate with sodium chlorate and hydrochloric acid and salting out the product with potassium chloride so soon as appreciable amounts of the original disulphonate are no longer apparent. Potasslum 1 -bromoanth~apuinome-5-su.!phomte,. yellow needles is produced in a similar manner by employing bromine instead of chlorate and hydrochloric acid. Similar results are obtained with anthraquinone-1 8- and -2 7-di- sulphonic acids the sulphonic groups being replaced by chlorine in two stages. G. T. M. Replacement of Halogen by Hydroxyl in Substituted An thraquinones. FARBENFABRIKEN VOHM. FRIEDR. BAYER & Go. (D.R.-P. 203083).-When the halogenated anthraquinones are heated with fuming sulphuric acid either with or without boric acid the halogen atoms are more or less replaced by hydroxyl.1 4-Dichloro- anthraquinone and 4-chloro-l-hydroxyanthraquinone give rise to quinizarin (1 4-dihgdroxyanthraquinone) and 2 4-dibromo- l-amino- anthraquinone furnishes 2-bromo - 4-amino- 1 - hydroxyanthraquinone m. p. 243'. G. T. M.ORGANIC CHEMISTRY. 243 [Preparation of Alkylaminoanthraquinone Derivatives.] FABBWEBKE VOBM. MEISTER LUCIUS L RRUNING (D.R-P. 205096).- Potassium 1 4-diethyltcrninoanthrquinone-5-8~&1honate blue needles with bronzy lustre is obtained by heating a t 100-120' aqueous ethylamine and the leuco-derivative of potassium quinizarin-5-sulphon- ate ; by using methylamine the corresponding dimsthyZaminoanthra- quinvne-5-sdphote was produced.Preparation of Derivatives of 1 SDiaminoanthraquinone. BADISCEE ANILIN- & SODA-FABRIK (D.R.-P. 205036).-o-Benzoyl- benzoic acid on treatment with concentrated nitric and sulphuric acids furnishes among other products 3 5-dinitro-o-benzoylbenzoic acid which on reduction gives rise to 3 5-diamino-o-benzoyl benzoic acid C,H,(NH,),* coo C,H,-CO,H this substance having the property of condensing with great readiness to form 1 3-diaminoanthraquinone. ~rinitro-2-p-toZuoyEbenxoic acid m. p. 21 7-2185O from the nitra- tion of 2-p-toluoylbenzoic acid is reduced by iron and acetic acid to trhirno-2-p- t oluo y I benzoic acid which on warming wit hr dilu t e ammonia gives 1 3 (?)-triami~o-2-msthy~nthrccquii~ yellowish-red needles m.p. above 300'. 1 3 - D i a m i ~ o - 2 - m e t h y ~ n t h r a q ~ i ~ yellowish-red needles m. p. 273-276' is obtained by reducing 1 3-dinitro-2-ptoluoylbenzoic acid with iron and dilute acetic acid ; the intermediate 1 3-diamino-2-p- toluoylbenzoic acid having largely condensed during reduction the remainder is condensed by warming with acetic acid. 1 3-Diamino-2~methoxyanthraquinone reddish-yellow needIes m. p. 225-230' is obtained by a similar set of operations from p-anisoyl- benzoic acid. G. T. M. [Preparation of Leuoo-derivatives of Diaminoanthraquinones f'rom the Corresponding Hydroxylic Compounds.] E'ABBWEBKE VORM. MEISTER LUCIUS Q BR~NINC) (D.R.-P. 2051 49).-The leuco- derivative of quinizarin when heated with alcoholic ammonia (25%) at 100' gives rise to the leuco-derivative of 1 4-diaminoanthra- quinone leaflets with green metallic reflex m.p. 272O (decomp.). The leuco-derivative of 1 4 5 8-tetrahydroxynnthraquinone obtained by reducing the tetrahydroxy-compound with alkali hyposulphite when treated with alcoholic ammonia gives rise to the leuco-derivative of 1 4diamino-5 8-dihydroxyanthraquinone needles decomposing at 284'. Other leuco-derivatives of the hydroxyanthraquinones undergo this change on treatment with ammonia. Preparation of Arylaminoanthraquinones. FARBWEBKE VOBM. MEISTEB LUCIUS & BRUNING (D.R.-P. 201905).-4-Amiru~1-ptoZ~E avmino-8-methoxyanthraquinone lustrous coppery leaflets m. p. 226* is prepared by heating 4-nitro-1 8-dimethoxyanthraquinone with ptoluidine and stannous chloride at 60-90'; its klphonic acids are wool dyes giving fast shades of blue.Preparation of 4Chloro-1-hydroxyanthraquinone. R. WEDE- KIND & Co. (D.R.-P. 202770).-4-Chloro-1-hydroxyanthraquinone is G. T. M. G. T. M. G. T. M.244 ABSTRACTS OF CHEMICAL PAPERS. readily obtained by adding simultaneously to 1-hydroxyanthraquinone suspended in strong sulphuric acid at 110-1 15' solutions of potassium chlorate and hydrochloric acid. G. T. M. Preparation of Thiocyanogen Derivatives of Anthraqiuinone. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 206054).-The replacement of the diazonium group by thiocyanogen occurs readily in the benzene and naphthalene series only in the presence of cuprous thiocyanate. I n the anthraquinone series this replacement takes place merely on boiling the diazonium thiocyanate with water.a-Thiocyanoanthraquinone CNS*C,,H70 yellow needles m. p. 23 lo was obtained by diazotising a-aminoanthraquinone in concentrated sulphuric acid and boiling the aqueous solution of the diazo-salt with potassium thiocyanate. Other thiocyano-derivatives with this group in positions 2 and 1 5 are similarly produced. G. T. M. Preparation of Benzanthrone and its Derivatives. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 204354. Compare Abstr. 1907 i 324 943 ; 1908 i 193 66l).-.The aminoanthraquinones and their derivatives coud ense with glycerol and concentrated sulphuric acid to yield benzanthrone derivatives; it has now been found that this condensation can be effectively carried out by using instead of glycerol such of its derivatives as mono- and di-chlorohydrin and acetin (glyceryl acetate).G. T. M. Preparation of Halogen Derivatives of Benzanthrone. BADISCHE ANXLIN- & SODA-FABRIK (D.R.-P. 205294).-fl-ChZ~o- benxanthrone dark green powder or yellow needles is obtained by con- densing /?-chloroan thraquinone with glycerol aniline sulphate and concentrated sulphuric acid at 140'. I n this condensation acetin may be employed instead of glycerol. More highly halogenated benzanthrones can be similarly prepared from dichloro- and dibromo-anthraquinone. G. T. M. Crystallography of the Anhydride of Menthyl Xanthate. N. SUR~UNOFF (Zeitsch. Kryat. Min. 1909 46 219-220 ; from BUZZ. Xoc. Nut. MOSCOU 1906 Nos. 1 and 2 142-152).-The crystals are hemihedral-rhombic [a 6 c = 1.4478 1 2.35331.L. J. S. The Preparation of Mixed Carbonates from Hydroaromatic Alcohols and Ethyl Salicylate. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 306055). -Menthyl scdol carbonate CO(OC,,H 7)*0*C,H:,*C02Ph colourless crystals m. p. 57-58 is produced by condensing salol and menthyl chlorocarbonate in benzene containing pyridine ; it is also formed by the interaction of salol chlorocarbonate and menthol in the presence of quinoline. Menthyl salicylacetol carbonate CO(OC,,H~7)*OC,H,*C02~CH2*COMe colourless tasteless crystals m. p. 87' is prepared from menthyl chlorocarbonate and acatonyl salicylate OH*C6H,*C0,*CH,*COMe.ORGANIC CHEMISTRY. 245 ThymyZ scclol cccrbonate from salol chlorocarbonate and thymol forms colourless and odourless needles m.p. 78-79'. Santdyl salacetol carbonate a yellow syrupy liquid is produced from santalol and salacetol chlorocarbonate the latter reagent being obtained by the interaction of carbonyl chloride and salacetol in the presence of dimethylaniline. The patent refers to several other mixed carbonates of a similar type. OTTO ZEITSCHEL (D.R.-P. 204163).-The existing process for the production of bornyl acetate f r o a pinene is expensive owing t o the large proportion of glacial acetic acid employed. It has now been found that this ester can be produced from its generators French turpentine and glacial acetic acid when icteracting in molecular proportions at 200' for about five hours. In this way 30-40% of bornyl acetate 30-40% of limonene and l0-15% of camphene are obtained. Preparation of Bornyl and isoBornyl Bromoisovalerates.CHEYISCHE FABRIK AUF ACTIEN VOBM. E. SCHEEINQ (D.R.-P. 205263 and 205264).-BornyZ bromoisovalerate CHMc,*CHBr*C0,*C,,H7,~ oil b. p. 163"/10 mm. is obtained by heating in chloroform solution equivalent . quantities of borneol and bromoisovaleryl chloride or bromide; i t may also be obtained from borneol and bromoisovaleric anhydride a t 1 OOO bromoisovaleric acid and concentrated sulphuric acid at 80° or from camphene and bromoisovaleric acid in the presence of zinc chloride. isoBornyl bromoisovalerate oil b. p. 1 60°/3 mm. is similarly prepared and can also be produced by mixing isobornyl isovalerate with bromine at 100' ; a bromine carrier accelerates this action which takes a similar course with bornyl isovalerate. Crystallography of Two Xanthogenamides (Thio- urethanes).EVGRAF S. FEDOROFF and D. N. ARTEM~EFF (Zeitsch. xryst. dfin. 1909 46 215-218 ; from Bull. SOC. Nat. Moscou 1906 Nos. 1 and 2 110-132. Compare Tschugaeff Abstr. 1902 i 604). -l-Phenyl-3-Z-bornyl-2-ethyl-iminoxnnthide monoclinic [a b c = 0.5785 1 :0.5008; p = 100°59']. 1 2-Diphenyl-3-fenchyl-iminoxanthide rhombic [a b c = 0.9484 1 0.95121. Optically Active Menthones. EBNST BECKMANN (Ber. 1909 42 846-850).-Z-Menthone obtained from I-menthol by oxidation with chromic acid has [aID - 28.5' ; when inverted with 90% sulphuric acid in the cold it has [a]= +228.1'. This product is a mixture of I-menthone with a highly dextrorotatory d-isomenthone. The mixture of oximes from the product can be separated by dissolving in ether and passing in dry hydrogen chloride.A crystalline precipitate m. p. 132' [aID + 35*9O is obtained whilst the mother liquors yield a com- pound having m. p. 117-118' [aID - 62.6'. These are identical with the oxime hydrochlorides of d-zsomenthone and I-menthone. The corresponding oximes have the following constants d-isomenthone- oxime +41' syrup; Lmenthoneoxime [a]. -42.5O m. p. 59O. G. T. M. [Preparation of Bornyl Acetate.] G. T. M. GI. T. M. L. 3. S. VOL. XCVI. i. 8246 ABSTRACTS OF CHEMICAL PAPERS. d-isoMenthone gives the same product on inversion as I-menthone. d-isoMenthone semicarbazone cry stallises in colourless needles m. p. 154' [ u ] ~ + 46.5'. E-Menthone semicarbazone has m.p. 184' [(;c]D - 64". From '' inverted " menthone a semicarbazone m. p. 116' + 26.6"' has been obtained (compare Barrowcliff Trans. 1907 91 863). E. F. A. Preparation of Camphor. SCHMITZ & Co. (D.R.-P. 203791).- The metallic derivatives of borneol andiisoborneol are readily oxidised to camphor and metallic hydroxide. A current of air passed through a cold toluene solution of sodium isobornyloxide or calcium bornyl- oxide leads to the production of camphor and sodium hydroxide or calcium hydroxide respectively. A similar result is obtained by warming together (in xylene) mercuric oxide and sodium isobornyl- oxide. G. T. M. [The Interaction of Hydroaromatic Ketones and Mag- nesium Aryl Halides.] BRUNO SZELINSKI (D.R.-P. 202720).- Carvone and pulegone when submitted to the Grignard reaction with magnesium aryl halides furnish the following compounds benxy l- dihydrocaruone m.p. 69' b. p. 204-206'/26 mm. oxiine m. p. 138'; a-naphthyldihydrocarvone viscid oil m. p. 150° b. p. 230-233'/34 mni. oxime oily; benxyldihydropulegone b. p. 2 10-215"/ 35 mm. oxime oily. These products when mixed with collodion wool or cellulose acetate give rise to transparent flexible celluloid which is more resistant to heat than camphor-celluloid and has a much higher decomposition point. G. T. M. isoPulegone. ALFRED EBERT (Chem Zentr. 1909 i 2 1 ; from Zeitsch Allg. Oesterr. Apoth.-Ver. 1908 545 561 573 589).-When iso- pulegone CH2:cMeo?H-Co-FH2 . prepared from citronell- CH; CH CHMe' aldehyde (Tiemann and &hmi*dt Abstr. 1897 i 198) is dissolved in ether and submitted to the action of magnesium methvl iodide It is a pale yellow liquid having a geranium-hke odour b.p. 93-94°/12mm.,D20 0.91085 [u] 19*54' ng 1.46992. I n cold ethereal solution this substance reacts with phosphorus trichloride forming methylisopulegyl chloride C,,H,,CI a colourless liquid b. p. 92-93O/ 10 mm. which loses HCI when boiled for three hours with alcohol and potassium acetate yielding met?qlisopulegene CH,:UMe*yH-CMe :YH CH,*CH,*CHMe' a colourless liquid b. p. 95-97"/12 mm. 182-184°/750 mm. D20 0.84 [a12 + 46-27' nz 1.4724. Methylisopulegene is also obtained by distilling under ordinary pressure the crude product of acetylating methykopulegyl alcohol. J. V. E.ORGANIC CHEMISTRY. 247 Preparation of Santalol Ethers.FARBENFABRIKEN VORM. FRIEDR. BAYER& Co. (D.R.-P. 202352).-Xantalyl methyl ether colourless liquid b. p. 149-156O/16 mm. was obtained by the following processes (1) boiling together santalyl chloride and methyl-alcoholic sodium methoxide ; (2) adding methyl sulphate to sodium santalol suspended in ether; (3) heating together sodium eantalol and methyl iodide in toluene. Santalyl ethyl ether colourless liquid b. p. 169-174'/22 mm. was prepared from santalyl bromide and alcoholic sodium ethoxide. Santalyl phenyl ether viscid oil b. p. 232'/20 mm. and santalyl menthyl ether colourless syrup b. p. 201-210°/5 mm. were obtained by heating santalyl chloride in xylene solution with sodium phenoxide and sodium meuthoxide respectively. Preparation of Santalyl Halides.FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D R.-P. 203849).-SantaZyZ chloride oil b. p. 162-167"/15 mm. is readily prepared by heating under reduced pressure saatalyl chlorocadonate obtained by the interaction of carbonyl chloride and santalol or sandal oil in the presence of dimethylaniline in benzene solution ; it may also be produced by the action of phosphorus pentachloride or thionyl chloride. Santalyl bromide is similarly obtained from phosphorus pentnbromide. G. T. M. G. T. M. Preparation of Santalyl Allophanate. VEREJNIGTE CHININ- FABBIKEN ZIMMER & Co. (D.R.-P. 204922).-Santaiyl allophccnate C1,H,,O*CO*NH*~O*NH white needles m. p. 162O may be prepared in a variety of ways (1) Cyanic acid is added to santalol dissolved in light petroleum ; (2) santalol is added to a benzene solution of carbamide chloride either alone or in presence of dimethylaniline ; (3) santalol and phenyl carbamate or allophanate are heated under reduced pressure.G. T. M. CARL D. HARRIES and HANS VON SPLAWA-NEYMAN (Ber. 1909 42 879-8SO).-By boiling pinene ozonide with water Harries and Neresheimer (Abstr. 1908 i 194) were unable to characterise the aldehydic substance formed but the present authors find that the decomposition proceeds more smoothly in glacial acetic acid solution at 90". After evaporating the acetic acid in a vacuum at 35" the residue is fractionated under 12 mm. pressure. The fraction distilling at 115-1 25O gives with semicarbazide the disemicarbaxone of pinonaldehyde C12H2202N6 which crystallises in small round aggregates m.p. 214-215'. CHEMISCHE FABRTK VORM. SANDOZ (D.R.-P. 204921).-It was already known that the velocity of hydrolysis of pinene hydrochloride by alkali hydroxide is increased by the presence of' feebly acidic substances such as phenols and naphthols. It is now found that this result is effected by nentral compounds such as sodium or calcium toluene-p-sulphonate sodium naphthalene-P-aulphonate and sodium naphthalene-2 7-disulphonate. An Aldehyde from Pinene. J. C. C. Preparation of Camphene. G. T. M. s 2248 ABSTRACTS OF CHEMICAL PAPERS. Elaterin and Some of its Derivatives. ABMAND BERQ (Compt. rend. 1909 148 566-568. Compare Abstr. 1898 ii 447; 1906 i 596 ; 1907 i 146 ; Pollak Abstr. 1406 i 973).-Polemical against Hemmelmayr (Abstr. 1907 i 230).The author maintains the accuracy of his formula for elaterin C28Hs807 which he has confirmed by determinations of the molecular weight of diacetylelaterin and other derivatives. Hemmelmayr’s ‘‘ elateridin,” obtained in the hydrolysis of elaterin by sulphuric acid is stated to have the formula C,,H,,O,. The author proposes t o call this compound anhydroelateridin and to reserve the name elateridin for the substance obtained when the hydrolysis is effected by alcoholic potassium hydroxide. Analysis and molecular- weight determinations by the cryoscopic method show that elateridin has the formula C,,H,,07. On treatment of elaterin with bromine a mixture of amorphous bromo-derivatives is obtained ; since these cannot be separated by crystallisation Hemmelmayr’s determination of the molecular weight of the product cannot be regarded as establishing his formula for ela terin .JULIUS STOKLASA VLADIMIR BRDLIK and ADOLF ERNEST (Ber. Deul. hot. Ges. 1907 27 10-20. Compare Abstr. 1908 i 279).-Polemical against Tsvett (Abstr. 1908 i 440) and Willstatter (Abstr. 1907 i 71). Chlorophyll contains phosphorus as glycero-phosphoric acid. Tsvett’s partial agreement with Willstatter (who denies that chlorophyll contains phosphorus) is not based on experimental results. The authors show by Tsvatt’s own ‘‘ chromatographic ” method (adsorption of the pigments by calcium carbonate) that phosphorus always accompanies the chlorophyll in adsorption and that in autumn when the green colour disappears from the leaves the phosphorus also disappears.G B. Completely Methylated Flavonol Derivatives. NICOLAI WALIASCHKO (Ber. 1909 42 726-728).-1n reply to Herzig and Hofmann (this vol. i 165) the author states that trimethyl- and pentamethyl-quercetin are readily obtained from quercetin methyl sulphate and potassium hydroxide under his conditions (Abstr. 1904 i 760). The ready formation of the pentamethylated derivative necessitates an alteration of Kostanecki and Dreher’s generalisation (Abstr. 1893 i 217) the revised version of which should read the alkylation of the hydroxyl group ortho to the carbonyl group whilst not accomplished or to only slight extent by an alkyl halide is readily effected by methyl sulphate and an alkali hydroxide. Constitution of the Fluorescein and Quinolphthalein Dyes. WALTER KROPP and HEBMAN DECKER (Ber.1909 42 578-584).- Kehrmann and Dengler have recently (Abstr. 1908 i 1002) prepared phenylfluorone the chromogen of fluorescein to which they assigned an ortho-quinonoid constitution and the present authors have endeavoured to prepare the corresponding chromogen of quinolphthalein by the hydrolysis of 2-methoxy-9-phenylxanthonium bromide (compare w. 0. w. The Phosphorus Content of Chlorophyll. C. S.ORGANIC CHEMISTRY. 249 Decker and von Fellenberg Abstr. 1907 i 1065) and subsequent neutralisation but they find the only product to be a colourless carbinol base namely 2-hydroxy-9-phenylxanthen-9-01 (formula I). There is thus a fundamental difference between the two series of compounds and the conclusion is drawn that Kehrmann and Dengler's phenylfluorone must have a para-quinonoid structure (11).and OH P h Ph /\/\\(\ (11.) \/Vd0 I I (14 /)+I 0 \/A/\/ 0 consequently fluorescein must also possess the older para-quinonoid constitution whilst the ortho-quinonoid formula for the alkali salts of quinolphthalein which is the only one that explains their colour cannot be upheld. CPh*fi= C H ?*OH 2-Hydroxy-9-phenylxanthonium bromide C6H,<bBr .c. CH:CH prepared by heating 2-methoxy-9-phenylxanthen-9-01 with hydro- bromic acid crystallises in dark red plates which darken on warming and melt and decompose a t about 300'. On hydrolysis it yields 2-hydroxy-9-phenylxanthen-9-02 crystallising in colourless rhombic prisms m. .p. 158-160' (decomp.). The chloride red rosettes of plates ; zodade long blackish-red plates ; platinichloride dark red needles and ferrichloride dark red crystals m.p. 193-1 9 4 O (corr.) are described. When 3-methoxy-9-phenylxanthonium chloride is heated with hydrochloric acid under pressure the corresponding hydroxy-compound is formed which with sodium hydroxide furnishes phenylfluorone. The properties of t h i s compound are not those of a phenolbetaine which should be soluble in water and not extractable from its solutions by ether or benzene. Moreover it should (were it a betaine) be at least as strongly coloured as the oxonium salts but it is only orange-yellow whilst the corresponding salts are red. It is therefore to be regarded as the chromogen of fuchsone a conclusion which is confirmed by R. Meyer's observation of the correspondence between the spectrum curves of the fluoresceins and phthaleins.J. C. C. Carboxonium Dyes. 11. Strongly Basic Neutral Salt- forming Nitrogen-free Oxonium Compounds and t h e Con- stitution of Fluorescein. PRIEDRICH KEHRMANN and 0. DENGLER [with KARL SCHEUNERT] (Ber. 1909 42 870-879).-By the inter- action of methyl sulphate and resorcinolbenzein and of methyl sulphate and fluorescein methyl ester the authors have been able to obtain on hydrolysis of the resulting metho- sulphate oxonium bases which are strongly basic and give neutral salts. d,J,&b~e 3-Methoxy-9-pheny~wone (annexed formula) I-(j prepared by the action of methyl sulphate on resorcinolbenzein in nitrobenzene solution at 150' CPh A/\/\250 ABSTRACTS OF CHEMICAL PAPERS. and subsequent hydrolysis of the product forms clusters of chrome- red needles m.p. 202'. It is more strongly basic than the parent base. The chloride forms reddish-yellow prisms with a blue reflex and the platinichloride is an orange-red CPh crystalline powder. On methylation under /\/\/\ the same conditions as above 3-methoxy-9- OMe} I I 1 0 ~ ~ phenylfluorone yields the carbinol base of \A//\/ 3 ; 6-dimethoxy-9-phenylxanthylium (annexed ? formula as methosui'phute). The chZoride O*SO,Me forms yellow prisms or plates with a blue reflex. The nitrate iodide dichroinate platini- chloride methyl ether m. p. 112" and ethyl ether colourless prisms m. p. 15S0 are described. By the interaction of methyl sulphate and fluorescein methyl ester a mixture of two comDounds is formed. The first 3:6-dimethoxu- L u y6 H4 c6H3'oMe)>0 crystallises in colourless tablets cfl'uoran CO*O>C<c6H,(OMe) m.p. 197' and the second; the phenozbetaine of methoxyfluorescein methyl ester (formula I) forms brick-red needles m. p. 176-1 77'. The chloride forms orange-red grains and undergoes hydrolysis only when the aqueous solution is kept for a long time or if it is warmed. /\ ()CO,Rle C /\ j?CO,Me C (1.1 (11.1 Treatment of the above compound with methyl sulphate as before furnishes the methosuZphate of methyl 3 6-dimethoxy-9-phenylxanthyZium- 2'-curboxylate from which the chloride (formula 11) amber-yellow prisms with a bluish-violet reflex the nitrate yellow leaflets the dichromate iodide and plcctinichloride were prepared. Syntheses in the Braean Group.A. GRAFMANN and STANISLAUS VON KOSTANECKI (Ber. 1909 42 822-824).-Liebermann's method for the preparation of bydroxybrazanquinones from dichloro-a-naphtha- quinone and phenols only holds for resorcinol and as is now found for orcinol. J. C. C. o*c*co 3-Hydroxy- 1 -rnethyZb~axanquinone OH*C,H,Me<_z. CO>C,H4 is obtained in red needles m. p. 315' which dissolve both in dilute sodium hydroxide and in concentrated sulphuric acid with a blue coloration. The 3-acetoxy-derivative crystallises in lustrous golden plates m. p. 278". If the acetylation is carried out in presence of zinc dust the acetylated leuco-compound 3 1' 4'-triacetoxy-1-methyl- biwzan is obtained ; this crystallises i n colourless needles m. p. 243-244' and is dissolved in concentrated sulphuric acid with aORGANIC CHEMISTRY. 251 green coloration and intense dark green fluorescence.3-Methoxy- 1-methylbramnquinone obtained on methylation with methyl sulphate forms orange-yellow needles m. p. 240° which can be distilled without decomposition and dissolve in concentrated sulphuric acid with a blue coloration. When acetylated in presence of zinc dust 3-methozy- lmethyl-1’ 4’-diacetoxybraxan is formed ; this separates in colourless glistening crystals or needles m. p 221-222”. The above compounds are formulated as 3-hydroxy-1 -methyl deriv- atives but they may with equal right be represented as l-hydroxy- 3-methylbrazanquinones. E. F. A. Reduction of the Thiophen Nucleus. VICTOR THOMAS (BUZZ. 8oc. chim. 1909 Livl 5 182)-In connexion with the publication of a note by Padoa and Ponti (Abstr. 1907 i 146) on the reduction of the furan nucleus by hot nickel the author points out that he is studying the reduction of the thiophen nucleus by this method and the results so far obtained show that the reaction takes a different course from that found for furan by the Italian chemists the ring being ruptured and benzene formed.T. A. H. Preparation of Leuco-derivatives. Subetituted ‘‘ Thio- indigotin.” FARBWERKE VORY. MEISTER LUCIUS & BRUNING (D. R. -P. 204763).-2-MethyZthioZ-4-methyZbenzoic acid C6H,Me(8Me)*C02H is prepared by diazotising 4-methylanthranilic acid and treating the diazo-solution successively with potassium xanthate and sodium methyl sulphate. Methylthiolcarboxymethylbenzoic acid [4-carboxy-m- dolylthiolacetic wid] CO,H*CH,*S*C,H,Me*CO,H yell0 w crystals m.p. 194-195’ is obtained by replacing sodium methyl sulphate by sodium chloroacetate in the preceding reaction. The former of these two substances yields 3-oxy-6-rnethyZthionaphthem m. p. 84’ and 3-my- 6-methyZtl~ionaphthencarboxyZic acid on treatment with sodium-lead in the presence of alkali hydroxide a t 210’; the latter gives the same products when heated at 180-1 90’ with aqueous alkali hydroxide. These thionaphthen derivatives when heated with sodium thio- sulphate and glycerol at 120-130’ furnish the leuco-derivative of “ dimethylthioindigotin,” from which on oxidation the red colouring matter is produced. The patent contains reference to other substituted ‘‘ thioindigotins.” G. T. M. [Preparation of a Thioindigoid Dye from Acenaphthene- quinone.] BASLER CHENISCHE FABRIK (D.R.-P.205377).-Acenaph- thenequinone when heated with carbomethoxy-o-thiobenzoic acid or 2-hydroxythionaphthen either alone or with a condensing agent such as anhydrous sodium carbonate or sodium acetate and acetic anhydride yields a colouring matter which crystallises from hot glacial acetic acid or benzene as a vellow or brownish-red Dowder. This com- .r L CO YO*V6H4 pound probably has the following constitution C,,H,<& c-s (compare Abstr. 1908 i 979). G . T. M.252 ABSTRACTS OF CHEMICAL PAPERS. Preparation of a Substituted a-Oxythionaphthen. KALLE B Co. (D.R.-P. 202696. Compare Abstr. 1908 i 953).-4-Chloro-2-nitro- thiophenol when reduced with iron and hydrochloric acid and the product treated with sodium chloroacetate gives rise to 4-chloro- 2-aminophenylthiolacetic acid.The latter substance when succes- cively diazotised and treated with cuprous cyanide furnishes p-chloro- o-cyanophenylthiolacetic m i d white needles m. p. 164-165'. 4-Chloro-2-arninothionaphthencarbo~yZic acid which results from the alkaline hydrolysis of the cyano-compound yields chloro-a-oxythio- rucphthen white needles m. p. 106' when heated with dilute sulphuric acid ammonia and carbon dioxide being simultaneously eliminated. G. T. M. Partial Racemism. ALBERT LADENBURG (Annulen 1909 364 227-271).-A rdsumb of the author's publications on this subject abstracts of which have already appeared (compare Ladenburg and Herz Abstr. 1898 i 296 405 ; Ladenburg and Doctor Abstr.1898 3 707 ; 1899 i 310 ; Ladenburg and Bobertag Abstr. 1903 i 575 ; Ladenburg and Fischl Abstr. 1907 i 586 ; Ladenburg and Herrmann Abstr. 1908 i 364). Cinchona Alkaloids. IX. Oxidation of Cinchona Alkaloids to Ketones. PAUL RABE [with WILHELM NAUMANN and ERICH KULIGA] (Annabn 1909 364 330-352).-It has been shown previously (Abetr. 1908 i 100) that cinchonine contains n secondary hydroxyl group since on oxidation it yields a ketone namely cinchoninone. It is now found that cinchonidine quinine quinidine and hydrocinchonine when oxidised with chromic acid also yield ketones and are con- sequently to be regarded as secondary alcohols. The ketone derived from cinchonidine is definitely proved to be identical with that obtained from cinchonine; a t first sight it would appear that two stereoisomeric ketones should be formed but it has been shown that cinchoninone is a tautomeric substance (Abstr.1908 i 100 361); consequently the stereoisomeric ketones derived from the two alkaloidg are able to pass one into the other thus W. H. G. The ketone derived k o m cinihonine and c'inchonidine is the less soluble of these isomeric forms which crystallises from the equilibrium mixture. Tbe fact that cinchoninone exhibits mutarotation is in agreement with this statement. Only one ketone namely quininone is obtained when quinine and quinidine are oxidised. Hydrocinchonine gives rise to hydrocinchon- inone. The final optica.1 rotatory power of an alcoholic solution of cinchon- inone from cinchonine is Cali3 + 76.25' ( c = 3,2791 [ay; + 75.52O (c = 3.270) and from cinchonidine is [a]? + 72-31' ( c = 5.305) and The difference in the optical behaviour of the two specimens is due to the presence of impurity since the methiodide of the compound from cinchonine has [a]" +65*39" Both these ketones exhibit mutarotation.+ 71-61' ( c = 3.3025).ORGANIC CHEMISTRY. 253 (c = 2.0645 in chloroform) and from cinchonidine [u] + 65.35' (c = 2.058 in chloroform). Quininone C,,H,,O,N prepared by oxidising quinine or quinidine with chromic acid in strong sulphuric acid crystallises in almoet colourless needles or leaflets m. p. 101' (heated slowly) or 108' (heated quickly) It is an amphoteric substdnce ; the Aydrochtoride C,,H,,O,N,,HCI obtained as a hygroscopic yellow crystalline powder has m.p. 210-2123 [a]E '+58*67O (final value; c=1-926 in alcohol); the sui'phate is an amorphous substance m. p. about 106-108' ; the picrate C2,H2.0,N forms canary-yellow crystals m. p. 232-233' ; the pacrolonate CBOH3007N6 crystallises in small yellow prismatic needles m. p. 197-198' ; the nzethiodids C,oH,,O,N,MeI forms almost colourless feathery crystals m. p. 213-214'; the oxime C2,H,30,N3 is a vitreous substance m. p. about 113'. Hydrocinchoninone C,,H,,ON prepared from hydrocinchonhe forms pale yellow crystals m. p. 138' [a] + 76.06O (final value ; c = 3*300) [a12 + 76.22' (final value ; c = 2.296). The methiodids C,9H2,0N,,MeI forms small pale yellow crystals m. p. 234-235O ; the hydrochloride C,,H,,ON?,ACl is white and sinters at 256O m. p. 265'; the dihydrochlorzde IS very deliquescent and could not be crystallised ; the picrate C,jH.&8N5 forms yellow crystals m.p. 186'; the picrolonate C,9H,o0,N is an orange crystalline substance m. p. about 90' (decomp.) ; the oxime C,,H,,ON is an amorphous yellow powder m. p. 88-100° (decomp.). + 73-79' (final value ; c = 2.141 in alcohol). W. H. G. Preparation of Quinine and Cinchonine p - Aminophenyl- arsinates. VEREINIQTE CHEMISCHE WERKE AKTIENGESELLSCHAFT (D.R.-P. 203081).-Quinine p-aminophenylarsinate white needles m. p. 202' is obtained by double decomposition from quinine hydrochloride and sodium p-aminophenylarsinate. Cinchonine p-aminopheriylarsinate small prisms m. p. 180° is obtained similarly. G. T. M. Preparation of Cotarnine Cholate. F. HOFFMANN-LA ROCHE & Co.(D.R.-P. 206696).-Cotasnine cholate yellow powder m. p. 118-120° (decomp.) readily soluble in water and alcohol is pro- duced by mixing cholic acid and cotarnine in water or some other suitable solvent and evaporating the solution t o dryness in a vacuum at 45'. This compound is employed in gynaecology. G. T. M. Strychnos Alkaloids. 111. Reactions of Brucinonic Acid and Fission of the Brucine Molecule. HERMANN LEUCHS and LOTHAR E. WEBER (Ber. 1909 42 770-777. Compare Abstr. 1908 i 5 6 3 ; this vol. i 120)-It has already been shown that the dibasic brucinonic acid contains two methoxyl groups and the > N*CO radicle groupings which are contained in brucine itself. The remaining oxygen atom is now shown to be ketonic as the acid gives brwimmic acid oxime C,,H,,O,N a crystalline powder m. p.293O (corr. decomp.) [a]$'+ 128.2' and a semicarbazone C2,H,,O,N,,3H,O which forms Coloyrless needles m. p. 250-851° (corr. decomp.) [ a g + 252'. On254 ABSTRACTS OF CHEMICAL PAPERS. reduction with sodium amalgam the semicarbazone is converted into the isomeric compound C24H2708N5 which forms crystals m. p. 237-238O [a$' + 128.4O; the nature of this derivative has not yet been elucidated. Brucinonic acid yields on reduction with sodium amalgam brucinolic mid C,,H,,O,N which separates from chloroform in crystals m. p. 250-25 1' (corr. decomp.) [a]? - 22' ; its acetyl deriv- ative has m. p. 295' (decomp.). The solution of t%s acid in normal sodium hydroxide (1 8 mols.) gradually deposits hrucinolone C2,H2,0,N2 which crystallises from glacial acetic acid in massive prisms 'm.p. 289O (corr.) [a] - 32-1 2' ; a molecular-weight determination in acetic acid gave 354 calc. 382; this substance is neutral. The alkaline mother liquor contains glycollic acid and these compounds have been derived from the hydrolysis of the brucine molecule C23H2608N2-3C2H403 + C21H2205N2' w. It. Crystallography of Pyridine Derivatives. EWRAF S. FEDO- ROFF (Zeitsch. G y s t . Bin. 1909 46 210-213 ; from Verh. rzcss. Min. Ges. 1905 43 207-236).-2-0ximinobenzoylpyridine (two modifica- cations colourless rhombic crystals and pale yellow monoclinic crystals) ; 4-oximinobenzoylpyridine (monoclinic) ; 4-benzoylpyridine picrate (monoclinic) ; phenyl-2-pyridylcarbinol (rhombic) ; 2-benzyl- pyridine picrate (monoclinic) ; 4-benzylpiperidine platinichloride (rhombic '1) ; 4-benzylpyridine picrate (triclinic).L. J. 8. Resolution of the Racernic Cincholeuponic Acids into their Active Forms. ALFRED WOHL and RUDOLF MAAG (Bsr. 1909 42 627-633. Compare Wohl and Losanitsch Abstr. 1908 i 47).- a- and P-Cincholeuponic acids have been resolved by the aid of brucine ; the P-d-acid is identical with the acid obtained from quinine or cinchonine; a further step in the synthesis of quinine has therefore been accomplished. Fractional cry stallisation of the brucine salt of a-r-cincholeuponic acid does not give a pure salt but a mixture of the r-salt with the salt of the Z-acid. The 2-acid can however be obtained from the acid derived from this salt by crystallisation from water. a-l-Cincholeuponic acid is anhydrous and forms prisms m.p. 253' (corr.) [a12 - 35.0' in a 4.42% solution. The d-acid from the syrupy filtrate of the brucine salt gave m. p. 253' and [a]$' + 34-90'. a-r-Acetylcincholeuponic anhychide prepared by boiling acetic anhydride and the hydrobromide for half an hour crystallises from a mixture of alcohol and ether in rosettes of needles m. p. 121° and is converted by hot water into a-r-acetyl- cincholeuponic acid C,,H,,O,N which forms needles m. p. 175' (corr.). The ,&acid was resolved by using the acetyl compound instead of the acid itself. P-r-Acetylcincholeuponic anlzydTide forms rosettes m. p. 135-136' (corr.) and the acid from anhydride and water has m. p. 184-185' (corr.). Resolution of this acid by brucine gave the P-d-acetyl- cincholeuponic acid m.p. 167-16So [a] + 19*86O which is identical with the compound from quinine. Hydrolysis by 20% hydrochloric acid gave P-d-cincholeuponic acid hydrochloride [a];(' 38*04' m. p. 192-194' ; a crystallographic examination showing that theORGANIC CHEMISTRY. 255 compound was identical in all respects with :that obtained from cinchonine by Skraup. The 1-hydrochloride has m. p. 192-194' and [a] - 36.51'. W. R. New Quinoline Derivatives and Examples of Steric Hindrance. OTTO STARK [with FELIX HOFFMANNJ (Bey. 1909 42 715-719. Compare Abstr. 1907 i 973).-Benzoylacetone condenses with an alcoholic solution of o-aminobenzaldehyde in the presence of a little piperidine yielding 3-benxoyl-2-methyZquinoline C,7H,,0N and not 3-acetyl-2-phenylquinoline. The compound crystallises from light petroleum in well-developed prisms m.p. 61-62'. The oxi'me CI7H1,ON2 forms colourless needles from alcohol and has m. p. 230-231'. When distilled with potassium hydroxide and a little water the ketone yields a-quinaldine. DibenzoylmethaQe reacts with o-aminobenzaldehyde a t 200-210' yielding 3-6enzoyl-2-phen,yZquinoZine C,,H,,ON which crystallises from methyl alcohol in needles m. p. 134-1 35'. It does not yield an oxime under ordinary conditions but R 7% yield of oxime C,,H,,?N can be obtained when a large excess of hydroxylamine hydrochloride (6 mols.) and sodium hydroxide (18 mols.) are usedin alcoholic solution. It has m. p. 210-21 1'. When decomposed by distillation with potassium hydroxide the ketone yields 2-phenylquinoline and benzoic acid.Examples of steric hindrance were noticed in the formation of the ketones and also in the formation of the oximes. J. J. S. Tetrahydroacridone. H. TIEDTKE (Bey. 1909,42,621-626).-1n analogous manner to the preparation of tetrahydroacridine from o-amino- benzaldehyde (Abstr. 1908 i 682) tetrahydroacridone is obtained by the condensation of anthranilic acid and cyclohexanone. In this case however the intermediate product can be isolated cyclohexanone-ad- o-carboxylic acid CO,H-C,H,-N:C,H,,. It is obtained by heating the acid and the hydroaromatic ketone at 120' during one to two hours and separates from benzene as a crystalline compound m. p. 148'. It decomposes spontaneously on keeping is hydrolysed by boiling water into its components and has basic as well as acidic properties.To - - C(0H) prepare the tetrahydroacridone C,H,< N>C,H8 the an thr- anilic acid and cyclohexanone are heated first at 120' and afterwards at 220'. The yield is 4Q% the remainder forming aniline and carbon dioxide. It crystallises from alcohol in small colourless needles m. p. 358' and is easily soluble in dilute sulphuric acid a property which can be utilised for the separation of acridone and tetrahydroacridone. It is oxidised by dry air at 280' into acridone and distillation with zinc dust results in the formation of acridine. W. R. New Method of Formation of Acridone. ALFRED KLIEGL (Ber. 1909,42 591-594. Compare Graebe and Lagodzinski Abstr. 1892 1086).-TvVhen 10-20 grams of o-nitrodiphenylmethane are carefully heated in a tubulated retort a vigorous reaction begins at 3009 This reaction can be controlled by immersing the retort in cold sand so that the mass boils regularly ; water and some o-nitrodiphenyl-256 ABSTRACTS OF CHEMICAL PAPERS. methane pass over and a residue is left which sets to a crystalline mass.When this is distilled (without thermometer) a small amount of o-aminobenzophenone passes over and then acridone. The reaction is less vigorous when the nitrohydrocarbon is mixed with liquid paraffin and heated on a sand-bath. Phenylanthranil c6H4<gh>09 appears to be formed as an intermediate product (compare Bamberger and Elger Abstr. 1903 i 560) and can be isolated by means of an alcoholic mercuric chloride solution. p-Tolylanthranil when heated yields 3methyZ-9 -acridone C,,H,,ON which crystallises from glacial acetic acid in microscopic needles resembling acridone.Both compounds yield hydrochlorides when hydrochloric acid is added to the suspension of the compound in hot glacial acetic acid. Preparation of Indoxylcarboxylic Acid and Indoxyl. KALLE & Co. (D.R.-P. 206903).-o-Nitrobenzonitrile when reduced at low temperatures with iron and acetic or hydrochloric acid gives a good yield of o-aminobenzonitrile from which o-cyanophenylglycine is readily obtained. The latter on heating with 35% sodium hydroxide J. J. S. and this intermediite product when further heated with alkali at 150-220° loses ammonia and passes into indoxylcarboxylio acid and indoxyl from which indigotin can be produced in the usual way.G . T. M. [Preparation of Pyridones of the Anthracene Series.] FABBENFABRIKEN VORM'. FRIEDR. BAYER & Co. (D.R.-P. 203752. Compare Abstr. 1908 i 456).-l-Acetylamino- co anthraquinone like its methyl derivetive undergoes A condensation to form a pyridone when heated in 8H YH nitrobenzene solution with finely-divided potassium I hydroxide at 140'. The product anthrapyridone \ (annexed formula) is sparingly soluble in organic media and dissolves in concentrated sulphuric acid t o Four other compounds of this type are described in the patent. \/\/\/ a yellow fluorescent solution. GO G. T. M. Preparation of p-Phenylenediamine. AKTIENGESELLSCHAFT FUR ANILIN FABRIKATION (D.R.-P. 2021 70).-p-Phenylenediamine is readily obtained by heating p-dichlorobenzene ammonia (25%) and copper sulphate for twenty hours at 170-180° and finally at 200'.G. T. M. Preparation of p-Phenylenediaminesulphonic Acid. AKTIEN- GESELLSCHAFT FUR ANJLIN FABRIKATION (D.R.-P. 202564 and 202565). -p-Phenylenediaminesulphonic acid is readily obtained by heating together p-dic hlorobensenesulphonic acid copper chloride andORGANIC CHEMISTRY. 257 ammonia (25%) at 170'. This acid is also produced in the foregoing manner when the dichloro-acid is replaced by p-chloroaniline-2- sulphonic acid. G. T. M. Preparation of p-Phenylenediaminesulphonic Acid. AKTIEN- GESELLSCHAFT FUR ANILIN FABRIEATION (D.R.-I?. 202564 204972).- p-Phenylenediaminesulphonic acid is obtained by heating 4-chloro- aniline-3-sulphonic acid with aqueous ammonia in presence of copper salts.G. T. M. Preparation of 4Amino-4'-hydroxydiphenylamine. AKTIEN- GESELLSCHAFT FUR ANILIN FABRIKATION (D.R.-P. 204596).-The oxida- tion of p-phenylenediamine and phenol to indophenol is readily effected by hypochlorite solution in the presence of copper salts. When reduced with sodium sulphide the indophenol gives rise to 4-amino-4'-hydroxy- diphen ylamine. G. T. M. Preparation of l-Aryl-2 4-dialkyl-Shalogenmethyl-5-pyr- azolones. EARBWERKE VORM. MEISTEB LUCIUS & RRUNINU (D.R.-P. 206637).-It has been found that the l-aryl-3-methyl-2 4-dialkyl-5- pyrazolones yield halogen additive productp which after removal of hydrogen halide furnish monohalogenated derivatives in which the halogen is situated in the methyl group. 1 -Phenyl-2 ; 4-dimethyl-3-bromomethyl-5-pyracxolone CO-GMe N P h < ~ Me*C*CH2B/ leaflets or prisms m.p. 113') produced from l-phenyl-2 3 :4- trimethyl-5-pyrazolone by the successive action of bromine and sodium carbonate yields on boiling with water 3-hydroxy-1-phenyl-2 3 4- trimethylpyraxolone colourless prisms m. p. 170'. 1- Phnyl-2 4-din~thyl-3-chloromethyl-5-pyraxolone colourless crystals m. p. 110-112° is similarly obtained and from l-phenyl-2 3- dimethyl-4-ethyl-5-pyrazolone a similar series of operations leads to 1 -phenyl-2 -methyl-3- bromomethy2-4-ethyl-5 -p yraxolone colourless crys- tals m. p. 112-1 13') and 1-phenyl-2-methyl-3-hydroxymeth~F4-ethyZ- 5-pyraxolone needles m. p. 122-123'. G. T. M. Condensation of Hydantoin with Formaldehyde. ROBERT BERBEND and RUDOLF NIEMEYER (Annalsn 1909 365 38-49)- Hydroxymethylhydantoin OH*CH,*N< CH,.70 CO-NH Or is readily prepared by heating hydantoin with 40% formaldehyde solution (1.3 mola.). It crystallises from alcohol in felted needles m. p. 125-135'. When heated a t 120-130" for several hours it forms a clear fused mass which yields the compound C,H,04N when crystallised from hot water. The hydroxymethyl derivative is completely hydrolysed when boiled with water for an hour.258 ABSTRACTS OF CHEMICAL PAPERS. Phosphorus pentachloride or even better concentrated hydrochloric acid transforms the hydroxy-compound into chloromethylhydantoin which crystallises from benzene or chloroform in well-developed prisms m. p. 150-157'. It has not been found possible to reduce the hydroxy- or chloro-derivative to methylhydantoin.When hydantion is warmed with formaldehyde in the presence of hydrochloric acid complex condensation products are formed. The compound C,H,,O,N is obtained when B few drops of con- centrated hydrochloric acid are used. It crystallises from hot water in the absence of hydrochloric acid as compact colourless prisms m. p. 203-212'. I n the presence of hydrochloric acid it yields the compound C7H804N,. This latter compound is also formed when hydantoin and formalde- hyde are condensed in a strongly acid liquid. It crystallises from hot water in which it is sparingly soluble in lancet-shaped needles m. p. 295'. after sintering at 285'. C4H,02N,C1 The formula is suggested. A compound CI4HJ8O9N6 is produced when equal volumes of con- centrated hydrochloric acid and 40% formaldehyde solution are used in the condensation.It crystallises from hot water in slender prisms rn. p. 183-188'. When boiled for some time with water or alcohol it loses formaldehyde and ultimately yields the compound C7H80,N,. In the preparation of the compound C,,H,,O,N considerable amounts of amorphous compounds are formed. When washed with alcohol these form a hard cake m. p. 83-85" and readily absorb water. J. J. S. Synthetical Experiments in the Iminazole [ Glyoxaline] Group. ADOLF WINDAUS (Ber. I 909 42 558-763).-4-Methyl- glyoxaline condenses with formaldehyde when heated for eight hours in a closed tube at 120' to form a crumbly hygroscopic mass not of glyoxaline-4-ethanol as might have been expected but of 4-methyl- glyoxaline-5-carbinol.Picrolonic and phosphotungstic acids give precipitates with its aqueous solution ; the platinichloride is difficultly soluble. Reduction of this substance with hydriodic acid gives 4 5-dimethylglyoxaline (oxalate m. p. 261' ; picrate CllHl107N5 m. p. 195'; aurichloride m. p. 179-180'; nitrate m. p. 175-176' compare Eiinne Abstr. 1895 i 685) a result which shows that the above conclusion is correct as otherwise ethylglyoxaline would be formed. The methyl group in position 4 is not therefore reactive; it is the methylene group in the ring which gives the derivative and this reaction which is a general one for aldehydes is not a possible method for the production of histidine derivatives. In the light of this result doubt is thrown on the correctness of the constitution assigned by Gerngross to the product obtained from methylglyoxaline and chloral (this vol.i 189). Dibennxoylbutylenediamine CSH1802N2 from dimethylglyoxaline benzoyl chloride and sodium hydroxide crystallises in long needles m. p. 241'.ORGANIC CHEMISTRY. 259 Methylglyoxaline when heated with nitric acid (D 1.5) at 80' for thirty minutes gives a 60% yield of a mitromethylgZyoxaline C4H502N3 which crystallises from water in long prisms decomp. 248'; solutions i n ammonia or potassium hydroxide are intensely yellow and bromine gives a bi.omonitromethylgZyoxaZine C,H,O,N,Br which forms prisms m. p. 228O (decomp.). 1 4-Dimethylgly oxaline gives a nitro-derivative C5H702N3 which separates from water in long needles m. p. 160-161° and which does not yield alkali salts.The 8 5-dimethylglyoxaline on nitration gives 4-nitro-2 5-dimethylgZyoxuZine C Me< this forms long needles from water m. p. 252'; its aqueous solution is neutral but itspotussium salt is intensely yellow and is supposed to have the EM. a conclusion which isoiminazole constitution CMe< is in harmony with the experimental fact that the 1-methyl nitro- derivative does not give a salt. NH-gMe. 'C(N0,) N ,N - C( :NO,E)=N W. R. Preparation of Pyridazine. SIEGMUND GABE~IEL (Ber. 1909,42 654-658).-The disadvantages attending the preparation of pyridazine bykhe three methods already known (Tauber Abstr. 1895 i 301; Gabriel and Colman ibid. 1899 i 390; Marquis ibid. 1903 i 370) are avoided by the author who obtains the substance in quantity by the following method.An aqueous solution of a-ketoglutaric acid (Blaise and Gault Abstr. 1908 i 713) is treated with hydrazine sulphate dissolved in N-sodium hydroxide and the mixture evapcjrat ed to dryness; the residue by crystallisation from hot water yields the sodium salt C,H,O,N,Na,C,B,U,N2,2H,O from which by boiling 10% hydrochloric acid hydrated pyridazinone-3 -carboxylic acid C O < ~ ~ 2 ~ ~ > C - C 0 2 H H 2 0 is obtained ; this when anhydrous has m. p. 19So and by treatment with bromine in glacial acetic acid - yields pyriduzone-3-curboxylic w i d CO<~~.&~>C*CO,H m. p. 259-260' (decomp.) which is changed quant,itntively by fusion into NH-N 6-p,yridaxone CO<CH.CH>CH m. p. 103-104°. The latter by warming with phosphoryl chloride yields 3-chZoropyriduzine m.p. 3 5 O from which pyridazine is obtained by means of hydriodic acid and red phosphorus. c. s. Constitution of Acetylacetonecarbamide [4 6-Dimethyl- 2-pyrimidone]. 11. Action of Bromine on Acetylacetone- carbamide and on its Benzylidene Derivatives. OTTO STARK (Ber. 1909 42 705-714. Compare Evans Abstr. 1893 i 129).- The dibenzylidene derivative of 4 6-dimethyl-2-pyrinlidone (following abstract) readily combines with bromine in acetic acid solution yield- ing a red dibromide. 4 6-Dimethyl-2-pyrimidone yields a similar yellow dibromide in chloroform solution provided that all traces of moisture are absent. In both compounds the bromine has added260 ABSTRACTS OF CHEMICAL PAPERS. itself on to a double linking in the ring.The bromides react readily with alcohol or water yielding bromo-hydroxy- or bromo-ethoxy- derivatives. It has not been found possible t o obtain tetrabromides. The dibomide of 4 6-dimethyl-2-pyrimidone is insoluble in most organic solvents ; it turns dark grey at 160° but is not molten at 360". When rubbed with water the yellow colour disappears and the bronzoh ydroxy-compound NH>Co CHeCMe(OH\*NBr CMe- is obtained. This crystallises from alcohol in slender needles which darken at 250° sinter at about 330° and decompose at 345'. The same product is obtained by the action of bromine on an acetic acid solution of the pyrimidone and when shaken with concentrated hydrobromic acid in the cold yields Evans's dibromodihydroxy- derivative CH2<cMe(oH).NBr>C0.CMe( OH) *NBr The corresponding bromo- ethoxy-derivative CsHl3O2N,Br obtained by the action of ethyl alcohol on the dibromide decomposes at 340-350° after siutering at 330O. The dibromide of the dibenzylidene derivative C2,,H160N2kr2 decomposes a t 322-325" after turning brown at 240Oand sinteriog a t 3 18O. The bromohyclroxy -derivative C2,Hl,02N2Br crystallises from alcohol in orange-yellow needles sinters a t 304O and decomposes a t S 10-3 I 2 O . crystallises from alcohol in orange-yellow needles which decompose at 308' after sintering at 303-3059 The corresponding bromoethoxy-derivative C22H21Om3r7 J. J. S. Constitution of Acetylacetonecarbamide (4 6-Dimethyl-2- pyrimidone). Condensation with Aromatic Aldehydes. I. OTTO STARK (Ber. 1909 42 699-708. Compare Evans Abstr.1893 i 129 ; Combes ibid i 454; de Haan Abstr. 1908 i 454).-Evans's com- pound condenses with alcoholic solutions of aromatic aldehydes in the presence of small amounts of piperidine. When benzaldehyde is used a mono- and a di-benzylidene derivative are formed and it is thus probable that it is the methyl and not the methylene hydrogen atoms which condense with the aldehydic oxygen. With p-hydroxybenz- aldehyde and vanillin only one molecule of aldehyde reacts. It is suggested that the condensation products are formed from the tautomeric form of the carbamide namely 4 6-dimethyl-2-pyrimidone ; thus the monobenzylidene derivative is represented as this is practically colourless but the corresponding p-hydroxy- and hydroxymethoxy-compounds are respectively dark yellow and yollowish-brown in colour.The salts derived from these condensation products have a muchORGANIC CHEMISTRY. 261 deeper colour namely yellowish-red to dark red and it is suggested that they have the quinonoid constitution for example N<Co*N(HNos)>C*CH CMe-CH :CHPh. A mixture of the mono- and di-benzylidene derivatives is formed even when less than 1 gram-molecule of benzaldehyde is used for each gram-molecule of the pyrimidone but with an excess of the aldehyde the dibenzylidene compound alone is formed. The two can be fairly readily separated as the di-compound is only sparingly soluble in alcohol. 4-Benzylidenemeth y I-6-methy I- 2 -p yrimidone C,,H,,ON cry stallises from aqueous alcohol to which a few drops of ammonia solution have been added in slender colourless needles m.p. 18S-1S9° after sintering at 184O. The presence of the least trace of acid produces a yellow coloration. It yields a colourless sodium salt a yellow sulphate an orange- yellow hydrochloyide and an orange-coloured nitrate. The dibenxylidene derivative C,,H,,ON crystallises from boiling methyl alcohol in glistening golden-yellow needles which turn brown at 230° sinter a t 270° and melt and decompose at 275". The salts have a red colour and are sparingly soluble. The p-hydroxybenxylidene derivative C13H1202N2 separates from methyl alcohol as a dark yellow crystalline powder m. p. 278-280° (decomp.) ; it dissolves in mineral acids,. yielding solutions with a blood-red colour and in sodium hydroxide to a yellow solution.J. J. 8. New Synthesis of Pyrazine Derivatives by the Action of Aromatic Nitroso-o-hydroxy-compounds on Acetaldehyde in the Presence of Ammonia or Primary Aliphatic Amines. MARTIN LANGE (Ber. 1909 42 574-5'77).-An account of this work has already a p p e b d i n D.R.-P 196563 (Abstr. 1908 i 839). W. H. G. Indigoid Dyes Derived from Phenyl~sooxazolone. ANDR~ WAHL (C'ompt. rend. l909,148,362-354).-Since phenylisooxazolone behaves as though it contains the grouping *CH,*CO (compare Wahl and Meyer Abstr. 1908 i 368) it reacts with isatin chloride yielding 3 -phen ylisooxazoZone-2-indol~ crystallising in garnet-red needles with a bronzy reflex. The corre- sponding indigoid dyes derived from the three methoxyphenyliso- oxazolones form reddish-brown crystals with a coppery reflex.The solutions of the compounds in aqueous sodium hydroxide or carbonate are almost colourless and yield the parent coloured compounds on the addition of acid. It is probable that the isooxazolone nucleus is hydrolysed by the alkali and is regenerated on the addition of acid CPh(N0H) C(CO,Na):C<CO>C,H N H -+x:EF>C C<CO>C,H,. NH The yellow solutions obtained by treating the substances with VOL. XCVI. i t >c:c<;;>w 7:CPh 0-co262 ABSTRACTS OF CHEMICAL PAPERS. sodium hyposulphite do not yield the parent compounds when treated with acids or oxidising agents for example hydrogen peroxide. The Zeuco-derivatives apparently do not combine with animal or vegetable fibres. Ethyl anisoylacetate has b. p. 189-190'/10-12 mm. (decomp.) (compare Schoonjans Abstr.1898 i 425). The following compounds were prepared o-methoxyphenylisooxazolone crystallises in white needles m. p. 106' ; m-methoxyphenylisooxazolone forms white plates m. p. 115'; the p-derivative forms white needles m. p. 143' (compare Schoonjans loc. cit.). The Antique Purple Dye from Murex brandaris. PAUL FRIEDLANDER (Bey. 1909 42 765-770. Compare Abstr. 1907 i 867).-This dye obtained from the above mollusc is now shown to be 6 6'-dibromoindigotin C,,H,O,N,Br by a direct comparison with the synthetic dye as regards its spectroscopic behaviour colour reactions and solubility. The influence on the colour of indigotins where positions 6 and 6' are occupied is emphasised. Preparation of Indazyl Derivatives by means of Ortho- ketonic Hydrazinea.PAUL CARR~ (Compt. rend . 1909 148 491-494." Compare Freundler Abstr. 1904 i lOS).-The following compounds are obtained when o-nitrobenzophenone is reduced by zinc dust and alcoholic sodium hydroxide (1) benzaldehyde ; (2) o-amino- benzophenone m. p. l l O - l l l o (compare Geigy Abstr. 1885 1236) ; this reacts with phenylthiocarbimide giving o-phenylbenzophenone- thiocarbamide NHPh*CS*NH*C,H,*COPh m. p. 156-157' ; (3) 4 4'-diamino-2 2'-dibenzyldiphenyl; (4) 4 4'-diamino-2- benxyldiphenyl NH,-C,H,:C,H,(NH,)*CH,Ph white prisms m. p 209' ; the hydrochlorade decomposes at ZOO'; (5) a minute quantity of a white substance having the characteristic properties of an indazyl derivative. o-Axobemophenone COPh*C,H,*N~*C,H,=COPh orange-red crystals m.p. 201-202° has been prepared by oxidising o-azodiphenylmethane (this vol. i 121) with chromic acid. When treated successively with ammonium hydrosulphide and mercuric oxide it forms W. H. G. W. R. C P h N 2-o-benxophenone-3-phenylinda~ole C,H,< I )Nf?,H,*COPh white crystals m. p. 134-135'. w. 0. w. [Anthrapyridone Derivatives.] BADISCHE ANILIN- & SODA- FABRIK (D.R.-P. 205095).-Those anthrapyridones containing a halogen atom in the para-position to the imino-group readily yield p-arylaminoanthrapyridones on heating with aromatic bases. These products on sulphonation yield fast wool dyes. 6-p-Tolylanzino-4-methylanthrapyridone reddish-brown crystals is produced by heating together 6-chloro-4-methylanthrapyridone p-toluidine and anhydrous sodium acetate. 4 6-Di-p-tolylaminoanthrapyridone is similarly obtained from 4 6- dichloroanthrapyridone.G. T. M. * and Bull. SOC. chint. 1909 [iv] 5 283-285.ORGANIC CHEMISTRY. 263 Preparation of Amino- Alkylamino- or Arylamino-snthra- pyridones. FARBENFABRTKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 201904. Compare Abstr. 1908 i 456).-The anthrapyridones which contain negative substit2ents in the benzene rings are readily acted on by primary or secondary bases giving rise to amino- derivatives which are either dyes or may be employed is the production of colouring matters. 6 -Me thylamino-3-methylanthrapyridone (an- nexed formula) separates in red crystals from a /\ pyridina solution of methylamine and p-bromo- EH NMe anthrapyridone after heating at 120" for five hours. 6 -p-To1 yl amino- 3-m et hylant hrapyridone is pro- ' ' duced by heating at 160-170' p-toluidine with either p-methoxyanthrapyridone or p - bromo- anthrapyridone; its sulphonic acid dyes wool in CO "><"JHM violet-red shades which are very fast to light. G.T. M. [Production of Iminazoles from 1 8-Naphthylenediamine.] FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 202354).-By condensing 1 8-naphthylenediamine with the polybasic acids or their anhydrides a series of coloured condensation products of the iminazole series are obtained Phthalic anhydride gives rise successively to the products ClSH,,O2N2 and ClsHloON2 represented respectively by formulae I and 11. co The former is a yellow compound m. p. 185'; the latter separates from glacial acetic acid in red needles with a golden reflex m.p. 227-228O. Similar condensation products are obtained by the use of citric acid maleic anhydride succinic anhydride and o-benzoic sulphinide. G. T. M. Preparation of Anthrapyrimidones. FARBWERKE VORM. MEISTER LUCIUS & BR~~NING (D.R.-P. 205038)-A new class of anthracene derivatives the anthrapyrimidones (formula I) are pro- duced by condensing the a-aminoant hraquinones or the a-alkylamino- anthraquinones with urethane alcohol and water being eliminated. The reaction is a general one. 1 -Anthrapylrimidone (with H replacing R in the formula) golden- yellow needles m. p. above 280' is obtained by heating together a-aminoanthraquinone urethane and zinc chloride at 170-180'. 1 5-Anthradipyrimidone (11) a brownish-red powder is similarly VOL.XCVI. i. 2.5264 ABSTRACTS OF CHEMICAL PAPERS. produced by heating together in nitrobenzene 1 5-diaminoanthra- quinone urethane and zinc chloride. co co /\A/\ I I I I \/\/\/ S I N jSR \/ co /'\ "7 w I C /!\A/\ I I I I \/\/\/ 8 1 N NH \/ CO Preparation of Anthrapyriinidon es. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 2059 14. Compare preceding abstract). -1-Anthrapyrimidone has now been prepared by condensing the a-halogenated anthraquinones with carbamide in the presence of metallic salts ; thus 1 -bromoanthraquinone car bamide and copper chloride when condensed give this product together with water and hydrogen bromide. G. T. M. 8 8'-Diquinolylcarboxylic Acids. ZYG. VON JAKUBOWSKI and STEFAN VON NIEMENTOWSKI (Ber. 1909 42 634-654).-Previous to this investigation no quinolylcarboxylic acids were known and the first to be examined are those derived from 5 5'-dimethyl-8 8'- diquinolyl (Abstr.1905 i 300). The oxidation of this compound is a matter of considerable difficulty ; acid or alkaline potassium per- manganate nitric acid chromic acid in acetic acid solution fusion with potassium hydroxide and lead peroxide were ineffective. Chromic anhydride in sulphuric acid was found to be suitable and the mono- or di-carboxylic acid could be obtained /-\N N/-\ by altering the conditions. 5-Methyl- \-/ \-/ 8 8'-diquinolyl-5'-ca~boxylic acid (an- Me( \-C)CO,H nexed formula) was prepared by con- centrating a mixture of dimethyl- quiuolyl (1 part) 50% sulphuric acid (10 parts) and chromic anhydride (1.4 parts) at 100' until the chromic acid disappears.The purification is carried out by neutralising first with ammonia then repeatedly crystallising the barium salt and afterwards converting into potassium salt and recrystallising this. The acid forrris a fine white micro- crystalline powder m. p. 331-332' (decornp.) and is amphoteric in character. The following salts have been prepared ammonium C2,,H,,O2N2(NH4),3H,0 rhombic plates m hich decompose a t 120' into water ammonia arld acid ; potassium C20H,302N2K,5H20 leaflets ; barium C4,H,,0,N,Ba 12H ,O leaflets and a silver eal t. Also the following the hydrochloride C,,H,402N2,2HCI,H20 ; nitrate -/ 0,0H,40,& 29ZHNO37ORGANIC CHEMISTRY. 265 and 8ulphate all of which crystallise in leaflets.8 8'-DiquinoZyZ-5 5'- dicarboxylic acid C,,H1,0,N2 is obtained from the reaction mixture of the base chromic anhydride and sulphuric acid after twenty-four hours at the ordinary temperature and is purified first by conversion into the barium salt. The acid is next separated from small quantities of the monocarboxylic acid by treatment with hydrochloric acid the monocarboxylic acid being soluble in dilute acid whereas the dicarb- oxylic acid has no basic properties and is insoluble in this menstrum. It is a microcrystalline powder m. p. 415' (decomp.) and has been characterised by the c~mmonium C,oH,,O,N,( NH,),,H,O potassium C2,Hio0,N2K2,5H,0 barium C20H,o0,N2Ba,7~H20 and silver saltP all of which crystallise in leaflets and are more easily soluble than the corresponding monocarboxylates.Distillation of the monocarboxylic acid under diminished pressure leads to the formation of carbon dioxide and 5-methyl-8 8'-diquinolyZ C,,H,,N which crystallises in colourless diagonal plates m. p. 21 1-5-212' ; the ?hydrochloride Ci,H,,N2,2HC1,5H,0 forms needles ; the nitrate C19H,,N2,2HN0,,3H,0 leaflets ; sulphate leaflets and the platinichloride C,,Hi,N2,H2PtCI orange crystalp. Dry distillation of the dicarboxylic acid yields an acid and a base. The acid 8 8'-diquinolyl-5-carboxylic acid C19H1202N2 is a white micro- crystalline powder m. p. 310-312" is amphoteric in character and is identical with the acid obtained by the oxidation of 5-methyl-8 8'- diquinolyl with chromic anhydride and sulphuric acid. The ammoniuni ClgHl102N2(NH ) 4H,o and barium salts C,,H,,O,N,Ba llH,O have been prepared."i'he base C,,H,,N forms colourless needles m. p. 182' (not sharp) and is resolved by fractional crystallisation of the hydriodide into a small quantity of 8 S'-diquinolyl and an isomeric diquinolyl m. p. 187'. The dicarboxylic acid has been synthesised in the following way. Oxidation of 2 2'-dinitro-4 4'-dimethyldiphenyl by potassium di- chromate and sulphuric acid leads to the formation of mono- and di-carboxylic acids in the ratio of 1 4. These are separated by fractional precipitation from a solution of the ammonium salts by hydrochloric acid 2 2'-Dinitro-4-melhyZdiphenyZ-4'-carboxylic acid (annexed formula) forms crystals m p. 335-5-236' ; the ammonium snlt baraum Me(-\-/-\CO,H salt C,,H,,O,,N4Ba,4H,O and silver salt have been prepared.2 2l'-Dinitrodiphenyl- 4 4'-dicarboxyZic acid C,,H,O,N forms white crystals m. p. 335-337' ; its ammonium salt and barium salt Cl4H,OsN,Ba,3H,O are yellow and the methyl ester has m. p. 155-156' (Ullmann and Bielecki Abstr. 1901 i 586 give 159-160'). By the reduction of these dinitro-compounds with tin and hydrochloric acid the corre- sponding diamino-derivatives :are obtained. 2 2'-Diamino- 4-methyl- diphenyl-4'-carboxylic acid C1,H1,O,N forms stout yellow crystals 1x1. p. 169-171" ; the hydrochloride C,,Hi,0,N,,2HC1 has m. p 280-285O (decomp.) whilst 2 2'-diamznoctaphenyl-4 4'-dicurboxylic acid C,,H,,O,N forms very small rhombic plates m. p. 307-309'; CigHi4N29 H,So 3H20 NO NO -/ \-/ '1L 2266 ABSTRACTS OF CHEMICAL PAPERS.its diacetyt derivative C,$1606N23 has m. p. 250’ ; the hydqsochloride C,,H,,O,N,,HCl is insoluble. Using arsenic acid as the oxidising agent this dicarboxylic acid undergoes Skraup’s reaction forming 8 8’-diquinolyl-5 5’-dicarboxylic acid apparently identical with the acid obtained from dimethyldiquinolyl yet on dry distillation under reduced pressure pure 8 8’-diquinolyl (m. p. 205’) was obtained. The relationships of these two isomeric diquinolyls are discussed. It is not possible to decide yet whether they are structural isomerides ; that of m. p. 187” might be the 8 7’- or /\/\ /\/\ 8 6’-modification but this is considered I l l 1 1 to be improbable. They may be stereo- \/\/ isomerides of the annexed formulse ; their simultaneous production from the same dicarboxylic acid would support this and the difference in behaviour of the acid I 1 I 1 1 obtained from different reactions might be \/ \/\/ accounted for by a certain fine difference between the acids themselves.Lastly (1.1 (11.) they may be analogous to the ana-substituted quinoline isomerides which have not yet been explained (Lellmann and co-workers Abstr. 1887 502 737 973; 1888 296 499). W. R. Preparation of 4-Dimethylamino-1-phenyl-2 3-dimethyl- 5-pyrazolone SOCIET~ CHIMIQUE DE L’AVANCHET (D.R.-P. 203753). -The alkylation of 4-amino-1-phenyl-2 3-dimethyl-5-pyrazolone leads to quaternary compounds and the yield of (( pyramidone ’’ (4-dimethyl- amino- 1-phenyl-2 3-dimethylpyrazolone) is accordingly diminished. An indirect alkylation can be effected by treating the aminopyrazolone with nitrosodimethylamine either alone at 110’ or in the presence of copper powder MeC=zC*NH2 Me? *N :N*NMe Mek 60 +NO*NMe -+ MeN CO -+ \/ NPh Me~==S*XMe MeN CO +N,.\/ NPh G. T. M. \/ NPh Preparation of 5 5-Dialkyliminobarbituric Acids (5 5-Di- alkylmttlonylguanidines). BASLER CHEMISCHE FABRIK (D. R.-P. 204795).-The dialkylmalonic acids can be condensed with guanidine when the acid and a salt of the base are suspended in concentrated sulphuric acid and the mixture treated with fuming sulphuric acid chlorosulphonic acid or phosphoric oxide 5 5-Diethylmalonic acid and guanidine thiocyannte or hydro- chloride were thus condensed to 2-imino-4 6-dioxy-5 5-diethyl- pyrimidine (diethylmalonylguanidine) and 2-imino-4 6-dioxy-5 5- dipropylpyrimidine was similarly prepared from 5 5-dipropylmalonic acid and guanidine hydrochloride G.T. M.ORGANIC CHEMISTRY. 267 Intramolecular Transformations. OTTO DIMROTH (Annalen 1909 364 183-226).-1t has been shown previously that esters of 5-hydroxy-1 -pheny 1-1 2 3 - triazole-4-carboxylic acid readily undergo desmotropic change (compare Abstr. 1905 i 98 384). With the object of ascertaining whether the corresponding 5 -amino-compounds behave in a similar manner these substances have been prepared and their chemical behaviour studied. It is found that they also undergo intramolecular change when fused yielding isomerides which unlike the parent substances possess acidic properties. The change under these conditions is a reversible one but complete conversion into the acidic form may be effected by treating the neutral isomeride with sodium ethoxide or pyridine.The velocity with which the reaction proceeds in this case unlike that of the corresponding hydroxy-derivative is exceedingly small. The isomeric esters when hydrolysed yield isomeric acids which wheu heated evolve carbon dioxide yielding the same acidic substance m. p. 139'. This substance is not 5-amino-1-phenyl-l 2 5-triazole consequently it must be derived from the ester having acidic pro- perties. It is also found that 5-amino-1-phenyl-1 2 3-triazole and 5-amino-1 4-diphenyl-1 2 3-triazole when fused completely change into their corresponding isomerides which are also soluble in alkalis. Consideration of the properties of the acidic isomerides shows that these are not the result of a desmotropic change ; instead i t is de- finitely proved that they are produced by the phenyl group changing places with a hydrogen atom of the amino-group.1 2 3-Triazoles may be regarded as cyclic diazoamino-compounds and this intra- molecular change is similar to that which diazoamino-compounds are known to undergo when treated with bases. The position of the imino-hydrogen atom in the ring is not yet definitely known. [With G. W~x~~~.]-&fethyl 5-amino-1-phenyl-1 2 3-triaxole-4 >C*NH is obtained by the condensation G€ ccwboxylate I I phenylazoimide with methyl cyanoacetate in the presence of sodium methoxide ; it crystallises in small white needles m. p. 173' and is converted by boiling with pyridine or sodium ethoxide dissolved in alcohol for three hours into methyl 5-anilino-1 2 3-triaxole-4- carbozylate Cl,H 002N4 crystallising in groups of small slender needles m.p. 154'. The corresponding eth9Z ester CllH1202N4 forms slender felted needles m. p. 129-130'; it passes into the isomeric ethyl 5-amino- 1-phenyl-1 2 3-triazole-4-carboxylate to the extent of 33-34% in alcoholic solution and 42-44% in benzene; the acetate CI3Hl3O3N4 crystallises in needles m. p. 90°. [With G. WERNER and FRITZ H~ss.]-5-Amino-1-phen?/&l 2 3- triaxole-4-carboxylic acid C,H,O,N formed by boiling the corre- sponding ester with alcoholic potassium hydroxide for thirty minutes crystallises in small prisms m. p. 142O (decomp.) ; the isomeric 5-unilinc- 1 2 3-triazole-4-carboxylic acid obtained from its ester by boiliug with alcoholic potassium hydroxide for twelve to fifteen hours crystallises in four-cornered scales m.p. 1 5 3 O (decomp.). Either of the preceding N- NPh N *C( C0,Me)268 ABSTRACTS OF CHEMICAL PAPERS. acids when fused evolve carbon dioxide and yield 5-anilinotriazole and when warmed with 20% sulphuric acid yield glycollic acid phenylamidine OH* CH,*C( NH) *NHPh crystallising in colourless needles m. p. 130'; it is very unstable and is decomposed by dilute alkalis forming glycollanilide and ammonia. [With J. MARSHALL and FRITZ HESS.] -1-Phenyl-1 2 3-triaxole-5- carboxylic acid hydruzide C~HQON~ obtained by heating the ester (Abstr. 1902 i 403) with hydrszine hydrate under pressure at 120' forms long colourless needles m.p. 143'; i t is converted by nitrous acid into the axoimide glistening leaflets m. p. 99' (decomp.) and by boiling ethyl alcohol into the urethane C,,H,,O,N colourless needles m. p. 98'. The latter substance when boiled with dilute alkali yields n g N P h > ~ * ~ ~ crystallising in 5-amino-l-phenyl-1 2 3-triaxole N-CH needles or leaflets m. p. 110'. C,H,O,N,Cl prepared by the action of phosphorus pentachloride on methyl l-phenyl-5-triazolone-4-carboxylate~ crystallises in a labile form colour- less needles m. p. 85-86') and a stable form compact rhombic crystals m. p. 87-88O. It may also be obtained by the action of amyl nitrite on a solution of methyl 5-amino-1-phenyl-1 2 3-triazole- 4-carboxylate in methyl alcohol containing hydrogen chloride.5-Chloro-1 -phenyl-l 2 3-tric6xole-4-cc6rboxylic acid crystallises in slender white needles m. p. 136' (decomp.) and when fused yields 5-chloro-1 -pheizyZ-l 2 3-triaxoZe7 C,H,N,Cl slender white needles m. p. 50'. The latter substance is converted by alcoholic ammonia at the ordinary temperature into 5-amino-1 -phenyl-1 2 3-triazole which when diazotised and coupled with /3-naphthol yields 1-phenyltriaxole-5- azo-/3-naphthol CI8Hl30N5 crystallising in red plates m. p. 2 1 5 O 5-AnzZznotriaxoEe C,B,N prepared by fusing 5-amino-1 -phenyl- 1 2 3-triazole or as described above crystallises in large glistening leaflets m. p. 139'; i t forms a silver salt C,H7N,Ag and a hydro- chloride m. p. 128'; the acetate CloHloON4 crystallises in white needles m.p. 137-138' ; the urethane CI1Hl2O2N4 forms white leaflets m. p. 147' ; the nityoso-derivative C,H70N5 forms yellow crystals m. p. 1 15-1 16' (decomp.). 5-Amino-1 4-diphenyltriazole (compare Dimroth and Werner Abstr. 1903 i 127) when diazotised and coupled with &naphthol yields 1 4-dipl~eizyltriasole-5-azo-/3-naphthol C2,H170N5 red needles m. p. 204'. The diazo-solution when treated with cuprous chloride yields 5-chloro-1 4-diphenyltriazole (compare A bstr. 1905 i 98). [With FRITZ H~~~.]-5-Anilino-4-phenyltriaso!e C14H12N4 prepared by boiling 5-amino-1 4-diphenyl triazole with pyridine crystallises in needles m. p. 167'; it forms salts with alkalis and acids. 5-Methylamino-1 -pheizyl-l 2 3-kiazole C,H,,O is obtained by the action of methylamine on 5-chloro- 1 -phenyltriazole ; it crystallises in slightly yellow compact prisms m.p. 102' and when boiled with water or pyridine passes into 5-anilino - 1 -inethyl-1 2 3- triaxole C9H10N4 white leaflets m. p. l'i2O. Metlhyl 5-chloro-1 -phenyl- 1 2 3-triaxole-4-ccirboxylate (demmp. !.ORGANIC CHEMISTRY. 269 Methyl 5-hydroxy-1 -methyltriaxoZe-4-carboxyZate C,H,03N3 prepared by the action of methylazoimids on methyl malonate in the presenoe of sodium methoxide forms hexagonal crystals m. p. 136'; when fused it passes into methyl 1 -methyl-5-t&zoZone-4-carbpxyZ~te T M e g C o > ~ ~ - ~ ~ ~ e N-N crystallising in yellow needles m. p. 75'. Either the enolic or ketonic ester when treated with phosphorus pentachloride yields methyE li-chloro-l-methyZtriaeoZe-4-carboxyZate crystallising in long white leaflets m.p. 112' ; the corresponding acid crystallises in white needles m. p. 167' and passes into 5-chloro-1-methyl-1 2 3-triazole when fused which substance when treated with aniline yields 5-anilino- 1-methyl-1 2 3-triazole identical with that just described. 5-Chloro- 1-phenyl-1 2 3-triazole is converted by aniline into 5-andimo- I-phenyltricczole C,4H!,N4 small glistening square plates m. p. 142' and by sodium ethoxide at the ordinary temperature into 5-ethoxy- 1-phenyl-1 2 3-triazole (compare Abstr. 1905 i 98). Action of Sulphur on m-Tolylenediamine. I. and 11. GUSTAV SCHULTZ and HEINRICH BEPSCHLAG (Ber. 1909 42 743-752 753-757).-m-Diamines are characterised by the ease with which elementary sulphur is introduced into the molecule.The gentle boiling of alcoholic m-tolylenediamine and sulphur for five to six hours leads t o the evolution of hydrogen sulphide and the formation of a mixture of polysulphides from which dithio-m-tolylenediamine (annexed formula) m. p. 215' has been isolated in tufts of yellow needles by NH /\ /\NH fractional crystallisation from alcohol. 21 I I I The constitution of the disulphide is proved from its formation by the reduction with stannous chloride and hydrochloric W. H. G. Me Me \/-s*s- \/ NH2 acid of 2 3 2' 3'-tetranitroditolyZ 5 5'-disulphide C,H2Me(N0,)2*8,*C,H,Me(N02)2 which decomposes before melting a t 265' and is obtained by the action of an alcoholic solution of crystallised sodium sulphide on alcoholic 5-chloro-2 4-dinitrotoluene. hTH Dithio-m-tolylenediamine forms a bernzoyl derivative C42H8,04N 4'2 9 and a benzylidene compound C,,H,,N4S m.p. 152-153' yields 4- acetylamino-l 5-dimethylbanzthiazole m. p. 180-18 lo by wLtrming with zinc dust glacial acetic acid and acetic anhydride and gives by treating its solution in dilute hydrochloric acid with hydrogen sulphide 2 4-diamino-m-tolyl mercccptan which forms yellow needles and on account of its extreme oxidisability is best kept in the form of the hydrochloride C7H,,N,S,,2HC1. Since dithio-m-tolylenediamine dissolved' in boiling alcohol takes up per mol. six atoms of sulphur without evolution of hydrogen sulphide giving a mixture of polysulphides whilst 2 4-dinmino-m- tolyl mercaptan under similar conditions combines with sulphur with the evolution of hydrogen sulphide giving the same mixture of poly- sulphides it is probable that the eqtrapce of sulphur into m-folylene-270 ABSTRACTS OF CHEMICAL PAPERS diamine is due to the initial formation of the mercaptan which then changes into the disulphide t o which the addition of sulphur leads to the formation of higher unstable polysulphides.These polysulphides then react with the unchanged base and with the intermediately formed mercaptan to give the mixture of lower stable polysulphides Preparation of o-Diaminopyrimidines c o n t a i n i n g Halo- genated Acyl Groups. FARBENFABRIREN VORM. FRIEDR. BAYER & Co. (D.R.-P. 206454).-It has now been found that 4 5-diaruino- pyrimidine derivatives having the general formula which is ultimately isolated c.s. >C*NH NX*CO- y:c <NX*C(NH,) (where X is hydrogen or an alkyl group and Y an oxygen or sulphur atom or an imino-or a cyanimino-group) readily react with halogenated carboxy-acids to give derivatives with an acyl group in position 5. 5-CidoroacetyZ-4 5-diamino-2 ; 6-dioxy-1 .3-dimethylpyrimidine CO<zge. e* CO-- C(NH21>C*NH*CO* CH,Cl white crystals m p. 21O0 is produced by heating together a t 120' chloroacetic acid and 4 5-diamino-2 6-dioxy-1 3-dimethylpyrimi- dine. ~-ChZoro-a-hydroxypropionyZ-4 5-diamino-2 ; 6-dioxypyrimidine e*CO- >C~NH~CO~CH(OH)~CH,C~ NMe*C(NH,) m. p. 215q is obtained in a iimilar manner by replacing chloroacetic by P-chlorolactic acid in the foregoing condensation. Preparation of 5-Oximino4-iminopyrimidine Derivatives.FABBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 206453).- 5-Oximino-4-imino-2 6-dioxypyrimidine is produced by condensing ethyl oximinocyanoacetate and carbimide with sodium ethoxide in absolute alcohol. A similar condensation between ethyl oximino- cyanoacetate dicyanodiamide and potassium ethoxide leads to the formation of 5-oximino-4-imino-6-oxy-2-cyanoiminopyrirnidine G. T. M. CNXC<;&G!)>C:NOH red needles insoluble in water and the organic media but yielding sparingly soluble salts with aqueous alkalis. Other condensations with ethyl oximinocyanoacetate are indicated in the patent but the products have already been described (compare Abstr. 1900 i 416 ; 1901 i 54). Derivatives of Osotetrazine and of Osotriazole.HANS VON PECHMANM and WILHELM BAUER (Ber. 1909 42 659-674).-By oxidising the dibenzoylhydrazones of diacetyl and of glyoxal to the corresponding dibenzoylosotetrazines and hydrolysing the latter the authors hoped to obtain osotetrazine and its dimethyl komologue. The hydrolysis of the dibenzoylosotetrazines however yields the corre- sponding amino-osotriazoles and thus furnishes another addition to the several recent instances of the conversion of tetrazines into amino- triazoles. Consequently the substances described previously (Abstr. G. T. M.ORGANIC CHEMISTRY 271 1900 i 3 14) as benzoyldimethylosotetrazine and dimethylosotetrazine are 1-benzoylamino-3 4-dimethyl-1 2 5-triazole m. p. 95O and 1-amino-3 4-dimethyl-1 2 5-triazole m. p. 95' respectively.The evidence for the constitutions of the two compounds is the following (1) By benzoylation the original dibenzoyldimethylosotetrazine is not reproduced but Stol1P;'s 1-dibenzoylamino-3 4-dimethyl-1 2 5-tnazole m. p. 115' (this vol. i 123); (2) the formation of the benxylidene compound I >N*N:CHPh m. p. SOo ; (3) by the action of nitrous acid aminodimerhyl-1 2 5-triazole yields 3 4-dimethyl-1 2 5-triaxole m. p. '70" (with 3H,O m. p. 97") the constitution of which is proved by nitrating 1-phenyl-3 4-dimethyl-1 2 5-triazole (Abstr. 1888 1287) in the cold reducing the nitro-compound CIg7:h0,N m. p. 227O to 1-aminophenyl-3 4-dimethyl-1 3 5-triaxole I >N*C,H,*NH2 m. p. 132' and oxidisicg the latter by potassium permanganate and dilute sulphuric acid whereby 3 4-dimethyl-1 2 5-triazole identical with the preceding is obtained.An aqueous solution of diacetyl and benzhydrazide yields diacetyl- benzoylhydrazone CH,*CO-CMe:N*NHBz m. p. about 167' (completely at 185O) which by recrystallisation from hot glacial acetic acid gives diacetylbenzoylosaxone NHBz*N:CMe-CMe:N*NHBz m. p. 2S6.5" (decomp.) which is also obtained by heating an excess of alcoholic benzhydrazide and diacetyl for six hours at 100'. The osazone by oxidation with alkaline 25% potassium ferricyanide yields StollB's 2 3-dibenzoyl-5 6-dimethyl-1 2 3 4-tetrazine (loc. cit.) m. p. 1409 which differs from the corresponding dipheuyltetrazine in being colourless and in not being capable of reduction to the -0sazone. By hydrolysis with concentrated hydrochloric acid the dibenzoyl- dimethyltetrazine yields 1 -benzoylamino-3 4-dimethyl-1 2 5-triazole.I-Amino-3 4-dimethyl-1 2 5-triazole obtained by hydrolysing the preceding compound in a sealed tube forms a hydrochloride m. p. 131' mercurichloride m. p. 145O picrate m. p. 124-125' and a platinichloride decomposing at 215O ; it is unaffected by mild oxidising agents is converted into diacetyl' by potassium dichromate or lead peroxide and sulphuric acid and yields PPyy-tetrabrornobutane by the action of bromine water. Compounds similar to the preceding have been obtained from glyoxal. When the sodium hydrogen sulphite compound is heated with dilute sulphuric acid until sulphur dioxide is eliminated the solution treated with an excess of sodium acetate and heated with benzhydrazide ylgoxalbenxoylogazone NHBz*N:OH*CH:N*NHBz is obtained as a white powder which melts above 300" and gives by oxidation with alkaline potassium ferricyanide 1-benxoykamino-1 3 5-triaxole CMe:N CMe:N CMe:N >N*NHBz QH:N CH N m.p. 151' which by hydrolysis with dilute hydrochloric acid in a sealed tube at 90-100' yields 1-amino-1 2 5-triazole m. p. 51' (picrate m. p. 130° decomp. ; hydrochloride m. p. 114" decomp.) from which Pech- mann's osotriazole is obtained by the action of nitrous acid. C. 8.272 ABSTRACTS OF CHEMICAL PAPERS. Oxidation of Uric Acid in Alkaline Solution. ROBERT BEHREND and ROLAND SCHULTZ (Annalen 1909 365 21-37).- Attempts have been made to confirm thd conclusion previously drawn (Abstr. 1904 i 950) namely that hydroxyglycurilcarboxylic acid is first formed during the oxidation and that this is transformed partly into uroxanic acid and partly into a substance which yields allantoin when acidified.When a larger quantity of permanganate was used the chief product mas biuret together with a small amount of the potassium salt of a dibasic acid U,H70,N, It is possible that the latter compound was formed by the oxidation of guanine contained in the crude uric acid. Attempts have been made to establish the constitution of uroxanic acid. Behrend's formula (2oc. cit.) namely diureidomalonic acid C(C0,H)2(NH*CO*NH,,)2 is supported by a study of the alkali salts and also by the behaviour of the acid towards methyl alcohol. The normal potassium salt is neutral t o litmus and phenolphthalein in aqueous solution whereas the acid potassium salts of diureides of the type of uric acid are distinctly alkaline.The behaviour of the normal salts is thus completely in harmony with the view that uroxanic acid is a substituted malonic acid containing two carboxyl groups. The readiness with which the acid loses carbon dioxide and yields allslntoic acid when shaken for several days with cold 95% methyl alcohol is also in hirmony with this formula whereas Medicus' formula (Bey. 1876 9 462) would necessitate the rupture by cold methyl alcohol of a ring whichis stable even in the presence of concentrated alkali. Norn~cd pheny&&mxine urozunate C,H,O,N,,~C,H,N crystallises in colourless plates m. p. 130-132' (decomp.) after turning yellow at 120'.Aniline and hydroxylamine also yield sparingly soluble salts ; the latter has M. p. 155" (decomp.). When boiled with water the phenylhydrazine uroxanate yields the phenylhydrazine salt of rnesoxalic mid phenylhydruzone which crystallises in yellow needles. It darkens at 140-1550" melts a t 154-15S0 solidifies again a t 160" and melts a second time at 183" (decomp.). Hydrochloric acid decomposes this salt yielding rnesoxa lic acid pheng W ydruzone C,H,O,N which crystal lises in minute needles m. p. 170-171" (decomp.). When heated with water uroxanic acid yields allanturic acid mesoxalic acid and carbamide. Production of Azoxy- and Azo-compounds of the Benzene Series. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 204653).-The sulphides of the heavy metals can be employed in the production of the reduction products of nitrobenzene.This substance when boiled with iron pyrites and 60% aqueous sodium hydroxide yields about 90% of azoxybenzene. When the reaction is carried out at 140' further reduction occurs and 85-90% of azobenzene is obtained. G. T. M. p-Nitrodiazobenzene Chloride. HANS T. BUCHEREB and S. WOLFF (Ber 1909 42 881-887).-111 preparing a nitrous acid-free C15H1604N49 4 H2°9 J. J. 5.ORGANIC CHEMISTRY. 273 solution of p-nitrodiazobenzene by acidifying the sodium isodiazotate (" nitrosamine " paste) the authors noticed that the solution always showed the presence of free nitrous acid and the paste when acidified with acetic acid instead of hydrochloric acid gave this reaction only after some time.The conclusion is drawn that the nitrous acid is produced by the hydrolytic decomposition of the diazonium hydroxide into nitrous acid and p-nitroaniline. After proving that excess of nitrous acid in a diazo-solution can be removed by means of hydrogen peroxide or potassium permanganate (whereby it is oxidised to nitric acid) the authors investigated the action of various reagents on a solution of p-nitrodiazobenzens chloride in order to ascertain if on slowly liberating the diazonium hydroxide the above reaction would proceed which would be shown by the combination of the p-nitroaniline with some of the diazo-salt present to form the corresponding diazoamino-compound. The addition of solutions of sodium hydroxide hydrogen carbonate carbonate acetate ammonia ammonium carbonate soap or a mixture of soap and sodium car- bonate gave rise to the formation of a diazoamino-compound in varying degrees but with ammonium acetate an almost quantitative yield of p-dinitrodiazoaminobenzene was obtained.I t is considered that this is due to the rapid removal of the nitrous acid liberated in the hydrolysis owing to the formation of ammonium nitrite which at once decomposes. The addition of ammonium chloride or carbamide to the diazo-solution produced no appreciable effect. Preliminary experiments with diazotised sulphanilic acid and o-nitrodiazobenzene chloride showed that the reactions do not proceed quite in the same may as those described above. J. C. C. Preparation of p-Aminodiaeobenzene and its Derivatives. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P.205037).-Acetyl-p- phenylenediamine is diazotised with sodium nitrite in hydrochloric acid a further quantity OF hydrochloric acid is added and the sodium heated at 70° for one hour. A t the end of this time the solution no longer gives the azo-coupling reaction with sodium P-naphthol-3 6- disulphonate ( R salt) in cold aqueous sodium carbonate. This diazo- solution now contains p-aminodiazobenzene which only gives an azo- derivative with l? salt either very slowly at the ordinary temperature or more rapidly on warming. G. T. M. Iodothyreoglobulin. A. NURENBERG (Biochem. Zeitsch. 1909,16 87-1 lo).-Iodothyreoglobulin is the name given by Oswald to the protein substmce in the colloid matter of the thyroid gland which contains iodine.The elementary analyses given are very like those of Oawald. Among its hydrolytic cleavage products arginine histidine (P) lysine tyrosine glutamic acid glycine alanine leucine phenylalanine aspartic acid and proline were separated. The iodine is united to the aromatic groups especially to tyrosine and trypto- phan. W. D. H. Partial Hydrolysis of Certain Proteins. EMIL ABDERHALDEN (Zeitsch. physiol. Chem. 1909 58 373-389).-The distinction274 ABSTRACTS OF CHEMICAL PAPERS. between proteins will probably rest not wholly in the kind and amount of the final cleavage products so much as on the way the individual amino-acids are linked together. For this purpose partial hydrolysis with the resulting yield of polypeptides is of great utility. I n the present preliminary attempt in this direction polypeptides were separated from the partial hydrolysis of edestin elastin and keratin.From the digest amino-acids were precipitated by phospho- tungstic acid and the polypeptides were separated from the filtrate ; one of these from edestin contained glutamic acid and tryptophan another glutamic acid tryptophan and leucine and a third tyrosine glycine and leucine. From keratin a polypeptide containing cystine g-lu- tamic acid and tyrosine and another containing histidine and leucine were separated. From elastin I-leucy 1-d-alanine and d-alanyl-Z-leucine were separated. W. D. H. Amyloid Protein. M. NAYEDA (Zeitsch. physiol. Chem. 1909,58 469-484).-The yield of hexone bases from the amyloid substance of the liver is the same as in the normal organ.The same is true for the spleen except that the amount of histidine is a little higher than usual. There is no ground for believing that amyloid is specially rich in bases or that it has anything in common with histone. W. D. H. The Protein Component of Chondro-mucoid. M. MAYEDA (Zeitsch. physiol. Chem. 1909 58 485-4S6).-The amount of hexone bases from the protein component of chondro-mucoid is about the same as in amyloid protein (see preceding abstract). W. D. H. Schmiedeberg’s Ferratin. ERNST SALKOWSKI (Zeitsch. physiol. Chem. 1909 58 282-289. Compare Scaffidi this vol. i 196).- Schmiedeberg’a f er ratin is simply the nucleo-protein of the liver which has a variable percentage of iron. It is not a ferri-albuminic acid and bas nothing in common with ferri-albuminic acids arti- ficially prepared.W. D. H. The Combination of Iron and the Nucleo-protein of the Liver. ERKST SALKOWSKI (Zeitsch. physiol. Chern. 1909 59 19-21). -The amount of iron in tbe nucleo-protein of the liver is very variable ; possibly the nucleo-protein is mixed with small and variable amounts of another compound rich in iron A t any rate the iron is very loosely bound and can be liberated by the action of dilute sodium carbonate solution at the boiling heat. W. D. H. Nucleo-protein of Pus. FERDINANDO STRADA (Biochem. Zeitsch. 1909 16 195-202).-The nucleo-protein which is precipitable by acetic acid from pus serum has been named pyin. Elementary analyses are given which differ mainly in the percentage of phosphorus (0.6 to 1*6%) according as the pus was autolysed or not previously.Its cleavage products were not investigated. It does not set up amyloid degeneration when injected into animals. W. D. H.ORGANIC CHEMISTRY. 275 Preparation of Bismuth Paranucleate. G. RICHTER (D.R.-P. 202955).-Bismuth paranucleate an insoluble white powder is produced by mixing solutions of calcium paranucleate and bismuth nitrate in concentrated aqueous sodium chloride and washing successively with sodium chloride solution water alcohol and ether. 0. T. M Tanning and Adsorption Compounds of Gelatin. LUPPO- CRAMER (Zeitsch. Chew. Ind. KoZZoide 1909 4 2 1-23).-Colloidal vanadic hydroxide is an active tanning agent ; a 1% solution of vanadic chloride coagulates a 10% gelatin solution immediately. Gelatin films which have been tanned by dipping into vanadic chloride solution are of a grey colour; the adsorbed vanadium compound can be removed by solutions of alkali hydroxides or oxalates.Egg-albumin and gum arabic are also quickly transformed into insoluble compounds by vanadic chloride solution. Nickel and cobalt salts have no appreciable tanning action on gelatin; if however gelatin films are dipped in sodium hydroxide solution and then exposed to the action of nickel and cobalt salts tanning results from the action of the colloidal hydroxides. That the higher oxides of many metals have the faculty of tanning whilst the lower oxides of the same metals produce no such effects is due to the fact that the salts corresponding with the higher oxides are more generally hydrolysed and that the hydroxides are very stable in the hydrosol form.H. M. D. Composition of Different Silks. EMIL ABDERHALDEN (Zeitsch. physiol. Chem. 1909 58 334-336).-Total hydrolysis may yield results of little value in distinguishing between proteins ; the amino- acids obtained may be equal in kind and quantity and yet their different methods of linking together may result in proteins of different characters. Partial hydrolysis reveals the difference. I n Italian silk . fibroin two dipeptides (glycyl-d-alanine and a glycyltyrosine) and a tetrapeptide were thus found. W. D. H. Composition of Different Silks. I. Neuchang Silk. EMIL ABDERHALDEN and AUGUSTE RILLTET (Zeitsch. physiol. Chem. 1909 58 337-34O).-Before it is possible to undertake the partial hydro- lysis alluded to in the preceding abstract total hydrolysis is a necessary first step.The Chinese silk here investigated yielded glycine 19.7 ; alanine 23.8 ; leucine 1.6 ; serine 1.0 ; aspartic acid 2.9 ; glutamic acid 1.7 ; tyrosine 9.8 ; proline Z -85% ; total 63.55. W. D. H. Kephalin. FRITZ FALK (Biochem. Zeitsch. 1909 16 187-194).- The kephalin obtained from sciatic nerve has an N P ratio of 1 1 as Thudichum and later Koch stated. That obtained from brain however has an X P ratio of 2 1. Methods of preparation are given in full and many details as to solubilities; it was not obtained crystalline. It has m. p. 176-1809 Thudichum described among its decomposition products three bases stearic acid and an unsaturated fatty acid called kephalic acid which according to Cousin belongs to276 ABSTRACTS OF CHEMICAL PAPERS.the linoleic series. In the present research it was obtained in crystalline form m. p. 122O ; its identification is not yet completed ; its elementary composition gives figures lying between those required by the formulae C19H3804 and C18H3604' W. D. H. Preparation of Glucothionic Acid. PHCEBUS A. LEVENE (Biochem. Zeitsch. 1909 16 246-249. Compare Mandel and Neuberg Abstr. 1908 i 1029).-Details are given of a modified method for the purification of glucothionic acids more especially for the removal of niicleic acids. The analysis of an acid barium salt agreed fairly well with the formula (C14H,,014NS),Ba,2H20. J. J. S. (' Glucothionic Acids." CARL NEUBERG (Biochem. Zeitsch. 1909 16 250-253).-A reply to Levene (preceding abstract).Largely polemical. The conclusions arrived at previously (Abstr. 1908 i 1029) are adhered to. J. J. S. Lipoids. 11. Unsaturated Phosphatides of the Kidney. SIGMUND FRANKEL and ALEXANDER NOGUEIRA (Biochem. Zeitsch. 1909 16,366-377. Compare Abstr. 1908 i 377).-Three unsaturated phos- phatides have been prepared from the ox-kidney. One of these present in only small quantity has the properties of kephalin ; when dry it is dark yellow and of a waxy consistence ; it begins to melt at 125' and decomposes a t 135'. The Hub1 iodine number is 70.38. The second compound an unsaturated triaminodiphosphatide C!'8H131021N8P29 is precipitated from the extract of the kidneys after removal of the kephalin as a cadmium compound CS8H13,021N3P2,2HC1,2CdC12.The free phosphatide is dibasic in character and has iodine number 82 whilst that of 1 he cadmium compound is 63.48. Two of the nitrogen atoms are in the form of choline that is combined with methyl groups It is a pale yellow powder m. p. 205' and optically inactive in dilute ethereal solution. Lastly a diaminornonophosphalide found in small quantities has no basic properties but forms a cadmium salt C34H,,0,0N2P BCdCI m. p. 215' which has an iodine value of 25.81 and is much less un- saturated than the previous compound ; the free phosphatide has a value of 37.83. Only one of the nitrogen atoms is in the form of choline. E. F. A. Lipoids. 111. Interaction between the Unsaturated Phos- phatides of the Kidney and Dyes. SIQMUND FRANKEL znd ALEXANDER NOQUEIRA (Biochem.Zeitsch 1909 16 378-382)- Dyes are excreted by the kidney in a changed state methylene-blue for example being converted into a leuco-derivative. The behaviour of the three unsaturated phosphatides of the kidney (see previous abstract) which have a marked affinity for oxygen towards methylene- blue has been studied outside the organism. Triaminodiphosphetide decolorises methylene-blue slightly in the cold more strongly on heating to 50'. The blue colour does not re-ORGANIC CHEMISTRY. 277 appear on shaking with air but is reformed to some extent although not entirely on adding acetic acid or on boiling. Chloroform extracts from the reduced liquid the same soluble methyleoe blue as occurs in human urine after administration of the dye. The leuco-derivative corresponds with the chromogen of Voisin and Hauser.The diaminomonophosphatide reduces methylene-blue strongly to a chromogbn but the primary colour is completely restored on adding acetic acid and boiling. The kephalin-like substance produces a greenish-blue solution. The original colour is not restored on shaking with air but a clouded blue liquid is produced by boiling with acetic acid. A similar green dye is often found in dog’s urine after administration of methylene-blue but seldom in human urine. The most com- pletely saturated of the three has the strongest decolorising action towards methylene-blue. E. F. A. None of the phosphatides react with indigo-carmin. Plwteins. 11. PH(EBUS A. LEVENE and DONALD D. VAN SLYKE (Biochem. Zeitsch. 1909 16 203-206.Compare Abstr. 1908 i 932).-The viscosity of plastein solutions in alkali is less than that of native proteins and is nearly as low as that of Wittd’s peptone. The viscosity sinks slightly after a short time and then remains practically constant. The viscosity of such native proteins as fibrin sinks more gradually and continues to fall until lower than that of plastein. Whether plastein is a decomposition product of protein cleavage which settles out on account of its insolubility or whether i t is synthetically formed from secondary proteoses is left uncertain. W. D. H Mechanical Destruction of Pepsin. A. 0. SHAKLEE and SAMUEL J. MELTZER (Proc. Amer. Physiol. Soc. 1908 xxix-xxx ; Amer. J. Physiol. =).-Shaking a solution of pepsin at room temperature diminishes its activity and finally destroys it.This action is more rapid at 3 3 O It is not due to oxidation but occurs just the same in inert gases. Mere shaking in the animal body lessens its strength as was determined by introducing a small bottle of pepsin solution into a dog’s stomach. W. D. H. Electrical Transportation of Ferments. I. Invertin. LEONOR MICHAELIS (Biochem. Zeitsch. 1909 16 81-86).-1n order to avoid injurious changes in reaction unpolsrisabl6 d8CtrOd8S (zinc in solutions of zinc sulphate) were employed. The experiments were made in a U-tube the bend of which containing the ferment could beclosed by taps and so separated from the side-tubes which contained water. The latter were fitted with glass tubes containing the electrode and zinc sulphate. Results obtained both without and in presence of acetic acid showed that as indicated by the absorption method invertin is an acid.N. H. J. IM. Enzymes which Hydrolyse (1) Salicin and (2) Arbutin. WTLHELN SIGMUND (Monatsh. 1809 30 77-87).-The leafy twigs ,of278 ABSTRACTS OF CHEMICAL PAPERS. various species of Salix and Populus contain an enzyme which is capable of hydrolysing salicin to dextrose and saligenin ; this the author names salikase. The action of the enzyme which differs from emulsin was shown by autolytic experiments and by mean8 of the precipitate obtained on adding alcohol to the aqueous extract of the twigs. Similarly the twigs of Calluna vulgaris and of Paccinium Myrtillus contain an enzyme to which th3 name arbutuse is given capable of hydrolysing arbutin into quinol and dextrose.T. H. P. Basiphil Rennets. C. GERBER (Compt. rend. 1909 148 56-58). -As a result of the study of the time of clotting of milk produced by rennets of different origin in the presence of varying quantities of acids and alkalis the conclusion is drawn that there are two extreme types of rennet namely oxyphil and basiphil. The former include the rennets from calf and pig the latter those from h?aclura and the decapod crustaceans. Between the extreme types there are other rennets which can be classified according to their action in the presence of various mineral and organic acids. 53. B. S. Rennet Action. W. VAN DAM (Zeitsch. physiol. Chern. 1908 58 295-330).-The investigation wits undertaken to determine why certain specimens of cow’s milk do not readily curdle with rennet.It was found by the electrical conductivity method that the coagula- tion-time is inversely proportional to the hydrogen ions present. The main reason of want of satisfactory curdling is poorness in calcium salts and this can be corrected by giving the cows calcium phosphate in their food. Theory of the Curdling of Milk by Rennet. GBRHARD WERNCKEN (Zeitsch. Biol. 1908 52 47-71).-Differences in the internal friction of solutions of caseinogen and casein (called in the paper casein and paracasein respectively) are so small as to come within the errors of analysis. Caseinogen solutions show a tryptophan reaction after a comparatively short lapse of time ; nevertheless the theory that casein is the result of fermentative change in caseinogen is considered untenable.W. D. H. W. D. H. Coagulation of Fresh Milk by the Rennet of the Papaw Tree (Carica Papaya). C. GERBER (Compt. rend. 1909 148 497-500).-The rennet in pepayotin-Merck is much more resistant to high temperatures than that of yeast and of pepsin and clots milk at Oo even when calcium is absent. The product of the quantity of ferment by the time taken to clot a given quantity of milk remains constant when the milk is perfectly fresh but when the milk is four hours’ old it clots too slowly with small quantities of ferment so that the above- mentioned product increases when the quantity of ferment is diminished. G. B. Tyrosinase. ALEXIS BACH (Ber. 1909 42 594-601. Compare Abstr. 1906 i 616 ; 1907 i 268 810 ; 1908 i 237 746).-NumerousORGANIC CHEMISTRY 279 experiments which have been made do not support Gonnermann’s hypothesis (P’iiger’s Archiv 1900 82) that tyrosinase is a hydrolysing enzyme and that the products of hydrolysis of tyrosine are subsequently oxidised by atmospheric oxygen.Gessard’s view (Abstr. 1’300 i 468) that the specific action of tyrosinase is due to the presence of certain metallic salts is also shown to be untenable. Experiments with some hundred different plant- juices and extracts prove that the oxidation of tyrosine by means of peroxydase hydrogen peroxide and a plant-juice or ferment preparation takes place only when the juice or preparation itself oxidises the base namely con- tains tyrosinase. I n many cases the activity of the tyrosinase is con- cealed by the presence of reducing substances but when these are removed by precipitation with alcohol the activity of the tyrosinase can be demonstrated.The activity of purified tyrosinase towards tyrosine is appreciably diminished by the addition of neutral peroxydase whether hydrogen peroxide is present or not. If the plant extract or tyrosinase preparation contains reducing or other substances which lower its activity the addition of peroxydase and hydrogen peroxide produces an initial acceleration in the oxidation but after a short time the inhibiting action of the peroxydase can be noticed. This initial acceleration is not due t o the oxidation of the tyrosine but t o the decomposition of the reducing or other substances present. J. J. S. Artificial Oxydases and Peroxydasea. V. MARTINAND (Compt. rend. 1909 148 182).-The oxides of alkalis and alkaline earths which form soluble peroxides and percarbonates give reactions similar t o organic peroxydase. Salts of metals which form several peroxides react in a similar way when they correspond with the higher oxides of the metal; those corresponding to the lower oxides do not act in this manner. Action of Acids on Peroxydwe. GABRIEL BERTRAND and MLLE. 31. ROZENBAND (Compt. rend. 1909 148 297-300. Compare &d. 1907 145 340)-In the case of lacease and tyrosinase certain acids inhibit the ferment in minute doses whilst other acids are almost without effect. As regards the action of acids in peroxydase (from wheat-bran) no such division into two groups can be traced the inhibitory effect being of the same order of magnitude as the electrical conductivity although not proportional to it. Some New Properties of the Oxydases of Russula Delica. JULES WOLFF (Compt. rend. 1909 148 500-502).-The oxydase from Russula Delica is most active on tyrosine and many other substances when the solution is neutral to phenolphthalein. Some colouring matters are oxidised both by this oxydase and by laccase but others are only oxidised by the ferment from Russula. FARBWERKE VORM. MEISTER LUCIUS & BRUNINO (D.R.-P. 20561 6).-p-Hydroxyphenyl- arsinic acid HO*C,H,-AsO(OH) yellow prisms m. p. 173-1 74O S. B. S. G. B. G. B. Preparation of Hydroxyarylarsinic Acids.280 ABSTRACTS OF CHEMICAL PAPERS. has now been prepared directly from phenol and crystallised arsenic acid by heating a t 150' for four hours. The product soluble in water is evaporated to dryness and the arsenic acid extracted from the residue with acetone. 4-Hydroxy-3-tolylarsinic acid is similarly obtained from o-cresol and arsenic acid at 140'. With m-cresol and arsenic acid the reaction takes place at 170". 4-Hydroxy-2-toZyZ~rsinic acid HO*C,H,Me*AsO(OH) sinters at 160" and decomposes at 183-185'. G. T. M. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 204664).-PhenyZgZycine - p - arsinic acid C0,H*CH2*NH*C,H4*AsO( OH) is prepared either by mixing sodium p-aminoarsinate and chloroacetic acid in hot water or by hydrolysing with alkalis the nitrite CN,*CH,*NH*C,H,*AsO(OH) produced by warming together in aqueous solution p-aminophenyl- arsinic acid potassium cyanide and formaldehyde (40%). Preparation of p-Arylglyoinearsinic Acids. G. T. M. Preparation of Sulphur Derivatives of p-Aminophenylarsinic Acid. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D. R .-P. 20561 7).-p- Amino~~~enylarsenious sulphide NH,*c6H,- Ass yellowish- white powder m. p. 180" is obtained by passing hydrogen sulphide into an acidified solution of p-aminophenylarsinic acid. The free sulphur is removed by carbon disulphide and the new sulphide dissolved in aqueous sodium hydroxide and reprecipitated by acids which dissolve it when present in excess. This sulphide is also produced by passing hydrogen sulphide into a methyl-alcoholic solution of p-aminophenylarsenious oxide. p - Acetykami.nophenyZarsenic sesquisulphide O(NHAs*C,H,As),S white lustrous needles m. p. 208" is produced by dissolving acetyl-p- aminophenylarsinic acid in 25% aqueous ammonia saturating the solution with hydrogen sulphide and precipitating with dilute hydrochloric acid. Phenylg Zycinarsenic diszclphide CO,H CH2 *NH* C,H,*AsS yellowish- white powder decomposing at 142" is produced by saturating with hydrogen sulphide an aqueous solution of phen ylglycin-p-arsinic acid. Preparation of the Salts of the Mercury Derivatives of Fluorescein. HERMANN PAULY and VIKTOR TRAUYANN (D.R.-P. 201 903)-The sodium salt of dimercurzyuorescein is produced by adding mercuric chloride to a solution of fluorescein in sodium hydroxide. The yellowish-red precipitate then obtained is dissolved in sodium carbonate and the red sodium salt isolated by evaporating the solution. The sodium salt of tetramercurifluorescein is similarly prepared by treating the foregoing dimercuri-derivative with more mercuric chloride in alkaline solutions. These mercuric derivatives of fluorescein have the property of giving very fast shades of red with fabrics mordanted with chromiilm iron uranium nickel cobalt aluminium and cerium. G. T. M. G. T. M.

ISSN:0368-1769    

DOI:10.1039/CA9099600197

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

224 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Hypohalogenous Acids and Hypohalogenites. 11. Kinetics of the Hypobromites in Weak Alkaline Solution. ANTON SKRABAL (Monatsh. 1909 30 51-76. Compare Abstr. 1907 ii 448).-The author has investigated the kinetics of the decomposition of a hypobromite into bromide and bromate in a solution containing hydroxyl ions in small but constant concentration. This constancy of concentration was effected by the use of sodium carbonate and sodium hydrogen carbonate i n proportions sufficiently large compared with that of the hypobromite. With reference to the concentration of hypobromite the decomposition of the latter is of the second order the velocity of formation of bromate being proportional to the concentration of hydrogen ions.Diminution of the concentration of the hydroxgl ions is accompanied by increase of the velocity of the change which is also accelerated by the presence of electrolytes this accelerating action being especially marked in the case of the bromides. The following kinetic equation represents the decom- position - d[HBrO]/dt~[H’]{[Br’] +e[E])K[HBr0I2 [ E l being the concentration of the electrolyte and e and K constant factors. The action of an electrolyte is \Dry approximately proportional t o the number of ionic charges but is independent of the nature of the electrolyte From the fact that with small concentration of the electrolyte the reaction proceeds according to the equation - d[HBrO]/dt = [H’][Br’]K[HBr0]2 the conclusion is drawn that the mechanism of the reaction is similar to that of the hypoiodite reaction (Zoc cit.).Accordingly in the hypobromite solution an equilibrium HBrO + Br’ + H’ t Br2 + H,O or 2 HBrO + Fr’ + H’ Z HBr,O + H20 must be rapidly set up the reaction determining the velocity being the decomposition of Br or HBr30 into bromide and bromate. T. H. P. The System Hydrogen Bromide and Bromine. ERNST H. BUCHNER and B. J. KARSTEN (Proc. K. Akad Vetensch. Amsterdam -1 909 11 504-508).-Sealed tubes containing weighed quahtities of bromine and hydrogen bromide dried by passing over phosphoric oxide were placed in a mixture of alcohol and solid carbon dioxide or of calcium chloride and ice and the temperature allowed to rise very slowly. The tubes were continually shaken and the temperatures at which the last trace of solid disappeared were recorded.The ond melting points when plotted indicate that there is an eutectic at about - 95O the composition corresponding with about 5 mols. % bromine. According to the curves no compound is formed. Although certain facts point to the formation of compounds between hydrogen bromide and bromine in solution the authors point out that this is only true of ionising solvents and that the union is probably determined by the bromine ion. I n non-ionising solvents it is improbable that such union takes place. H. M. D.INORGANIC CHEMISTRY. 225 Revision of the Atomic Weights of Iodine and Silver. GREGOXY P. BAXTER and GEORGE S. TILLEY (J. Amer. Chem. Xoc. 1909 31 201-221 ; Zeitsch. ccnorg. Chem. 1909 61 293-319).- With the object of obtaining a trustworthy value for the ratio of the atomic weight of silver to that of oxygen careful analyses have been made of iodine pentoxide the ratio of tha atomic meights of silver and iodine being already known with great exactitude.A method is described for ‘preparing pure iodic acid and confirmation has been obtained of the existence of the compound I,O,,HIO (compare Groschuff Abstr. 1906 ii 16). Iodic acid is almost completely converted into the pentoxide when heated at 240° but a small quantity of water remains. The analysis of the iodine pentoxide was effected by dissolving the substance in water reducing it to hydriodic acid with a suitable reducing agent and titrating the hydriodic acid against a weighed amount of silver It was found that hydrazine was the most satisfactory reducing agent and that sulphur dioxide could not be used as silver iodide occludes silver sulphate.Experiments have been carried out which prove that this substance does not absorb appreciable quantities of air. Two series of analyses have been made in which three different samples of iodine pentoxide and four samples of pure silver were employed. The ratio 2Ag :1205 has been found to be 0.646230 whence the atomic weight of -silver is 107.850 and that of iodine 126.891 (0= 16). E. G. JOEL H. HILDEBRAND and BEN LEON GLASCOCK (J. Amer. Chem. Soc. 1909 31 26-31).-Since Beckmann (Abstr. 1907 ii 340) showed that the molecular weight of iodine in all solvents corresponds with the formula 12 it has usually been accepted t h a t the brown colour of certain soliitions of iodine is connected with combination between the latter and the solvent. ‘1’0 test this view the freezing-point depression produced by iodine and certain liquids separately and then together has been determined with bromoform and ethylene dibromide as solvents.Only for liquids which form brown solutions is the total depression less than the sum of the separate depressions showing that combination has taken place. The equilibrium between iodine and certain “ active ’’ solvents (those which can combine with iodine) has been investigated in such inactive solvents as carbon disulphide and carbon tetrachloride by a colorimetric method and it is shown that for ethyl alcohol acetic acid ethyl acetate and nitrobenzene the respective compounds contain 1 molecule each of the solvent and iodine.From the displacement of the equilibrium with temperature it is calculated that the heat of combination of iodine and ethyl acetate is 3,600 cal. per mol. Iodine pentoxide has DT 4.80. Colour of Iodine Solutions. G. S. Behaviour of Solutions of Hydriodic Acid in Light in the Presence of Oxygen. H. JERMAIN M. CREIGHTON (Trans. Nova Scotia Inst. Sci. 1908 12 49-60).-The object of the investigation is to account for the fact that the amount of iodine liberated from226 ABSTRACTS OF CHEMICAL PAPERS. a solution of hydriodic acid or of acidified potassium iodide by oxygen and light reaches a maximum and then falls to zero. The solution used contained one volume of aqueous potassium iodide (1 gram per litre) to eight volumes of dilute sulphuric acid (1 vol.of acid D 1.84 to 5 vols. of water). The liberated iodine was titrated by N/1250 sodium thiosulphate. A preliminary experiment showed that evaporation of the iodine is not wholly responsible for its disappearance and also that the change of the iodine is accelerated by sunlight. The acidified potassium iodide solution 500 c.c. absorbed about 25 litres of oxygen in ten weeks but neither iodine nor iodate could be detected in the solution and strong reducing agents failed to liberate any iodine. c. 8. The nature of the product is still a mystery. Polyiodides. F. OLIVARI (Atti R. Accad. Lincei 1908 [v] 17 ii 717-722).-The freezing-point curves have been determined for mixtures of metallic iodides with iodine using an ordinary cryoscopic apparatus.Mercuric iodide does not form a polyiodide ; the curve has a eutectic point at 101.4’ and 12.5 molecular % HgI,. The curve for mixtures of calcium iodide and iodine has no distinct maximum but an almost horizontal branch having a eutectic point on the iodine side. The polyiodide if formed must be greatJy dissociated at the melting point . Tetramethylammonium iodide and iodine give a freezing-poin t curve presenting several maxima ; some of the results are uncertain owing t o the hygroscopic nature of the substances. The polyiodide NMe,*NI crystallises well in silky needles. Phenyltrimethylammonium iodide forms four polpiodides RI RI RI and RI (R=NPhMe,) freezing at 112O 834 63” and 25’ respectively. The results confirm the conclusion of Abegg and Hamburger (Abstr.1906 ii 747) that the stability of the poly- iodides increases with the electro-positive character of the cation. C. H. D. Fluoro-salts. FRITZ EPHRAIM and PAUL BARTECZKO (Zeitsch. anorg. Chem. 1909 61 258-264).-A tabular review of the known double fluorides is given. The Werner co-ordination number 6 is exceeded in a large number of cases. The number of hydrofluoro- metallic acids is also larger than with other halogen acids. The type M’,M”E’ is remarkable a copper cobalt and nickel salt being known. 0. H. D. Measurements of the Efflciency of Ozone Tubes. VII. EMIL WARBURQ and G. LEITHAUSER (Ann. Physik 1909 [iv] 28 1-16. Compare Abstr. 1906 ii 740 741).-The action of an ozone tubs regarded as a system of condensers in series with one another is subjected to mathematical treatment.Some experiments are communicated which show the influence of the current strength and the frequency on the efficiency. With increasing current strengthINORGANIC CHEMISTRY. 227 the efficiency falls but rises with increase in the frequency until a certain limiting value is reached. Ozonisers with an inner metal tube are more efficient than those with an inner tube of glass. A t a given discharge potential small ozonisers combined with a high frequency of discharge yield as much ozone as larger ozonisers with a smaller frequency. H. 31. D. Production of Ozone from Oxygen and Atmospheric Air by means of Ozonisers. VIII. EMIL WARBURG and G. LEITHAUSER (Ann. Physik 1909 [iv] 28 17-36. Compare preceding abstract).-The dependence of the yield of ozone on the amount of ozone already present in the gas operated on has been examined. Eiuations are deduced for the case in which the ozoniser contains a motionless and homogeneous mixture and also for that in which a steady flow of gas is maintained through the ozoniser. In the latter case the percentage of ozone in the gas acted on by the discharge increases gradually from one end of the tube to the other. The yields of ozone determined experimentally are in most cases in agreement with the theoretical formulte but when oxygen is passed through the ozoniser the observed limiting ozone concentration is greater than that expected theoretically. In the second part of the paper tho authors have investigated the variation of the yield of ozone with the current density and with the form of the induced current as modified by placing an induction-free resistance in parallel current ; further with the temperature and the nature and form of the ozoniser.Per kilowatt hour the best yields are obtained when the diameter of the discharge chamber is large but on the other hand if R high concentration is required the two tubes of the ozoniser should be comparatively close together. H. M. D. Formation af Ozone at Stationary Linear Electrodes. FRANZ FISCHER and KURD BENDIXSOHN (Zeitsch. anorg. Chem. 1909 61 153-180. Compare this vol. ii 136).-A device is described by which the length of the anode consisting of a strip of platinum foil 0.01 mm. wide and sealed into glass could be varied. Such electrodes are stable but not those of only 0.005 mm.width. A critical current density is observed at which the potential difference shows a sudden increase the current at the same time falling slightly. The current density at which this occurs is inde- pendent of the anode area and falls with increasing concentration of acid. When it is exceeded the yield of ozone diminishes greatly. On reducing the current after this point has been passed the original potential is not observed one several volts higher being always found. This behaviour of the anode is found to be due to incrustation of the anode at a high current density with platinum sulphate. Experi- ment shows that platinum siilphate Pt(SO,) is insoluble in concen- tiated but soluble in dilute sulphuric acid.A reduction in the width of a stationary anode increases the yield of ozone as does a reduction of temperature the yield increasing t o 27% when the electrolyte is cooled to -3.5". Since however the228 ABSTRACTS OF CHEMICAL PAPERS. critical current density falls with decreasing temperature a limit is set to the advantage to be derived from cooling. The critical point is aiso observed with rotating electrodes. C. H. D. Dynamic Allotropy of Sulphur. 11. [Binary] Systems con- taining Sulphur. HUGO R. KRUYT (Zeitsch. physikal. Chem. 1909 65 486-510. Compare Abstr. 1908 ii 1028).-In liquid sulphur there is equilibrium between the forms Sh and S,. The theoretical part of the present paper contains a general discussion of the possible types of partial miscibility in liquid systems where a pseudo-binary subatance such as sulphur forms one of the components and no appreciable chemical reaction takes place.A number of substances which react with sulphur between 100' and 200' are mentioned. Benzene toluene rn-xylene and triphenyl- methane proved suitable for the investigation as very little chemical reaction took place. Benzene and sulphur are completely miscible above 160" and below 226' ; the forms of the miscibility curves below and above these tem- peratures have been determined. Sulphur and toluene and sulphur and triphenylmethane show curves of similar type to the sulphur- benzene system; in the former system the limits of complete miscibility are lS0" and 220'; in the latter case 145' and 200". The system sulphur-m-xylene gives a curve of entirely different type as the components are not completely miscible in all proportions at any temperature within the limits employed.The types of curve observed are in accord with the theoretical deductions. In several cases notably in the system m-xylene-sulphur retardation in the attainment of miscibility was observed a result ascribed to the peculiarities in the behaviour of sulphur. G. S. Statics of Liquid Sulphur in the Dark and under the Influence of Light. ALBERT WIGAND (Zeitsch. physihl. Chern. 1909 65 442-457. Compare Abstr. 19OS ii 676).-The melting point of pure monoclinic sulphur is 118.95'. S Inso,. has already been determined by Schaum between 121' and 140" and the author has now extended the observations from 11 7.1' to 11 9.6' by Schaum's method.The results fit in well with those of Schaum. From the results it is calculated that t h e heat of transition from the soluble to the insoluble form is - 7180 cal. per gram-molecule S at 118*34O as compared with - 6000 cal. at 126-3' -5390 cal. at 131.0° and - 4700 cal. at 135.9 cal- culated from Schaum's observations. Some preliminary experiments indicate that the equilibrium is slightly displaced by light in favour of the insoluble form. As a source of light arc lamps were used. The equilibrium S sol. The possible constitution of the S molecule is discussed. G. S. An Automatic Hydrogen Sulphide Generator. HOWARD WATERS DOUGHTY (J. Anzer. Chern. Soc. 1909 31 60-62).-A modi- fication of the apparatus devised by Bradley (Abstr. 1899 ii 41 3).INORGANIC CHEMISTRY.229 The essential difference consists in an arrangement for drawing off the spent acid as fast as it settles t o the bottom of the sulphide compartment. L. DE K. Action of Sulphur Chloride S2C1 on Metallic Oxides. FRANQOIS BOURION (Compt. rend. 1909 148 170-171. Compare Abstr. 1907 ii 690).-The joint action of chlorine and sulphur perchloride on some oxides is so violent that the oxide becomes incandescent and a certain amount of oxychloride is formed instead of chloride. Ordinary sulphur chloride is now found t o convert metallic oxides into chlorides even in those cases where the older method gave poor results. The vapour of sulphur chloride is passed over the oxide contained in a tube heated just sufficiently to start the action during which sulphur is liberated 2M0 + 2S2C1 = SO + 2MC1 + 3s.Most oxides are attacked slightly below or at the boiling point of sulphur and the products are quite free from oxychloride. Samarium chloride prepared by this method contained 41.40% of chlorine instead of the calculated 41047%. R. J. C. Hyposulphites. VI. ARTHUR BINZ (Ber. 1909 42 381-384. Compare A bstr. 1908 i 940).-Purely theoretical. Reviewing recent work the author decides that O:S,Na*O*SO,Na best repre- sents the constitution of sodium hyposulphite. c. s. Electrochemical Reactions Induced by Sulphur Ions. MARIO G. LEVI and E. MIGLIORINI (Gccxxettcc 1909 39 i 110-120. Compare Levi and Voghera Abstr. 1906 ii 81 348 436).-As sodium thiosulphate may be formed electrolytically by the action of sulphur ions migrating and discharging themselves on sodium sulphite the authors have made experiments to see whether other thio-salts and thio-organic acids are formed in this way.With sodium arsenate appreciable quantities of the thio-arsenate are formed but with sodium antimonate and molybdate no thio-salt is obtained ; in all cases most of the S”-ions undergo oxidation With formic and acetic acids no thio-acid is formed but hydrogen sulphide is always formed in the anode chamber containing the organic acid ; the same phenomenon is observed when dilute sulphuric acid is used as anodic liquid. This hydrogen sulphide is formed electrochemically and is not due to the direct action of the acid on the sulphide since experiment shows that such action will not take place through the Puckall diaphragms employed in the time occupied by the electrolysis.The amount of hydrogen sulphide formed is proportional to the quantity of electricity passing if the current is low but diminishes relatively when higher currents are used. to so,”. T. H. P. Preparation of Hydrogen Selenide. HENRI WUYTS and AL. STEWART (Bull. Xoc. chim. Belg. 1909 23 9-ll).-Moisean and Etard obtained hydrogen selenide by heating selenium with colophene VOL. XCVI. ii. 16230 ABSTRACTS OF CHEMICAL PAPERS. an expensive hydrocarbon obtained by polymerisation of terebenthene. The authors find it advantageous to replace colophene with paraffin wax which commences to boil at 380'. Paraffin wax is attacked by sulphur at 245O but selenium requires a temperature of 335-340".A regular evolution of hydrogen selenide is obtained by heating selenium with four times its weight of paraffin in an air-bath. Organic selenium compounds which accompany the gas are mostly condensed a t 60'. The hydrogen selenide may then be further purified by condensation by a mixture of solid carbon dioxide and acetone and fractional distillation. The yield is 75 t o 80% of the theoretical. R. J. C. Electrolysis of Solutions of Selenious Acid. I. CAMILLO MANUELLI and GUIDO LAZZARINI (Gazxetta 1909 39 i 50-69).- When solutions of selenious acid are electrolysed the acid undergoes simultaneous reduction to selenium and oxidation to selenic acid HPSeO + 2H2 = 3H20 + Se and 2H2Se0 + 2 0 = 2H2Se0,. Selenic acid may be conveniently prepared in this way since the electrolysis gives rise neither to intermediate reduction products nor to complex acids as is the case when sulphurous acid is electrolysed.The authors have studied the influence of the conditions of electrolysis on the yields of selenium and selenic acid ; theoretically 0*'73SS gram of selenium should be separated a t the cathode per ampere-hour whilst at the anode a quantity of selenious acid corresponding with 1.4776 gram of selenium should be oxidised. The results show that diminution of the concentration of selenious acid and increase of the concentration of selenic acid are accompanied by a fall in the current yield both of selenium and selenic acid. When a large anode and consequently a small anodic current density is employed the yield of the oxidation product is large whilst with a large cathode a high yield of selenium is obtained. The diminished yield of selenic acid obtained when the quantity of this acid increases is not due to the establishment of an equilibrium between the oxidation of the selenious acid and the reduction of the selenic acid since in the electrolysis of the latter only a small amount of reduction occurs.The yields at 54-58' are not markedly different from those a t 25'. T. H. P. Atomic Weight of Tellurium. VICTOR LENHER (J. Amer. Chern. Xoc. 1909 31 20-24).-The method depends on the fact that when potassium telluribromide K2TeBr is heated strongly in a current of chlorine and finally in hydrogen chloride only potassium chloride remains behind ; the latter is then weighed. The oxide obtained from the ores was converted into the double bromide by the action of hydrobromic acid and potassium bromide; the double bromide was crystallised repeatedly from water containing a little dilute hydrobromic acid and was finally kept over soda-lime in a vacuum for eight months.As a mean of sixteen concordant experiments the value Te = 127.55 was obtained (C1= 35.46 Br = 79-92 K = 39*095) in exact agreement Tellurium ores from three different sources were employed.INORGANIC CHEMISTRY. 231 with the International value. gave identical results. G. S. The products from different sources Non-existence of Tellurium Oxychloride. VICTOR LENHER (J. Amer. Chem. SOC. l909,31,243-244).-Tellurium dioxide (1 mol.) unites at about 0' with hydrogen chloride (3 mols.) and on raising the temperature 1 mol.of hydrogen chloride is eliminated with formation of the compound Te02,2HC1. When this substance is heated at 280-300° it is not converted into the oxychloride TeOCl as stated by Ditte (Abstr. 1877 i 45). but into a mixture of the tetrachloride and dioxide without the intermediate formation of an oxychloride. If the tetrachloride and dioxide are heated together combination does not take place but on cooling the original compounds are recovered unchanged. E. G. Reaction between Fused Potassium Nitrate and Tellurium Dioxide. VICTOR LENHER and P. D. POTTER (J. Amer. Chem. Soc. 1909 31 24-26).-When tellurium dioxide is fused with potassium nitrate yellowish-brown substances are noticed swimming in the fused mass; on continued heating the mass becomes clear the conversion to potassium tellurate being then complete.The brown products have been isolated by extracting with water until nothing further dissolves and on analysis prove to be compounds of potassium tellurate with tellurium dioxide in proportions depending on the time of heating and other conditions. The same brown compounds have been prepared by fusing together potassium tellurate and tellurium dioxide; they are insoluble in dilute acids and alkalis but are slowly decomposed by hot strong hydrochloric acid with evolution of chlorine. Analogous compounds are obtained by fusing tellurium dioxide with sodium nitrate. G. S. Atomic Weights of Nitrogen and Silver. THEODORE W. RICHARDS PAUL KOTHNER and ERICH TIEDE ( J . Amer. Chm. Soc.1909 31 6-20 ; Zeitsch. anorg. Chem. 1909 61 320-337).-The method employed was the analysis of ammonium chloride by decompos- i n g with silver nitrate and weighing the resulting silver chloride. The results of Scott (Trans. 1901 70 147) are regarded as untrustworthy because the solubility of silver chloride was not sufficiently allowed for ; the earlier investigations of Stas are unsatisfactory for the same reason and also because the ammonium salt was not free from organic impurities. One specimen of the salt was prepared as follows Organic impuritieR were removed by heating the ammonium sulphate with concentrated sulphuric acid and a little potassium permanganate until the solution became perfectly colourless (Kjeldahl). To a solution of the acid ammonium sulphate pure calcium oxide was added and the mixture placed in a desiccator which also contained a platinum dish filled with hydrochloric acid.On exhausting the ammonia was absorbed by the acid. Another sample was prepared by the electrolytic reduction of nitric acid as described by Hinrichsen (Abstr. 1908 ii 494). The samples were recrystallised from dilute ammonia and perfect 16-2232 ABSTRACTS OF CHEMICAL PAPERS. neutrality and complete dryness were secured by subliming first in an atmosphere of ammonia and then in a Sprengel vacuum (to remove excess of amnionia) quartz vessels being used throughout. The methods employed are fully described. The ratio NH,Cl AgCl was determined by methods analogous to those fully described i n previous papers and nine very concordant results are quoted.From these and previous results of. Richards and his co-workers the following values are obtained Ag = 107.881 ; Cl=35*4574 ; N = 14.0085 based on O = 16.000 and H= 1.0076 (Morley). The results furnish striking evidence in favour of the low values for nitrogen and silver recently advocated from different quarters. G. S. Products of the Arc and Spark Electric Discharge in Liquid Argon or Nitrogen. 111. Tin Nitride and Pyro- phoric Tin. FRANZ FISCHEB and GEORGE ILIOVICI (Ber. 1909 42 527-53’7. Compare Abstr. 1908 ii 1034; this vol. ii 139).-By using tin as electrode in argon 86-114 mg. per hour of a substance was prepared which behaves abnormally as compared with the other substances obtained (Zoc. cit.) towards cold concentrated nitric acid.It is slightly altered by exposure to air and a special apparatus was con- structed so that not only the substance could be prepared but it could also be heated in the absence of air. When heated to redness in a quartz tube nitrogen mas evolved (proved by spectrum and sparking with oxygen) ; the maximum amount obtained was 3.18% but analysis of various specimens gave generally less nitrogen and the substance is a mixture of metal nitride and some oxide. Calcium as an electrode when placed in a gasometer removes the oxygen and nitrogen from argon. The calcium arc discharge acts best when the calcium sublimes on the walls of the vessel; by this means the argon is rendered very pure the “substance” from the tin electrode discharge containing no oxygen and only 0.8% of nitrogen.I n this case the tin was rendered pyrophoric due to the fine state of division. W. R. Ghloroamine. FRITZ RASCHIG ( Verh. Ges. deut. Natulrforsch. Aertae. 1907 11 i I20-123).-The well-known hypochlorite colour reaction of aniline is or is not obtained according as ammonia is added after or before the hypochlorite and the aniline solutions are mixed. Moreover whilst concentrated solutions of ammonium hydroxide and sodium hypochlorite immediately evolve nitrogen when mixed gas is evolved from dilute solutions only after some time. These facts led the author to deduce the existence of a compound intermediate between ammonia and nitrogen. Solutions containing equal molecular quantities of ammonia and sodium hydroxide react quantitatively thus NaOCl + NH3 = NH,Cl+ NaOH ; by distilling the solution in a vacuum at a low temperature chlo~oamine NH,Cl can be obtained as an unstable faintly yellow oil floating in the distillate water.The solution of chloroamine obtained as above yields with potassium iodide at first a brown solution and then a black precipitate of nitrogen iodide and with potassium cyanide cyanogen chloride andINORGANIC CHEMISTRY. 233 ammonia oxidises sulphurous acid and reacts with alkali hydroxides the more rapidly the greater the concentration of the alkali to form ammonia nitrogen and potassium chloride 3NH,C1+ 3EOH = NH + N + 3KCl+ 3 H,O. The reaction with ammonia is similar (I) 3NH,Cl+ 2NH = N + 3NH,Cl but in addition a small quantity of hydrazine is formed (11) NH,Cl + NH = N,H,,HCl.After many trials the author has succeeded in hindering reaction I and accelerating reaction I1 to such an extent that by treating normal sodium hypo- chlorite solution with fifty times the calculated quantity of ammonium hydroxide in the presence of a little glue 75-80% of the calculated quantity of the ammonia is converted into hydrazine. c. s. Oxidation of Hydrazine. 111. ARTHUR W. BROWNE and F. F. SHETTERLY (J. Amer. Chern. Soc. 1909 31 221-237).-In earlier papers (Abstr. 1907 ii 863 ; 1908 ii 373) an account has been given of the oxidation of hydrazine sul phate by ammonium metavanadate and potassium chlorate bromate and iodate. Experiments are now described on the behaviour of aqueous solutions of hydrazine sulphate towards potassium persulphate permanganate and perchlorate hydrogen peroxide sodium periodate red lead and lead and man- ganese dioxides with the object of determining the amounts of azoimide and ammonia produced in each case under certain conditions.When hydrazine sulphate was heated with potassiuui persulphate in presence of sulphuric acid the maximum yield of azoimide was 40.3%. whilst that of ammonia was 1.5 mols. from 2 mols. of hydrazine. In alkaline solution only small amounts of azoimide were produced and about 20% of ammonia. The methods desciibed by Pannain (Abstr. 1904 ii 638) and Rimini (Abstr. 1906 ii 898) for estimating persulphates by means of hydrazine sulphate are inaccurate on account of the formation of azoimide and ammonia. When hydrazine sulphate was treated in acid solution with potass- ium permanganate maximum yields of 3.19% of azoimide and 1.65 mols.of ammonia from 2 mols. of hydrazine were obtained whilst in alkaline solution only small quantities of aaoimide were formed. Petersen (Abstr. 1893 ii 605) has expressed t h e renction between hydrazine sulphate and potassium permsnganate in presence of sulphuric acid by the equation 17N,H4,H,S0 +. 130 = 13 H,O + 7(NE4),S04 + 10N + 10H2S04. It is now proved that the greater part of the hydrazine is converted into uitrogen and ammonia as Petersen has stated but that under certain conditions appreciable quantities of azoimide are formed. With hydrogen peroxide in acid solution maximum yields of 38.5% of azoimide and 1-10 mols. of ammonia from 2 mols. of hydrazine were produced whilst in alkaline solution only small amounts of azo- imide and fairly large amounts of ammonia were formed.The maximum yields produced by potassium perchlorate in acid solution were 22.4% of azoimide and 44% of ammonia. When hydrazine sulphate was treated with sodium periodate in acid solution in presence of silver sulphate t o prevent the liberation of iodine considerable quantities of azoimide were formed. With lead dioxide in acid solution maximum yields of 4.1% of azoimide and 13.2OL234 ABSTRACTS OF CHEMICAL PAPERS. of ammonia were obtained. Red lead and manganese dioxide also oxidise hydraziae sulphate to azoimide and ammonia the maximum yields in the latter case being 2.32% of azoimide and 1-53 mols. of ammonia from 2 mols. of hydrazine. E. G. Action of Zinc on Hydrazine Hydrate. ERICH EBLER and E.SCHOTT (J.pr. Chem. 1909 [ii] 79 72-74. Compare Abstr. 1908 ii 1029).-When zinc is partly immersed in hydrazine hydrate and exposed to the action of the air a white crystalline substance is formed with the evolution of hydrogen. Analyses show that this compound is zinc I8 ydruzinecarboxylate dihydraxinate NH,*NH*CO*O "*NH,*NH ' it does not give a precipitate with a solution of a chloride of an alkaline earth but when the solution is boiled the substance is hydrolysed and the carbonate of the alkaline earth precipitated. NH2*NH*CO*O>Zn/N K2*NH2 . W. H. G. Action of Air and Oxidising Agents on Coals. OCTAVE BOUDOUARD (Compt. rend. 1909 148 284-286).-In contact with air at looo coal readily undergoes oxidation the increase in weight through absorption of oxygen may amount t o 10%.After oxidation in this way coal is found to contain humic acid and to have lost its property of coking. Concentrated nitric acid causes more complete oxidation and increases the yield of humic acid. Analyses are given of anthracite coal and lignite before and after oxidation. w. 0. w. Weight of Carbon Dioxide with a Table of Calculated Results. SAMUEL W. PARR (J. Amer. Chern. Soc. 1909 31 237-243).-1n view of the discrepancies between the various tables of the weights of 1 litre of carbon dioxide at different temperatures and pressures a new series of values has been calculated. Dietrich (Zeitsch. anal. Chem. 1864 4 142) published a table in which he employed the value 1.9678 for the observed weight of 1 litre of carbon dioxide a t 0' and 760 mm.which agrees fairly well with those usually employed at the present time (compare Guye Abstr. 1907 ii 605). On correcting this value for the latitude 41" and an elevation of 100 metres it becomes 1.9760. The coefficient of expansion of carbon dioxide at constant volume has been given by Chappuis as 0.0037135. Employing these values a new table has been compiled the calcula- tions being made by means of the formula W= 1.976(P - w - b)/760(1+ 0.0037135 x t ) where W is the weight of 1 litre observed voiume reduced to 0" and 760 mm.; P the observed pressure; w the correction for tension of aqueous vapour ; and 6 correction for barometer glass scale. E. G. Properties of Hydrogels when Dehydrated. JAKOB M. VAN BEMMELEN (Chem.Weekblad 1909 6 63-82 ; Zeitsch. unorg. Chem. 1909,62 1-23).-A continuation of the author's criticism (Abstr. 1908 ii 838) of Tschermnk's silicic acid formulae (Abstr. 1905 ii. 816). A. J. WINORGANIC CHEMlSTRY. 235 Phenomenon Observed in the Action of Hydrochloric Acid on very Dilute Alkali Amalgams. G. MCPHAIL SMITH (J. A m r . Chenz. Soc. 1909 31 31-35).-1n the decomposition of the alkali amalgams by means of hydrochloric acid a point is reached at which there is a sudden increase in the surface-tension of the amalgams which is accompanied by the sudden evolution of a cloud of very small bubbles of hydrogen and by a sudden fall in the potential between the amalgam and the solution. G. S. Theory of Bell-chamber Process for Electrolysis of Alkali Chlorides.M. F. CHANCEL (Bull. Xoc. chim. 1909 [ivl 5 58-61). -The author controverts some of Brochet’s conclusions (Abstr. 1908 ii 1034). The concentration of the alkali obtained in this process should be proportional to the conductivity of the salt solution but independent of the mobility of hydroxyl ions. I n order to obtain a theoretical yield of sodium hydroxide on the current used the velocity of the liquid away from the cathode must exceed a certain minimum. With a slower flow a more concentrated solution is obtained but the yield on the current is less owing to the alkali hydroxide taking part in the electrolysis. I n practice convection currents interfere and the theoretical conditions are never realised. R. J. C. Colloidal Potassium Chloride. CARL PAAL and KURT ZAHN (Bey.1909 42 277-290. Compare Abstr. 1906 ii 351 749 ; 1908 ii 179).-Organosols of potassium chloride similar t o those of sodium chloride are obtained by the action of ethyl chloroacetate chloroaceto- phenone chloroacetone and acetyl chloride on ethyl potassiomalonate and its ethyl benzyl and i-amyl derivatives. The liquid and suspended organosols are more stable than those of sodium chloride and contain as a rule a higher percentage of the salt; thus solid potassium chloride organosols containing 93.6 and 9604% KC1 have been obtained. On drying however the organosols pass quickly into solid irreversible gels. The intermediate colloidal solution which is seemingly a homogeneous liquid gives on filtration through paper the liquid gel the solvent being separated.This liquid gel is converted by light petroleum into a solid reversible gel this being re-converted into the liquid form by benzene which gradually passes on keeping into the irreversible form. Increase in the molecular weight of the malonate does not give any increase in stability of the colloidal potassium chloride. There are therefore five forms of these adsorption compounds of colloidal potassium chloride a solid and liquid organosol a liquid gel and two solid gels one of which is reversible. The importance of solvents free from water in this work is emphasised. W. R. Colloidal Potassium Bromide and Iodide. CABL PAAL and KURT ZAHN (Ber. 1909,42,291-300. Compare preceding abstract).- Adsorption compounds of colloidal potassium bromide are obtained by the action of ethyl bromoacetate bromoacetophenone bromoacetone and acetgl bromide on ethyl potasaiomalonate and its ethyl and benzyl derivatives in benzene xylene or ether solutions.The potassium236 ABSTRACTS OF CHEMICAL PAPERS bromide organosol cannot be obtained from the condensation of ethyl bromoacetate and ethyl potassiomalonate the gel being formed but it may be obtained.from the potassium derivativesof ethyl ethyl- or benzyl- malonates. Liquid organosols and gels are given with benzene whereas with ether the more stable solid organosol is obtained which often may be preserved under ether for some days. On drying the organosols pass into irreversible gels. The liquid gels by transmitted light appear as cloudy liquids (compare sodium bromide Abstr.1908 ii 179) due to separation of small quantities of irreversible gels probably occasioned by traces of water. These substances are therefore less stable than the colloidal potassium chloride compounds. By the action of ethyl P-iodopropionate on ethyl potassiobenzyl- malonate in benzene or ether solution there result a labile organosol as well as the irreversible gel of potassium iodide. W. R. Double Salts of Ammonium Sulphate and Ammonium Nitrate. FRANS A. €3. SCHREINEMAKERS and P. H. J. HOENEN (Chem. Weekblad 1909 6 51 -56).-From aqueous solutions of ammonium sulphate and ammonium nitrate at 30° the two double salts (NH,),SO,,(N H,NO,) and (NH4),SO4,(NH,NO3) have been isolated. They are decomposed by water but are stable in presence of excess of ammonium nitrate. A.J. W. Effect of Water on the Freezing Point of Molten CaCl2,6H,O. J. LIVINGSTON R. MORGAN (J. Amer. Chem. Soc. 1909 31 251-252 ; Zeitsch. anorg. Chem. 1909 61 347-34S).-An acknowledgment of the error in calculation pointed out by Cock (this vol. ii 18) in Morgan and Benson’s paper on molten hydrated salts as solvents for the freezing-point method (Abstr. 1907 ii 747). E. G. Rapid Preparation of Calcium Phosphide for the Bvolution of Hydrogen Phosphide. CAMILLE MATIGNON and R. TRANNOY (Compt. rend. 1909 148 167-1 70)-Hydrogen phosphide usually prepared by the action of dilute acid on aluminium phosphide may albo be prepared from calcium phosphide. Calcium phosphate the source of all phosphorus compounds is intimately mixed with the correct amount of aluminium powder and ignited.A mixture of calcium phosphide aluminium oxide and a trace of calcium results which readily yields hydrogen phosphide with acidified water. The gas is not spontaneously inflammable and its only impurity is a small proportion of hydrogen. A small acetylene generator may be employed or the powdered phosphide may be placed in a flask with water and dilute hydrochloric acid run in from a dropping funnel. Double Fluorides and Chlorides of Univalent Thallium. FRITZ EPHRAIM and PAUL BARTECZKO (Zeitsch. unorg. Chem. 1909 61 238-257).-Thallous fluoride is best prepared by dissolving thallium in dilute sulphuric acid removing lead as sulphide precipitat- ing thallous sulphide from alkaline solution and dissolving in hydro- fluoric acid. R. J.C.INORGANIC CHEMISTRY. 237 Ferric thallous JEuoride 3T1F,2FeF3 prepared by evaporating a solution of ferric and thallous fluorides the former being in excess separates in bright pink crystals. Chromic thallous fluoride 3TlF 2CrF prepared in similar manner forms a green crystalline powder. The aluminium compound 3T1F,2A1F3 forms white crystals. All these salts are decomposed only slowly by sodium carbonate especially the aluminium compound indicating the presence of complex ions. An aqueous solution of thalloiis and lead chlorides deposits only the original mixture of salts on evaporation. In hydrochloric acid sola- tion tliallous lead chloride TICl,PbCl is formed and crystallises in six-sided elongated leaflets. Thallous chloride dissolves in molten antimony trichloride and on the addition of concentrated hydrochloric acid the double salt 3TlC1 S bCI is precipitated in light yellow lustrous scales.When antimony pentachloride is used in the same way it rapidly loses chlorine and a double salt of thallous chloride and antimony tetrachloride is obtained as a dark violet solid TlCl,SbCl the yellow compound first formed which is probably TlCl,SbCl being unstable and blackening in the air. By passing chlorine into a solution of thallous chloride in antimony trichloride a black felted mass is obtained containing quadrivalent antimony and probably having the formula T1Ul3,2T1C1 2SbC1 part of the thallium being oxidised to the thallic state. Thallous bismuth chlmide 3T1C1,BiC13 prepared in hydrochloric acid solution forms large very thin colourless plates rapidly breaking up into opaque white scales.When a less excess of bismuth chloride is employed a second compound 6T1C1,BiC13 is obtained resembling the first in appearance. Thallium is best estimated as iodide a slight excess of potassium iodide being added a t 50-60'. After twelve hours the precipitate is collected on a Gooch filter using only very gentle suction and mashed with pure water. C. H. D. Burning of Admixtures pn Refining Copper in a Rever- beratory Furnace. V VANJUKOFF (J. Russ. Yhys. Chem. Soc. 1908,40,1649-1675).-After discussing the literature of the purifica- tion of copper by the so-called Swansea or dry refining process the author gives the results of his own investigations in this direction. Before the copper is melted in the reverberatory furnace its temperature apparently falls whilst during boiling the temperature rises the exothermic reaction 2Cu,O + Cu2S = 6Cu + SO + 39 Cal.then taking place. The end attained by the second refining is the removal of arsenic and antimony; the fact that only a slight amount of arsenic is burnt away during the first refining is explained by the layer of slag and sulphur compounds covering the copper this layer preventing oxidation. Up to the end of the oxidation period sulphur exists inthe copper in the forms of cuprous sulphide and sulphur di- oxide. The course of the refining was followed by snalysing the gases evolved. T. H. P.238 ABSTRACTS OF CHEMICAL PAPERS. Ancient Copper Objects from Transcaucasia. WLADINIR A. SEINDER (Bull.Acad. Sci. Xt. Petedmrg 1909 1 75-78).-The specimens investigated were covered with a greenish-red layer which in one case reached a depth of 2 mm. Three specimens were analysed with the following results (1) Copper = 94*75% iron = 0.37% sulphur = 0.39%. (2) Copper = 96*80% sulphur = 0.13%. (3) Copper = 97.01% antimony = 0.05% iron = 0.45%. The remainder in each case consisting of silicon carbon dioxide and oxygen in the adhering slag. The supeificial layer of the first specimen consists of malachite mixed with a small quantity of silica. Z . I(. Solid Solutions in the Dissociation of Cupric Oxide LOTHAR WOHLER and W. FREY (Zeitsch. Elektrochem. 1909 15 34-38. Cornpare Abstr. 2907 ii 33).-Motallic copper is not formed in the dissociation of cupric oxide; cuprous oxide has therefore a lower dissociation pressure than cupric oxide.The first small quantities of cuprous oxide formed by the dissociation of cupric oxide diminished the pressure a t which oxygen is in equilibrium with the mixture of oxides in a very marked way. If the oxide is not heated for very long the same equilibrium pressure is attained at a given temperature and for a given cornposition whether oxygen has been removed from a higher oxide or caused to combine with a lower one. Very pro- longed heating however somewhat diminishes the pressure. This is probably due in part at least to false equilibrium resulting from the very slow rate of solution of cuprous and cupric oxide in each other. T. E. Phase Equilibrium of the Red Cupri-ferrous Sulphates.ARTHUR J. ALLMAND (Zeitsch. ccnorq. Chem. 1909 61 202-23'7).- The red or yellow salts obtained by Etard (Abstr. 1879 104) and by Scott (Trans. 1897 71 564) by the action of sulphuric acid on a concentrated mixed solution of cupric and ferrous sulphates correspond in composition with solid solutions of the general formula (Cu Fe)SO,,H,O. This does not account for the colour FeSO,,H,O being white and CuS0,,H20 pale blue. The possibility that cuprous-ferric salts may also be present is not to be tested analytically on account of the reactions taking place when the salts are dissolved in water I n the study of the phase equilibrium 60 C.C. of a 0.8 molar solution of cupric and ferrous sulphates were taken and 75 C.C. of concentrated sulphuric acid added in an atmosphere of carbon dioxide.The mixture was then shaken for three weeks in a thermostat a t 25" and the liquid and solid phases analysed separately the solid being previ- ously washed first with sulphuric acid of the same concentration as the mother liquor and then with alcohol. The brown colour of the mixed salts increases in depth from both ends of the series reaching a maximum in the crystals containing 18% Fe and 16% Cu. All the crystals are microscopically homogeneous. When heated gently in a test-tube their reddish-brown colour becomes chocolate-brown and finally mauve the original colour being restored on exposwe to air.INORGANIC CHEMISTRY. 239 Only a very small quantity of ferric iron is present and is to be regarded partly as an impurity being formed by the reaction Cu"+ E'e" -+ Cu' + Fe"'.The quantity of SO is always somewhat deficient the salts being slightly basic in spite of the acidity of the solution. This basicity is probably due t o hydrolysis of the ferric salt . The curves expressing the relation of the liquid and solid phases present certain peculiarities the origin of which is not fully explained. It appears that cupric sulphate dissolves in solid ferrous sulphate in the form of normal molecules up to about 75%. Beyond this limit polymerisation occurs. A suggestion is made that the cause of the colour may be an oscillation of electrons due to the presence of metals in different stages of oxida- tion as in Baly's explanation of the colour of organic compounds since ferric ferrocyanide and ferrous ferricyanide in which similar conditions occur are also coloured.The red colour is not due t o ferric salts or to cuprous oxide. C. H. D. Preparation of Metallic Aluminium from Aluminium Silicate. MAX MOLDENHAUER (Metallurgie 1909 6 14-1 9).- Aluminium silicate may be freed from silicon by reducing with carbon in the presence of ferric oxide when iron silicide is formed. In practice the dry clay having the formula A1,0,,2Si02 is fused in an electric furnace with ferro-silicon (10% Si) the products being alumina containing 13.4% SiO and an iron silicide containing 49% Si. The alumina is then fused in a separate furnace with haematite and carbon the products being practically pure alumina and 10% ferro-silicon. The alumina is freed from mechanically admixed ferro-silicon by grinding and extracting with a magnet and is electrolysed in solution in cryolite. The freezing-point curve of mixtures of cryolite and alumina shows a rapid fall from the freezing point of cryolite (975') t o a eutectic point at 880" and 20% Al,O,.The Apparent Retardation of Fusion of Aluminium. CAMILLE MATIGNON (Bull. SOC. chim. 1909 [iv] 5 91-92).-With reference to von Bolton's observation that aluminium wire may be heated above its melting point without losing its shape (Zeitsch. h'lektrochem. 1908 14 7 6 6 ) the author points out that he has recorded this fact already (Mon. Sci. 1900 [iv] 14 357) and explained it as due t o the formation of a protective layer of alumina. T. A. H. C. H. D. Sodium Alum. WARREN R. SMITH (J. Amer. Chem. Xoc. 1909 31 245-247).-The existence of sodium alum (Aug6 Abstr.1890 1059 ; Wadmore Proc. 1905 21 150) has been confirmed and experiments are described which prove that it is a definite chemical compound It is a true alum since it forms mixed and layer crystals with other alums. The following solubility data are recorded which express the number of grams of the anhydrous salt Na2S0,,AI,(S0,) contained in 100 grams of a saturated solution.240 ABSTRA’CTS OF CHEMICAL PAPERS. A t loo 26.9 ; at 1 5 O 27-9 ; at 20° 29.0; at 25’ 30.1 and at 30° 31.4. The quantities of the crystalline salt contained in 100 grams of the saturated solution are at loo 50.8; at 1 5 O 52.7; at 20° 54.8 ; at 25O 56.9 and at 30° 59.4. E. G. The Constitution of Blast-Furnace Slags. M. THEUSNER (Metallurgie 1908 5 657-667).-Finely-powdered slags containing 25-31% SiO 14-18% Al,? and 43-51% CaO were extracted with various solvents the composition of the solution and of the residue being determined in each case by analysis.Citric acid ammonium citrate and ammonium chloride were used as solvents. The basicity of the slags depends on the ratio of lime to silica and is practically independent of the proportion of alumina. From the more basic slags solvents at first extract lime the ratio of alumina to silica in the residue remaining constant whilst less basic slags are less attacked and the residue contains more lime than the residue from the originally more basic specimens. Acid slags are found microscopically to contain much melilite which is absent from the basic slags.An artificial melilite behaves towards solvents in exactly the same manner as an acid slag. Artificial mixtures in different proportions show that the attack by solvents is greatest when the ratio of silica to alumina is highest. Water attacks the slags much less readily than salt solutions. The lime is chiefly dissolved small quantities of silica and alumina being also taken up in a colloidal form. C. H. D. Magnetieable Manganese Alloys. X. Manganese- Aluminium-Copper FRIEDRICH HEUSLER and FRANZ RICHARZ (Zeitsch. anorg. Chem. 1909 61 265-279).-Forged alloys containing 20% or less manganese and 6% or more aluminium the remainder being copper are entirely non-magnetic when quenched from a red heat in water or mercury but after heating for several hours in boiling xylene a maximum degree of magnetisability is reached and the alloy is found to be free from hysteresis.The same alloys slowly cooled show hysteresis which is the greater the dower the cooling through the critical range. The magnetic susceptibility decreases rapidly with increase in the proportion of aluminium. The variation of magnetic properties with composition is expressed on a diagram with triangular co-ordinates. The conclusion is drawn that the maximum susceptibility is obtained when the alloys have the composition AlM in which M represents manganese and copper which replace one another isomorphously in the compound. I n this isomorphous series the magnetic susceptibility increases with increas- ing manganese and a maximum should be reached by the compound AlMn which is to be examined for its magnetic properties.C. H. D. The Production of Malleable Cast-Iron. FEDERICO GIOLITTI F. CARNEVALI and G. GHERARDI ( A t t i R. Accad. Lincei 1908 [v] 1’7 ii 748-754. Compare Wust Abstr. 1908 ii 287).-The pearlitic zone observed by Wust is also observed i u mild steel (0*05%C) expoaedINORGANIC CHEMISTRY. 241 to pure methane at llOO' under which conditions carbon is freely deposited. The carbon varies in the first place regularly with the depth increasing from the outside inwards but in cooling segregation takes place the ferrite crystals at the surface and the cementite crystals lower down growing a t the expense of the intermediate zone. It is shown microscopically that the process of decarburisation depends much more on the action of gases than on the diffusion of solid carbon.C. H. D. The Structure of Hardened Steel. W. J. KURBATOFF [and in part M. M. MATWEIEFF] (&fetdurg& 1908 5 721-728).-Austenite is best prepared by quenching steel containing 1-8-2*2% of carbon from 1250' in mercury a t 130O. No change is produced by heating such steel containing austenite at 65-85' for several months. A t 118' recrystallisation is visible in a few days. At 180' austenite changes to troostite this transformation reaching a maximum at 245'. The reaction austenite troostite proceeds from right to left at 110-150' from left to right above 150° and again from right to left above 1000'. Austenite is regarded as a lower carbide of iron the composition of which approaches the formula Fe,C.Troostite and sorbite appear to be solutions of carbon in p- and a-iron respectively. C. H. D. Influence of Manganese on the System Iron-Carbon. FRIEDRICH WOST (MetalZurgie 1909 6 3-1 4).-Manganese readily vaporises and attacks the platinum of an electric furnace A magnesite crucible is therefore placed inside a vertical iron tube through which a current of nitrogen is passed. The iron tube is coated externally with asbestos and kaolin and is surrounded by the heating tube of the resistance furnace. The addition of manganese up to 13% lowers the freezing point of iron saturated with carbon. Further additions raise the freezing point which is a t 1250' in an alloy containing 80% of manganese. The temperature at which the eutectoid pearlite is formed is rapidly lowered by the addition of manganese becoming 580' at 5% Mn and disappearing at higher concentrations.The difference between the transition points on heating and on cooling is also increased. Microscopically the increase in the proportion of manganese is shown by the disappearance of graphite and the increase of cementite. The plates of cementite also increase in size and the eutectic dis- appears its place being taken bya solid solution of carbon in iron and manganese. The iron-graphite eutectic point is' displaced by manganese being at 4005% C for an alloy containing 50% Mn. Manganese thus enters into both series of solid solutions that rich in iron and that rich in carbon. C. H. D Metdlio Hydroxides. HERMANN WALDEMAR FISCHER (Habilitatiorns- schrift Braslau 1907).-The red colloidal hydroxide a t first obtained by the hydrolysis of ferric chloride solutions is converted by the hydro-242 ABSTRACTS OF CHEMICAL PAPERS.chloric acid also formed into a yellow modification insoluble in hydro- chloric acid. Fresh suspensions of this modification show a green fluor- escenc9. Neutralisation of a part of the acid hinders the formation of the yellow colloid. At 150-170° in a sealed tube in concentrated solution a violet-black dense colloid is also formed distinct layers of the yellow and black modifications being found together. The black colloid contains only 1*5-30A of water. Similar results are obtained with hydrolysable salts of other metals a t 310’. A study of the dehydration of the mineral ferric hydroxides leads to the conclusion that limonite and xanthosiderite are only colloidal goethite containing various quantities of adsorbed water.Xantho- siderite is thought to be identical with the yellow colloid described above. Goethite is a definite compound whilst the existence of hydrohsmatite is doubtful. When sodium hydroxide is added to a solution of chromic chloride the precipitate formed soon re-dissolves and a further addition of alkali is necessary to produce a precipitate. This process may be repeated several times. A mechod is also described of determining by observations of the conductivity of such solutions whether basic chlorides are formed. Barium hydroxide is used as the base being added to solutions of metallic chlorides (0.1Nchlorine) a t Oo. The existence of the compounds Fe2C15*OH and Fe2C1(0€l) is clearly shown by the curves as is that of Al,Cl(OH) Cr.,Cl,*OH and Cr2C14(OH)2.C. H. D. Resistance of Ferrous Solutions to Oxidation by the Air. T. WARYNSKI (Ann. Chim. anal. 1909 14 45-47).-Experiments showing that solutions of ferrous sulphate in presence of free sulphuric acid are very stable in contact with the air. Addition of strong hydrochloric acid renders them more liable to oxidation. Traces of certain substances such as cupric chloride platinic chloride and palladium nitrate greatly favour the oxidation process. Absorption of Hydrogen by Metallic Nickel. ADOLF SIEVERTS and JOH. HAGENACKER (Bey. 1909 49 338-347).-The authors are unable to account for the discrepancy between Sieverts’ work (Abstr. 1907 ii 741) and Mayer and Altmayer’s (Ahstr.1908 ii 950) as to the amount of hydrogen absorbed by nickel at 360’ and 560O. They have repeated and confirmed Sieverts’ experiments using about 3 grams 16.5 grams and 27 grams of nickel ; Mayer and Altmayer’s contention that equilibrium was not attained in Sieverts’ experiments owing to the large quantity of nickel used is thus disproved. Henry’s law does not hold for hydrogen and nickel a t 822O and 9239 the amount of hydrogen absorbed being more nearly proportional to L. DE K. the square root of the pressure. c. s. Alloys of Cobalt and Bismuth. F. DUCELLIEZ (BUZZ. Xoc. ci~im. 1909 [iv] 5 61-63).-The author has attempted to obtain alloys of cobalt and bismuth by heating mixtures of the powdered elements to various temperatures in an atmosphere of hydrogen.No development of heat is observed and malleable products are obtained in which theINORGANIC CHEMISTRY. 243 cobalt retains its magnetic properties and from which the bismuth can be distilled. R. J. C. Solubility of Chromic Oxide. MILORAD Z . JOVITSCHITSCH (Monatsh. 1909,30,47-50).-The author finds that the statement that strongly ignited chromic oxide is insoluble in acids is incorrect. In two experiments 2-85 grams and 0.815 gram of chromic oxide after ignition first by means of a Bunsen flame and subsequently for ten to fifteen minutes by a blowpipe flame dissolved in con- centrated nitric acid to the extents of 2.585 grams and 0.772 gram respectively ; the residue in each case proved highly resistant t o the action of the acid and only dissolved in traces.Evaporation of the acid solution until nearly all odour of nitric acid has disappeared yields a dark brown mass the absolute alcoholic solution of which gives on evaporation a green crystalline crust recrystallisable from hot water. On analysis this crust is found to be a neutral chromic nitrate Cr2(0N0,) which is stable towards light and takes up moisture (maximum 3H,O) from the air becoming a darker green. T. H. P. Thorium. H. KARSTENS (Zeitsch. Elektrochem. 1909 15 33-34). -In reply to Meyer's criticism (this vol. ii 53) the author gives further details of the chemical part of the work described by Bolton (this vol. ii 53). The thorium chloride used was a pure white crystalline substance which dissolves completely in water and contains thorium and chlorine in the ratio required by the formula ThCI,.If the temperature is allowed to rise too high a yellow non-crystalline product is obtained which contains oxygen. When the metal is shaken with 5% hydrochloric acid 85% of it dissolves but only 10% is present in the solution in the form of the complex acid. Comparison of the acid with meta-thorium chloride showed their properties to be different. T. E. The Newly Discovered Element of the Tin Group. ANTON SKRABAL and PAUL ARTMANN (Chem. Zeit. 1909 33 143).-The metal of the tin group obtained by Evans (Trans. 1905 03 660) from thorianite and by Ogawa (Abstr. 1908 ii 953) from molybdenite closely resembles molybdenum in its reactions. A metal resembling molybdenum but differing from it in some reactions was observed in certain specimens of iron and steel in 1897 (Boucher Abstr.1898 ii 7 3 ; Ruddock Chem. News 1897 76 118 ; Jones ibid. 171). The authors have obtained from a ferro-vanadium a small quantity of a sulphide resembling that of molybdenum in its reactions but failing to give the characteristic blue coloration when dissolved in nitric acid and evaporated with sulphuric acid. This metal may be identical with the new metal from thorianite. C. H. D. Tetragenic Double Salts of Antimony Fluoride and their Applicability as Mordants. ARTHUR ROSENHEIH and HERBERT GB~NBAUM (Zeitsch. anorg. Chern. 1909 61 187-20l).-Tetragenic244 ABSTRACTS OF CHEMICAL PAPERS. double salts are those containing four different elements or radicles exclusive of water of crystallisation (Meyerhoffer Abstr.1903 ii 292). Salts containing antimony fluoride as a component find application as mordants. Antimony trifluoride prepared from antimony trioxide and hydro- fluoric acid is best stored in vessels of white celluloid. Three hundred and eighty-five grams dissolve in 100 grams of water a t O' and 564 grams in 100 at 30'. There is no appreciable hydrolysis below 30'. The solubility is increased by the addition of alkali salts but very unequally potassium sulphate having only a small effect whilst potassium chloride oxalate or tartrate increases the solubility greatly. When the quantity of alkali salt exceeds a certain limit the tetragenic double salt separates. More dilute solutions have been investigated by means of their conductivity.The conductivity of the mixed solution is compared with the sum of the conductivities of antimony fluoride and of the alkali s a l t at 0'. The solutions containing potassium nitrate sulphate and hydrogen oxalate do not give any evidence of the presence of complex ions whilst solutions coutaining normal potassium oxalate and tartrate ammonium oxalate and potassium antimony tartrate indicate considerable formation of complex ions even in dilute solution. The two classes of salts are very sharply distinguished by plotting curves of which the ordinates are h,(SbP + X) - X,SbF and the abscissae J k Only those salts the complex ions of which persist in dilute solutions are of use as mordants. Several of the double salts have been isolated in the crystalline solid state.Potassium nitrate forms the salt 3KN0,,PbF3 ; ammonium oxalate forms large transparent crystals of 4(NH4),C,0,,3SbF ; sodium oxalate forms 2Na,C,0,,3SbF3 crystallising unchanged from water ; potassium antimony oxalate forms the stable salt K,SbO( C,O4),,SbF,,8H,O. Mercuric chloride and cyanide like antimony fluoride have the power of forming tetragenic double salts and all of these are very weak electrolytes having also the power of forming complex ions. C. H. D; Some New Fluorides. OTTO RUFF JULIAN ZEDNER EMIL SCHILLER and ALFRED HEINZELMANN (Bey. 1909 42 492-497).-CoZumbium pntajuoride CbF was prepared by the action of fluorine on columbium containing about 3% of aluminium. The roughly-powdered metal con- tained in a boat was placed in a platinum tube 25 cm.long and 1 *2 cm. diameter the middle portion of which is insertedi n an asbestos box ; the constricted end of the tube is cooled by a lead worm and connected to a receiver from which moisture is carefully excluded. The fluorine when passed over the merely warmed columbium at once combined and the reaction was finished when the tube began to cool. The box was next heated at 250° when the pentafluoride distilled into the cooled portion of the tube the aluminium fluoride remaining behind. On re-distillation in a vacuum at l l O o it is obtained as colourless strongly refractive monoclinic prisms m. p. 72-73O (corr.) and b. p. 236'/760 mm. (corr.). It is very hygroscopic and dissolves in water,INORGANIC CHEMISTRY. 2 45 from which sodium hydroxide and ammonia precipitate columbic acid ; yield 75% Tantalum pentc@uoYide TaF prepared in a similar manner and purified by distillation in a vacuum at 90-lOO" forms colourless strongly refractive prisms m.p. 94" (corr.) and b. p. 225-226-5"/'760 mm. (corr.). It it very hygroscopic dissolving in water from which alkali and ammonia precipitate tantalic acid containing fluorine. It attacks glass slowly at ordinary temperatures quickly at higher ; yield SO-S5%. The reaction between uranium and fluorine is a very vigorous one and the product chiefly consists of tetrafluoride mixed with some oxygenated substance and the hexafluoride in small quantities. Uranium hexacfEuoride UF is best prepared from the pentachloride cooled in an alcohol-carbon dioxide mixture. After the reaction is over carbon dioxide is passed through the apparatus the tube evacuated and the product distilled.It forms glistening colourless fuming monoclinic prisms which do not melt but sublime at the ordinary temperature under diminished pressure. It is very hygro- scopic is soluble in water and attacks glass in presence of a trace of water forming silicon tetrafluoride and uranium oxyfluoride. Its aqueous solution does not decolorise potassium permanganate and ammonia forms ammonium uranate and fluoride W. R. Alloys of Platinum and Antimony. I(. FRIEDRICH and A. LEROUX (Uetallurgie 1909 6 1-3).-The freezing point of antimony is not appreciably lowered by the addition of platinum. The freezing- point curve rises to a maximum at 1226" and 44.7% Pt corre- sponding with the compound PtSb,. A second compound probably PtSb is formed at 1045". The curve then falls to a eutectic point at 685' and 77% Pt and rises to the freezing point of platinum. Two reactions take place in the solid state the compound PtSb being transformed into one richer in antimony and a third compound Pt,Sb being formed from alloys rich in platinum at 644O the eutectic structure disappearing when the alloys are maintained for some hours at this temperature. The compound PtSb readily blackens when heated. C. H. D. The Platinum Compound Analogous to Purple of Cassius. LOTHAR WOHLER (Ye&. deut. Naturforsch. Aemte. 1907 ii 105-106). -The blood-red colour produced by stannous chloride in solutions of platinum salts darkens after a time more rapidly on warming and finally the solution becomes black and slightly turbid. The red colour is extracted by shaking with ether or ethyl acetate and on addition of water a chocolate- brown precipitate forms consisting of platinum tin and oxygen in varying proportions. When freshly precipitated the substance is soluble in dilute hydrochloric acid but becomes almost insoluble on drying. It does not diffuse through parchment paper and is therefore regarded as an adsorption compound of colloidal platinum and colloidal stannic acid. The adsorbed metal does not show the ordinary reactions of colloidal platinum. A similar red solution is obtained by reducing platinic VOL. XCVI. ii. 17246 ABSTRACTS OF CHEMICAL PAPERS. chloride with an ethereal solution of phosphorus in the presence of gelatin. When stannous bromide and platinum tetrabromide are brought together there is a reversible equilibrium 2SnBrz + PtBr Z Pt+ZSnBr which is displaced towards the left by raising the temperature. G. S.

ISSN:0368-1769    

DOI:10.1039/CA9099605224

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

246 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Optical Investigation of Sakhalin Naphtha. MICHAEL A. RAKUSIN (J. Buss. Phys. Chem. Xoc. 1908 40 1735-1746. Compare Abatr. 1907 ii 882 883).-The author has carried out an optical investigation of the various fractions of Sakhalin naphtha from the results of which conclusions are drawn as t o the geological age of the naphtha. This age is divided into two periods (1) that during which filtration and distillation occurred and (2) that of car bonisation. T. H. P. New Chromium Mineral from Servia. MILORAD Z. JOVITSCHITSCH (Monatsh. 1909 30 39-46).-The brooks below one of the branches of the Kopaonik mountains contain a small-grained glittering sand from which a magnet removes a dark dull portion leaving light shining crystals behind.After purifying from sandy impurities these two constituents were examined separately. The shining crystals D 3.1 to which the author gives the name chromitite give analytical numbers which if small proportions of aluminium and magnesium are neglected correspond with the formula FeCrO Fe,Cr,O or Fe,O,,Cr,O,. The dull crystals resemble magnetite both in their appearance and in their magnetic properties but on separating by means of a magnet placed at varying distances from the sand three fractions were obtained containing (1) 66.99% Fe and 6.01% C r ; (2) 43-45% Fe and 21-5-25% Cr; (3) 34-38% Fe and 34-36% Cr. Fraction (2) corresponds with a compound having the formula 2Fe203,Cr203 which the author regards as a transition stage t o the chromitite crystals. T.H. P. Rosasite a New Mineral from the Mines of Rosas (Sulcis Sardinia). DOMENICO LOVISATO (Atti R. Accad. fincei 1908 [v] 17 ii 723-'728).-The new mineral occurs sparingly in small veins associated with- malachite and aurichalcite as compact apparently fibrous light green mammellated masses D20 4.074 H 4.5. COP CUO. ZnO. PbO. H,O. Total. 30'44 36-34 33'57 trace 0'21 100-56 2Cu0,3CuC0,,5ZnC03. The analysis corresponds approximately with the formulaMINERALOGICAL CHEMISTRY. 247 It does not appear to be merely an intimate mixture of malachite and smi t hsonite. A dark green mineral was found coating the rosasite but in quantity insufficient for analysis. Brugnatellite a New Mineral Species Found in Val Malenco. ETTORE ARTINI (Atti R. Accad. Lincei 1909 [v] 18 i 3-6).-The asbestos strata of Val Malenco contain a mineral which has not been previously described and which occurs in the form of flesh-red lamins or laminar aggregates resembling mica and exhibiting ready cleavage and slight nacreous lustre.This mineral to which the author gives the name Brugnatellite is a hydrated ultra-basic carbonate having the composition Insol. in HCI. H,O. CO,. Fe,O,. MnO. MgO. Total. C. H. D. 1 -03 33.77 7-78 13-20 1 -80 42.79 100'37 Replacing the small proportion of MnO by an equivalent amount of MgO the above numbers are in good agreement with those required by the formula Mg,FeCO H or MgC03,5Mg(OH)$'e(OH),,4H20. In its natural position Brugnatellite is accompanied by asbestos aragonite magnesite artinite and brucite.T. H. P. Composition of Warwickite. W. M. BRADLEY (Amer. J. Sci. 1909 [iv] 27,179-184).-TTnder I is given the mean of two analyses of material D 3.342 separated by means of heavy liquids from a metamorphic limestone occurring in contact with granite at Amity New York. The mineral has the form of minute slender crystals showing the characteristic copper-red reflections on the cleavage surfaces. B,O,. TiO,. SiO,. MgO. FeO. Fe,O,. Al,O,. Total. I. 21-29 24-86 1-39 35'71 9-15 4.76 2-91 100.07 11. 23.87 27.87 1-56 38.63 8.07 - - 100 -00 Spinel and magnetite are intimately associated and intergrown with the mineral and deducting alumina and ferric oxide together with equivalent amounts of magnesia and ferrous oxide the composition of the pure mineral is recalculated under 11.This corresponds with the formula B,O,,TiO 3( Mg,Fe)O or (Mg,Fe),TiB,O,. L. J. S. Diopside and its Relations to GalciuE and Magnesium Metasilicates. EUGENE T. ALLEN and W. P. WHITE with optical study by FRED. EUGENE WRIGHT and ESPER S. LARSEN (Amer. J. Xci. 1909 [iv] 2'7 1-47).-The thermal and optical relatoions of calcium metasilicate and of magnesium metasilicate have been previously studied (Abstr. 1906 ii 683 865) and the investigation is now extended to mixtures of these. CaMg(SiO,) was obtained this being identical with diopside; it melts at 1380° and has D 3.275 ; well-formed crystals were crystallised from molten calcium chloride. Two eutectics with melting points of 1348' and 1 3 7 5 O occur; the former cousists of 60% diopside and 40% pseudo- Only one stable compound 17-2248 ABSTRACTS OF CHEMICAL PAPERS.wollastonite and the latter of 95.5% of mixed crystals (these contain- ing 62.5% diopside and 37.5% MgSiO,) and 4.5% a-MgSi03. A method for the more accurate determination of the composition of eutectic mixtures is described. Six different series of solid solutions are recognised only two of which contain more than 3 or 4% of the minor component ; wollastonite may take up 17% of diopside and diopside dissolves 60% of magnesium silicate. The specific- volume curve consists of three well-defined branches the first corresponding with mechanical mixtures of pseudo-wollastonite and diopside the second with solid solutions of a-MgSi03 in diopside and the third with mixtures of the saturated mixed crystals and free P-MgSiO,.There is a sharp minimum in the curve correspondhg with diopside. A new method is described for determining the inversion temperatures of magnesium silicate and of the mixed crystals. L. J. S. Glaucophane-rocks from Switzerland. ULRICH GRUBENMANN (Zeitsch. Kryst. Min,. 1909 46 I28 ; from Festschr. H. Rosenbusch Xtuttgart 1906).-Analysis of glaucophane from Lavintzie in the Bagne valley Wallis gave SiO,. TiO,. A1,0,. Fe,03. FeO. CaO. MgO. R,O. Na,O. 100"). tion. Total. Sp. gr. 52-76 0'94 6.80 10-38 8'45 2.25 9.38 1'11 7'20 0.08 0.44 99 79 3.155 corresponding with 64Na,Al2Si4Ol2 + 64Na,Fe,Si,O + 40Ca(Mg,Fe),Si40 + 5 1 (Mg,Fe),Si,O,,. The material differs from other glaucophanes in the high percentage of iron and approaches crossite in composition.H,O Loss (at on igni- L. J. S. Mineralogy of Sardinia. Andesine [Plagioclase] from Monte Palmas (between Sassari and Alghero). FEDERICO MILLOSEVICH (Atti R. Accad. Lincei 1909 [v] 18 i 28-24).-The author gives measurements of andesine found a t Monte Palmas the numbers being in good agreement with von Rath's values corrected by Dana. The crystals found have D 2.679 and are in nearly all cases twinned various types of twinning being observed. Analysis gives the following numbers SiO,. A1,0,. Fe,O,. CaO. Na,O. K,O. Total. 59-14 25'74 0.32 7.87 6.87 0'61 100.55 The crystallographic and optical characters are in accord with the acid character indicated by the analytical numbers T. H. P. Meteorite of St. Christophe-la-Chartreuse (Vendee). ALFRED LACROIX (Chem.Zentr. 1909 i 316; from Bull. SOC. Sci. nat. de Z'Owst France 1906 [ii] 6 81-1 12)-The stone weighing 5396 grams which fell on November 5 1841 at St. Christophe-la-Char- treuse near Rocheservihe is a grey chrondrito with the following mineralogical composition nickel-iron 9.5 7 ; schreibersite and graph- ite traces ; troilite 6.9 ; chromite 0.67 ; olivine (near hyalosiderite) 42.83 ; hypersthene 28.39 ; diopside 3.46 ; felspar 8.39. There is also present in small amount a monoclinic pyroxene similar to rhombicPHYSIOLOGICAL CHEMISTRY. 249 pyroxene in composition which is referred to as clinohypersthem ; this has crystallised out from the fused rhombic pyroxene md it is identical with the artificially prepared magnesia-pyroxene ; its presence has been detected in several chronditic meteorites. Maskelynite and an undetermined mineral resembling monticellite are also present. The felspar has the composition (Ab,Or)loAnll. The nickel-iron contains Fe 81.1 ; Ni 17.8 ; Co 1.1 ; P trace. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9099605246

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological C he mi s tr y. 249 Influence of Oxygen on Athletes. LEONARD E. HILL and MARTIN ELACK (Proc. physiol. Soc. 1909 xxviii-xxxvi ; J. Physiol. =).-Experiments on athletes designed to show the beneficial effect of oxygen inhalation. Oxygen Capacity. ARTHUR E. BOYCOTT and C. G. DOUGLAS (J. Path. Bact. 1909 13 256-295).-The carbon monoxide method for determining the total oxygen capacity and volume of the blood gives satisfactory results in rabbits. Normal rabbits have about 5-5 C.C. of blood and 0.7 C.C. of oxygen capacity per 100 grams of body- weight ; females have more dilute blood than males. About 93% of the total haemoglobin in rabbits is in the blood. Experiments are given in detail showing the rate of regeneration of the blood after single and multiple haemorrhages.Apparent ansmia after haemorrhage and in aniline poisoning may be due to increase in the blood-volume. W. D. H. W. D. H. The Sugar of the Blood. V. PETER RONA and LEONOR MICHAELIS (Biochem. Zeitsch. 1909 16 60-67. Compare Abstr. 1908 ii 117).-By the use of the methods previously described i t is shown that a considerable fraction of the blood-sugar is contained in the corpuscles. W. D. H. Activation of Haemolysin by Amino-acids. TAKAOTI SASAKI (Biochem. Zeitsch. 1909 16 71-80).-Guinea-pig’s serum has very little haemolytic action on the corpuscles of the goat and horse; the addition of glycine or alnnine leads t o active hsmolysis. W. D. H. The Gastric Digestion of Caseinogen. LOUIS GAUCHER (Cmpt. rend. 1909 148 53-56).-The digestion of milk was studied in the case of a dog with a duodenal fistula.Three phases could be dis- tinguished (I) I n the first quarter of an hour after ingestion the milk could be obtained from the fistula in a practically unchanged state. (111) In the third phase it was more altered and coloured with bile. The ctiseinogen passes the stomach without peptonisation and clotting is not necessary for the subsequeat stages of digestion. (11) It was afterwards obtained in a clotted form. S. B. S.250 ABSTRACTS OF CHEMICAL PAPERS. The Part Played by Elementary Hydrogen in Metabolism. CARL OPPENHEIMER (Biochem. Zeitsch. 1909 18 45-59).-Elementary hydrogen like elementary nitrogen plays no part in metabolism in the animal body W. D. H. JOHN A. 31 URLIN (Pr oc Amer.physiol. Soc. 1908 xxxi-xxxiii ; Amer. J. Yhysiol. %).-In pregnaot dogs there is a minus nitrogen balance in the first four weeks and an increasing plus balance in the last five weeks of gesta- tion. On a creatine-free diet the creatinine output was constant but during uterine involution after parturition creatine appeared in the urine. The differences obtained by subtracting the total resting metabolism of the mother dog from the total metabolism of the mother and puppies after parturition are not quite proportional to the weights probably because the metabolism in the puppies was reduced as they helped to keep each other warm. I n the puppies immediately after birth the respiratory quotient was unity ; this indicates com- bustion of carbohydrate (glycogen).Fate of the Non-hydroxylated Benzene Ring of Protein in the Animal Body. HARALAMB VASILIU (Bled. Zentr. 1909 38 46-48 ; from Hitt. landw. Inst. K. Univ. Breslau 1908 4 355-374).-The benzoic acid obtained by oxidising foods with permanganate is derived from the a-phenylaminopropionic acid group of the protein; the benzene ring of the tyrosine group is destroyed. The benzene ring of a-phenylaminopropionic acid is only to a very slight extent destroyed by herbivorous animals ; most of it appears in the urine partly as hippuric acid and partly as a-phenylaminopropionic acid In the human body and most probably in the case of carnivorous animals the greater part is destroyed and only small amounts of a-pheny laminopropionic acid pass into the urine. Experiments with sheep showed that 42% of the non-hydroxylated benzene was present in the urine as hippuric acid; the remainder 58% is presumably in the form of a-phenylaminopropionic acid or its polypeptide. The destruction of the benzene ring by carnivorous animals is attributed to the co-operation of acid products due to animal food.Indications were obtained in experiments with a calf fed with milk of the breaking up of the benzene ring. Effect of Carbon Dioxide on the Frog’s Pupil. JOHN AUER (Proc. Amer. physiol. Soc. 1908 xvi; Amer. J. Physiol. =).-In asphyxia the pupils of mammals are dilated. I n the frog exposure to carbon dioxide causes extreme contraction; this also occurs in the isolated eyeball. The gas is however unable to overcome fully the opposite effect produced by adrenaline and adrenaline is unable to exert its full effect when the iris is under the influence of carbon dioxide. W.D. H. Autolysis. S. YOSHIMOTO (Zeitsch. physiol. CItem. 1909 58 341-368).-The commonly used preservatives boric and salicylic acids hasten fermentation actions in the liver at certain small ‘‘ optimum ” Protein Metabolism in Development. W. D. H. N. H. J. M.PHYSIOLOGICAL CHEMISTRY. 251 concentrations; excess slows or stops the action. The same is true for allylthiocarbimide and alcohol although the actual figures of optimum concentration are naturally different in all cases. Normal autolysis and that which is produced by carbon dioxide in chloroform water run the same course; there is no lessening of the yield of purine bases such as is said to occur with other acids.The following table gives the optimum concentrations of the substances mentioned together with the amount of autolysis as judged by the proportion of the total nitrogen going into solution under similar conditions %* Chloroform water (taken as the normal) ............................. 21 -59 Alcohol (concentration 5%) ............................................... 32.01 38 -78 Boric acid (concentration 1%) ............................................. 40.80 47 -37 Allylthiocarbimide (concentration 1/8% saturated solution) ...... Salicylic acid (concentration half saturated solution) ............... W. D. H. Heat-coagulation in Plain Muscle. EDWARD B. MEIGS (Proc. Amer. physiol. Xoc. 1908 xv-xvi ; Amer. J. Physiol. 23).-In both plain and striated muscle of the frog irritability is lost about 40° ; the shortening of striated muscle is marked a t 50° but a t this tempera- ture the plain muscle lengthens.I n both cases the protein is coagulated and lactic acid liberated ; the swelling of the sarcostyles in the case of striated muscle !so produced causes shortening whereas the swelling of the plain fibre with a different histological structure produces lengthening. W. D. H. The Influence of Sodium Chloride and Calcium Chloride in the Potassium Contraction. WILLIAM D. ZOETHOUT (Bmer. J. Physiol. 1909 23 374-388).-The amount of sodium in a muscle is sufficient to counteract the stimulating effect of a small quantity of potassium salt. The removal of this sodium by immersion in a 6% sugar solution renders the muscle more irritable toward potassium ; the same is probably true for calcium.Both sodium and calcium favour the relaxation of a muscle in potassium contraction. Ringer’s solution and 0.7% sodium chloride solution speedily reduce the irritability of muscle toward potassium. Although such solutions preserve muscular irritability toward electrical stimulation for a long time they cannot be regarded as altogether inert fluids. W. D. H. The Influence of Salts of Strong Organic Bases on the Resting Current and Excitability of Frog’s Muscle. RUDOLF HOBER and HEINRICH WALDENBERG (YJiiger’s Archiv 1909 126 331-350).-The salts of quaternary ammonium bases piperidine guanidine and trimethylsulphine that is of strong organic bases affect the resting current and excitability of frog’s muscle in the same way as do salts of strong inorganic bases and most closely resemble the effects of cssium salts. The action is a reversible one.The resting current and excitability are both affected in the same way. W. D. H.252 ABSTRACTS OF CHEMICAL PAPERY. Cholesterol in Eeart Muscle. G. W. ELLIS and JOHN A. GARDNER (Proc. physiol. Soc. 1908 viii-x ; J. Physiol. =).-The amount of cholesterol in heart muscle is approximately the same as in other kinds of muscular tissue. W. D. H. Cycloses. FRANZ ROSENBERGER (Zeitsch. physiol. Chem. 1909 58 369-372).-Polemical. A reply to Starkenstein (this vol. ii 77). W. D. H. Black Cephalopod Inks. RAFFAELE PALADINO (Biochem. Zeitsch. 1909 16 37-44).-The black excretion of Eledone moscata has the following composition water 40 soluble mineral substances 4.06 soluble organic substances 2 -32 insoluble mineral substances 6.67 in- soluble organic material 40 6%.The secretion of Sepia oficirudis has the values water 20 soluble mineral 8.5 soluble organic 3.5 insoluble mineral 15-0 insoluble organic 34.0%. The composition of the black insoluble pigment melanin is C 52.4 H 4.02 N 5*6% together with sulphur and iron. The following were shown to be present in the inks sodium potassium calcium iron chloride carbonate and sulphate. Urea uric acid and dextrose could not be detected. Parent Substance of Hippuric Acid. HARALAMB VASILIU (Bied. Zentr. 1909 38 132-133; from Mitt. landw. Inst. K. Univ. Breslau 1908 4 374-378. Compare Abstr. 1908 ii 211).-The hippuric acid produced from clover hay is derived partly (3/5) from proteins and partly (215) from a non-nitrogenous substance.I n the case of meadow hay the amount produced from non-nitrogenous sub- stances is fifteen times as great as the portion derived from proteins. It seems probable that as regards foods such as leguminous foods oil cakes etc. which give rise to relatively small amounts of hippuric acid most of the acid is derived from proteins whilst in the case of foods which furnish large amounts of the acid its production is mainly from non-nitrogenous substances. The parent substance in the latter cace seems to contain a hydroxylated benzene ring ; it is possibly quinic acid which is always present in meadow hay and yields in the animal body 36% of the theoretically possible amount of hippuric acid.J. J. S. N. H. J. M. The Influence of Calcium Chloride on the Formation of Transudates. LEO LOEB S. M. FLEISCHER and D. M. HOYT (Zentr. Physiol. 1908 22 No. 16 reprint).-The addition of calcium chloride to 0.85% salt solution diminishes the rate of excretion of liquid by the kidneys and also into the intestine when the solution is injected intravenously into rabbits. It increases on the other hand the rate of transudation into the peritoneal cavity. The latter action is due to two factors namely the indirect factor which results from diminivhed kidney excretion and the direct factor due to the action of the calcium salt on the endothelium of the vessels or peritoneum. The labter can take place when the action of the kidneys is excluded.G . C. MATHISON (Proc. physiol. Soc. 1909 xx-xxii ; J. Fhysiol. 38).-The total phosphorus was estimated by S. B. S. Phosphorus of Urine.PHYSIOLOGICAL CHEMISTRY. 253 Bayliss and Plimmer’s modification of Neumann’s method and inorganic phosphates by precipitation with magnesia mrxture ; the difference represents organic phosphorus. The latter represents 5 to 10% of the total a higher figure than has been previously obtained. W. D. H. Excretion of Magnesium and Calcium. LAFAYETTE B. MENDEL- and STANLEY R. BENEDICT (Proc. Arner. physiol. Xoc. 1908 xviii; Amer. J. Physiol. 23).-When magnesium salts are introduced parenterally elimination occurs through the urine in about forty-eight hours although some may be retained for two weeks. There is no purgation.There is accompanying this an increased excretioq of calcium by the kidney and a lessened excretion of calcium by the bowel. If calcium salts are introduced into the circulation the calcium especially in rabbits is abundantly excreted in the urine’; this is accompanied by an increased output of magnesium Acetone Substances in the Organs of Cases of Diabetic Coma. 11. H. CHRISTIAN GEELMUYDEN (Zeitsch. physiol. Chem. 1909 58 255-272. Compare Abstr. 1904 ii 275).-The investigations of the amounts of acetone substances were ‘made in surviving organs ; during the life of diabetics other relationships may prevail. The view put forward is that during life /3-hydroxy- butyric acid is formed mainly in the liver ; it is thence carried by the blood to other organs and taken up by them; the increase of fat metabolism owing to the small amount of carbohydrate metabolism leads to a greater production of the acid than occiirs in health ; but as it leaves the liver for distribution the amount remain- ing in the liver is comparatively small.The formation of the acid and its conversion into acetoacetic acid are oxidation processes. I n diabetes the glycogenic function of the liver is in abeyance and little or none of the substance is found there. W. D. H. JOHN LIGHTERWOOD GREEN (J. Path. Bact. 1909 13 296-310).-In nephritis produced in rabbits by potassium chromate the quantity of urine on the first two days sinks to 50% of the normal and then gradually-returns to normal. The protein rises to maximum on the second day and then gradually dis- appears.The protein consists of albumin and globulin in inconstant proportions. In a dog the total nitrogen was reduced by 20% the chlorides by 50% the creatinine was slightly reduced and the phosphates were unaltered. In three cases of the disease in man the urea nitrogen was found to follow the total nitrogen but there is no constancy in the reduction of either; in two cases the ammonium excretion was lorn and in the third high; the creatinine was slightly reduced in two cases. In the blood in the experimental cases there was a fall of 14% in the red corpuscles on the onset of nephritis and a rise of 43% in the colourless corpuscles (especially of polynuclear leucocytes) ; the return to normal was gradual. JOHN AUER and SAMUEL J. MELTZER (Proc.Amer. physiol. Soc. 1908 xx-xxi ; Arner. J. Physiol. 23).-Calcium restores the irritability of the cardiac vagus Nitrogen and chlorine are not appreciably altered. W. D. H. Experimental Nephritis. W. D. H. Effect of Calcium on the Cardiac Vagus.254 ABSTRACTS OF CHEMICAL PAPERS. in animals poisoned by magnesium salts but in the normal animal calcium infused in M / 8 solutions reduces or even abolishes the irritability of the inhibitory fibres of this nerve leaving its motor fibres unaffected. W. D. H. The Behaviour of Phthalic Acid in the Animal Organism. JULIUS POHL (Biochem. Zeitsch. 1909 16 68-70).-Porcher states that 75% of isophthalic and terephthalic acids appear in the urine whilst phthalic acid is almost completely burnt in the organism of the dog.The last statement is in contradiction of work by Pribram. The present experiments confirm the observation of Pribram that the ort ho-acid is almost completely recoverable in dog’s urine. W. D. H. Pressor Substances from Putrid Meat. GEORGE BARGER and GEORGE S. WALPOLE (Proc. physiol. SOC. 1909 xxiii ; J. Physiol. 38). -The presence of a substance or substances producing a rise of arterial pressure has been noted by Abelous in putrid meat and by Dixon Taylor and Rosenheim in putrid placenta. Two substances was separated from putrid meat namely isoamylamine and p-hydroxy- phenylethylamine ; both are pressor substances especially the latter. The relation of these two bases to leucine and tyrosine respectively is clear and the possibility of their formation in the intestine is of interest.W. D. H. Physiological Action of Primary Fatty Amines. GEORGE BARGER and HENRY H. DALE (Proc. physiol. SOC. 1909 xxii; J. Physiol. 38).-Barger and Walpole’s work (see preceding abstract) suggested the examination of other amines. The following were tested methylamine ethylamine 12-propylamine isopropylamine n-butylamine isobutylamine isoamylamine n-amylamine n-hexylamine n-heptylamine and n-octyl- amine. The hydrochlorides were used in all cases in N/10 solution. The first to give a pressor effect is isobutylamine ; the activity rapidly increases on ascending the series up to hexylamine; those still higher show a decreasing action. Action of Digitalin and Allied Substaqces on Striated Muscle. AUGUSTUS D. WALLER (PYOC. physiol. Soc. 1908 x-xvi ; J.Physiol. 38).-Natroelle’s digitalin has no action on muscle ; Merck’s digitonin cryst. digitalinum pulv. pur. (Merck) digitalinum venum (Schmiedeberg) and digitoxin (Merck) were also employed. The last-named has also no action ; the other three vary in degree of activity but all produce characteristic effects namely well-marked contraction and loss of contractility. The action of saponin is very similar. W. D. H. W. D. H. Action of Muscarine a n d Pilocarpine on the Heart. HUGH MACLEAN (Bio-Chem. J. 1909 4 66-71).-The effect of these drugs is to be ascribed t o their stimulating influence doubtless by chemical interaction on the nerve endings of the inhibitory nerve fibres of the heart. W. D. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 255 The Passage of Phenolphthalein aEd of its Disodium Derivative Through the Organism.C. FLEIU (J. Pham. Chirn. 1909 [vi] -aS 55-57. Compare Abstr. 1908 ii 313).-When given by the mouth 85% of the phenolphthalein is found in the faeces ; it does not appear in the urine unless very large quantities are given per os or unless it is administered hypodermically or intravenously. Phenol- phthalein is never hydrolpsed in the tissues but probably passes into the urine in combination with sulphuric or glycuronic acid. G. B. Atoxyl. 111. FERDINAND BLUMENTHAL and ERNST JACOBY (Biochem. Zeitsch. 1909 16 20-36).-The introduction of acid radicles (for example acetyl) into the amino-group of the sodium salt of p-amino- phenylarsinic acid (atoxyl) lessens its toxicity ; the introduction of a methyl group does not. Complete substitution of the amino-group by iodine increases the toxic action; as also does its replacement by hydroxyl (Ehrlich). The toxicity of the mercury salt depends on the amount of mercury given. Reduction products of atoxyl are more toxic than atoxyl itself. Details are given regarding its deposition in the tissues and its excretion in the urine. I n the body atoxyl acts directly as an antiseptic. W. D. H. The Present State of Chemotherapeutics. PAUL EHRLICH (Ber. 1909 42 17-47).-A lecture delivered before the German Chemical Society. c. s.

ISSN:0368-1769    

DOI:10.1039/CA9099605249

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 255 Chemistry of Vegetable Physiology and Agriculture. Ammoniacal Fermentation. JEAN EFFRONT (Compt. rend. 1909 148 238-840).-The author gives details OF some experiments which throw light on the function of butyric ferments in the conver- sion of atmospheric nitrogen into a form assimilable by plants. Distillery residues sown with an earth culture undergo symbiotic fermentation through the action of aerobic ferments and an anaerobic butyric ferment. The latter has been isolated and its action studied on dextrose solutions containing various amino-acids. I n the case of aminoacetic acid asparagine and glutamic acid the ammonia formed was free from nmines but when betaine was present pure trimethyl- amine mas obtained. Distillery residues gave ammonia and trimethyl- amine.The ammoniacal fermentation in each case proceeded at the same rate as the destruction of the dextrose. Analogous results were obtained using ordinary earth in place of the pure culture but Decomposition of Nitrates by Bacteria. S. A. SEWERIN (Centr. Bakt. Par. 1909 ii 22 348-370. Compare Abstr. 1900 ii 232).-Under anaerobic conditions (in an atmosphere of hydrogen) the action was more rapid and complete. w. 0. w.256 ABSTRACTS OF CHEMICAL PAPERS. the denitrifying power of Vibrio demitrifcans is increased whilst in the case of Bacillus pyocyaneus there is a still more marked increase. Nitrites are also reduced under anaerobic conditions by both organisms although less readily than nitrates. In the reduction of nitrates by B. pyocyaneus there is always a production of nitrites both in aerobic and anaerobic cultures.With Vibrio denitrijficans nitrites could not be detected in the majority of cases and when present at all generally showed a legs distinct reaction. The reducing power of both organisms is diminished when hydrogen is replaced by carbon dioxide; and B. pyocyaneus failed to grow in broth free from nitrates in an atmosphere of carbon dioxide. Results of experiments with different soils indicated that a total destruction of nitrates does not take place in soils in their natural condition. Addition of 2% of horse dung and 4% of straw to garden soil and other soils resulted in complete reduction of nitrates by B. pyocyaneus. With V. denilriJcans complete reduction only occurred in one soil a marl t o which S% of dung had been added.Nitrites were not found in any of the experiments with soils. N. H J. M. Use of Silver Salts in Sterilising Water. F. TRAETTA-MOSCA (Gazxetta 1909 39 i 69-log).- The author has examined isotachyol and silver chlorate perchlorate and sulphate in regard to their powers of disinfecting water (compare Paterno and Cingolani Abstr. 1907 ii 713). All these compounds exhibit marked germicidal characters and can be advantageously employed for the sterilisation of drinking water pathological organisms such as those of cholera typhoid and dysentery being rapidly destroyed by very small proportions of the disinfectant. This bactericidal action which is exhibited to a far greater degree by isotachyol than by the other silver compounds examined depends principally although not entirely on the silver ions.According to D’Anna (Arch. Parm. sper. sci. afini 1904) the acid radicle of a metallic salt influences the disinfecting action of the latter only in so far as it varies the proportion of active metal present. But the author’s results are not in agreement with this view since silver sulphate containing 69.2% of silver is inferior as a sterilising agent to the chlorate and perchlorate containing 56.3 aQd 52.0% of silver respectively. T. H. P. The R61e of Oxalate in the Germination of Beet Seed. G. DOBY (Landw. Versuchs-Stat. 1909 70 155-158).-During germina- tion the alkali oxnlate disappeared completely whilst the amount of calcium oxalate remained unchanged. Only the former substance can therefore be considered as reserve material.N. H. J. M. Chemical Nature of Root Secretions. JULIUS STOKLASA and ADOLF %ERNEST (Jahrb. wiss. Bot. 1908 46 55-102. Compare Abstr. 1905 ii 607).-Water-culture experiments with maize oats,VEGETABLE PEYSIOLOGY AND AGRICULTURE. 257 and buckwheat showed that when oxygen i s deficient the roots secrete very marked amounts of fatty acids (formic and acetic acids). In the case of barley there was only a slight production of acids. Sugar beet secreted oxalic and acetic acids. Under conditions of abundant aeration no acids are secreted being oxidised to carbon dioxide within the roots ; in some cases traces of hydrogen mere given off along with the carbon dioxide. No secretion of mineral acids took place either under conditions of aeration or without aeration.The amount of carbon dioxide given off by roots varies considerably with different plants. Of the various plants employed barley pro- duced the greatest amount of dry matter in roots and also kave off the greatest amount of carbon dioxide. When however the amount of carbon dioxide given off in twenty-four hours is expressed in mg. per gram of dry matter it is seen that barley produces the smalleet amount. The quantities for the different plants are as follows barley 63.2-74-6 ; oats 111*5-135*4 j wheat 87-6-94.8 and rye 100*7-131*0 mg. CO per gram. In accordance with these results i t was found that when the four plants were grown in powdered gneiss and in basalt manured with ammonium nitrate sulphate and chloride barley produced the least growth and assimilated the smallest amount of potassium and phosphoric acid whilst oats produced the greatest amount of dry matter.All the plants as was also the case with water saturated with carbon dioxide extracted more mineral matter from basalt than from gneiss. Signiflcance of the Colloidal Nature of Aqueous Dye- solutions for their Penetration into Living Cells. WILLY RUHLAND (Ber. Deut. bot. Ges. 1908 ma 772-782).-8 study of the colloidal nature of dyes does not lead the author to modify his criticism of Overton’s theory according to which theory the cell wall is a semi-permeable lipoid membrane. The rate at which various dyes (both basic and acidic) are taken up by living cells bears apparently no relation to the degree of colloidity of their aqueous solutions.G. B. N. H. J. 35. Amounts of Iron and Phosphorus in Vegetables. E. HAENSEL (Biochsm. Zeitsch. 1909 16 9-1 9).-Determinations of dry matter ash iron and phosphorus in twenty-four vegetables and fruits. N. H. J. M. Loss of Nitrates and of Hydrogen Cyanide during the Desiccation of Plants. E. COUPEROT (J. Pharm. Chim. 1909 [vi] 29 100-1 02).-Experiments with the leaves and other parts of Sambucus nigra S. Zaciniata and S. racemosa show t h a t when these are allowed t o dry by mere exposure to the air at atmospheric temperature the quantity of nitrates present may be reduced hy from 20 to 50%. The first two species also yield hydrogen cyanide and the quantity of this substance obtainable from the fresh parts of these plants is similarly reduced after air-drying.On the contrary if the fresh parts of these plants are placed immediately in258 ABSTRACTS OF CHEMICAL PAPERS. a drying apparatus at 60" and maintained a t this temperature until dry there is no loss of nitrates or of hydrogen cyanide. The conclusion is drawn therefore that the losses referred to are due to the utilisation of nitrates and cyanogenetic products by the living cells as reserve materials. T. A. H. Composition of Amapa latex. A RATHJE (Arch. Phccmn. 1909 247 49-53).-This latex (sp. gr. 1.0304) which is used by the South American Indians in the Amazon valley as 8 remedy for consumption is probably derived from a Hancorizia sp. It is acid in reaction and taste and contains neither alkaloids nor glucosides.The resinous product obtained on coagulation has m. p. 45O saponifica- tion number 96.4 (156.7 when saponified under pressure) iodine number (Wys' method) 39.3-53.4 depending on the time the product is left in contact with iodine solution and Reichert-Meissl number 9.2. It contains gum sugars water formic acetic propionic and butyric acids fatty acids melting at 53-54' 63-64O 69-70' and 78-79" phytosterol and other fatty alcohols and hydrocarbons or their near allies having m. p. 120-121° 196-197" 2OO-20lo and 205-206". T. A. H. Maltase of Maize. R. HUERRE (Compt. rend. 1909 148 3O0-3q. -The dibcrepancies in the observations of various authors aIe due to the dissimilarity of the ferment in different varieties. The (ungerminated) seeds from one variety of maize from the Landes (" blanc hiitif ") have a maltase acting between 0' and 65" with optimum a t 40' (and a n amylase with a much lower optimum tempera- ture).Another variety of maize (" jaune hdtif ") has a maltase acting between 30" and SOc with optimum a t 60-62". G. B. Pentosans of Soja hispida. G. BORGHESANI (Bied. Zentr. 1909 38 141 ; from Stm. sper. ugrw. itaZ. 1907 40 118).-The following percentage results are givon Furfur- aldehyde. Pentose. Pentosan. Xoja hibpida fwnida var. pallida .......... 1.67 3 *25 2'86 ,) ,) platyempa var. pallida ......... 1.74 3'38 2.97 > * 9 7 Y nzelanosperma. 2'26 4.39 3.86 Y 7 ' 2 castanea ......... 2.15 4 -17 3-67 (green) ................................. 2-11 4-09 3-60 Y N. H. J. M. Is the Omission of Magnesium in Soil Analysis Justifiable ? OSCAR LOEW (Chem.Zeit. 1909 33 118-119).-Attention is called to the importance of determining magnesium in soil in addition to potassium calcium phosphoric acid and nitrogen. Experiments on the effect of magnesium manures have frequently been made without ascertaining the amount already present in the soil. A large number of soils in the Rhine Palatinate were found by Kling to contain only 0*04-0.06% MgO whilst more than half contained only traces and some none at all. On the other hand a soil near Munich contains over 10% MgO (as dolomite),VEGETABLE PHYSIOLOGY AND AGRICULTURE. 259 The frequently discordant results of experiments on the relative values of sodium and calcium nitrates are attributed in part to varying relations of the amounts of calcium and magnesium in the soil.Soil already containing a high relation of calcium to magnesium would be injured by further applications of calcium especially when in a readily available form such as nitrate. Decomposition of Soil-producing Rocks. EMIL HASELHOFF (Landw. Veivuchs-Stat. 1909 70 53-1 43).-Gramineous arid legu- minous plants are able to produce more or less growth in freshly- broken unweathered rocks such as basalt muschelkalk etc. Of the two groups the leguminous plants owing to their greater range of roots and their power of utilising atmospheric nitrogen have a much greater power of obtaining nutrients from the minerals than gramineous plants. The different plants of the two groups also vary in this respect among themselves. Addition of nitrogenous manures distinctly increased the yields and also the amounts of nitrogen in the plants ; there was however no increase in the amounts of other constituents. Diffusion of Manurial Salts in Soil.ACHILLE MUNTZ and H. GAUDECHON (Compt. rend. 1909,148 253-258).-When soluble salts such as sodium nitrate and potassium chloride are applied to air-dried soils in small patches the soil gradually darkens in the places con- taining the salt owing to deposition of moisture from the surrounding portions. Determinations of moisture after a week or ten days showed that the parts of the soil to which the salts were applied con- tained more whilst the intermediate portions contained less moisture than was originally present. I n the case of potassium chloride it was found that in ten days no lateral diffusion had taken place to a distance of 20 mm.whilst the soil of the spot to which the salt had been applied contained 1.48%. These results are considered t o explain the failure of crops when the seed and manure have been sown about the same time in dry weather; some of the seeds become surrounded by concentrated solutions !of salts whilst the remaining seeds fail to germinate because of the diminished amount of water. Similar experiments with a wet soil (containing 15.6% water) which received a t different points 2 grams of sodium nitrate and potassium chloride at a depth of 1 cm. showed that in six days no appreciable lateral or vertical diffusion had taken place at a distauce of 25 mm. In another experiment in soil containing 16.1% of water a slight diffusion at a distance of 20 mm.was detected at the end of a month but not at 40 mm. When rain falls the solutions of the particles are carried straight down without appreciable lateral diffusion of the Salk It is only during very prolonged falls of rain that a gradual distribution OF the salts occurs. Under ordinary conditions,.the diffusion of salts in the soil is ex- tremely slow. Physiological Characterisation of Ammonium Salts. DYITRI PBIANISCHNIKOFF (Ber. Deut. bot. Ges. 1908 26a 7 16-724).-The N. H. J. M. N. H. J. M. N. H. J. M.260 ABSTRACTS OF CHEMICAL PAPERS. partial replacement of sodium nitrate by ammonium sulphate in sand cultures has a beneficial effect on the absorption of crude phosphates but when the whole of the nitrogen is supplied as ammonium sulphate the ‘‘ physiological acidity ” of the latter salt acts unfavourably and calcium carbonate must be added in order to neutralise the sulphuliic acid set free.The calcium carbonate can be replaced by sodium nitrate but only partly by ammonium nitrate. Properties and Action of Ammonium Sulphate Containing an Excess of Sulphuric Acid. OTTO LEMMERMANN (Bied. Zentr. 1909 38,15-17 ; from Fiihling’s Landw. Zeit. 1908-9.).-The two chief varieties of ammonium sulphate contain excess of sulphuric acid amounting to 1-1-5 and 05% respectively. The presence of hydrogen ammonium sulphate even when the excess of sulphuric acid reaches the amount of 3% does not render the manure appreciably more hygroscopic whilst the results of pot experiments with barley failed to show any injurious action.G. B. N. H. J. M. Manurial Experiments with the Two Commercial Forms of Calcium Cyanamide and with Calcium Nitrate. BR. STEGLICH (Verhandl. Ges. deut. Ncbturforsch. Aertxe. 1907 11 147-150).- Experiments on various crops from 1903 to 1907 in which the action of the three manures is compared with that of sodium nitrate and in most cases with ammonium sulphate as well. The averages over the whole period indicated that ‘‘ kalkstickstoff ” has a value of 96 as compared with sodium nitrate = 100 and ammonium sulphate = 95. “ Stickstoffkalk,” which was only included in the experiments of 1906 and 1907 and calcium nitrate (1907) showed values of 94 and 101 respectively. The percentage of nitrogen in a sample of ‘‘ kalkstickstoff ” which was kept for three years fell from 18.5 to 12.The results vary considerably in different years. N. H. J. M. Manurial Experiments with Calcium Cyanamide. JOHANNES BEHRENS (Bied. Zenntr. 1909 38 67 ; from Ber. Zandw. Versuchastat. Augustenberg 1906 40).-Field experiments with barley in which calcium cyanamide was applied a week before the seed was sown showed an increase of about 20% of grain as compared with the unmanured plot whilst sodium nitrate more than doubled the yield. When applied as a top-dressing to buckwheat and barley the former was injured beyond recovery whilst the latter although injured at first recovered later on. N. H. J. M. Action of Calcium Cyanamide on Carrots Kohl-rabi and Mangolds under Damp Climatic Conditions.ALBERT STUTZER (Bied. Zentr. 1909 38 104-106 ; from Fiihling’s Lrcndw. Zeit. 1908).-Sodium nitrate ammonium sulphate and calcium cyanamide applied to carrots gave similar results as regards total dry matter whilst the relations of roots to leaf varied sodium nitrate producing the greatest amount of leaf and cyanamide the most root (both as dry matter). The cost of producing an increase of 10 kilos.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 261 of dry matter (roots) of carrots kohl-rabi and mangolds was less when calcium cyanamide was employed than with sodium nitrate. The rainfall had been excessive in June July and August and August was cold and windy. N. H. J. M. Action of Calcium Nitrate and Calcium Cyanamide on Peat Soils. HJALMAR VON FEILITZEN (Mitt. Vey.F&d. Moo&dtzcr 1909 Heft. 1 and 2 ; and Svenska Mosskultmfor. Z'idskv. 1909 No. l).-Calcium nitrate applied to oats potatoes and hemp grown in peaty soil deficient in nitrogen and in sandy soil gave results equal to those obtained with sodium nitrate; in some cases calcium nitrabe produced higher yields than sodium nitrate Calcium cyanamide yielded good results when applied to different peaty soils. As compared with sodium nitrate the yields were sometimes higher and sometimes lower. When used for grass it should be applied some time before the commencement of growth to avoid injurious action. N. H. J. M. Manul=ial Experiments with Calcium Nitrate on Potatoes. ALBERT SruTzER ( B i d Zentr. 1909 38 138-139 ; from blitt. deut. Ziindw. Ges. 1908 St. 4 19).-Equal amounts of nitrogen as sodium and calcium nitrates gave equally increased yields of tubers.The greatest amount of starch was produced by 50 kilos. of nitrogen per hectare as sodium nitrate and the next largest amount by 25 kilos. of nitrogen as calcium nitrate. Larger amounts of calcium nitrate reduced the amount of starch. I n experiments with tobacco calcium nitrate acted very favourably on leaf development and the burning quantity of the leaf was better than with sodium nitrate. N. H. J. M. Amount and Composition of the Drainage Waters Collected during the Year 1907-8. B. C. BURT (Rep. Cawnpore Agric. Stat. for the year ending June 30 1908 18-19. Compare Abstr. 1908 ii 890).-The total amounts of rain and drainage and of nitrogen as nitrates in the drainage from June 1 to October 31 were as follows :- Depth Nitrogen as nitrates. of soil Rainfall Drainage ,- A \ No. in inches. inches. inches. Per million. lb. per acre. l...... 72 17-15 3.645 11-70 9 -65 2 . . . . . . 72 17.15 4.844 12-61 13-83 3...... 36 17.15 5-920 24 *26 32.49 4 ...... 36 17.15 6.756 24-30 37-15 N. H. J. M. TJse of Ferrous Arsenate against Insect Parasites of Plants. VERYOREL and DANTONY (Compt. rend. 1909,148,302-304). -A 4% solution of crystallised ferrous sulphate is slowly added t o a 4% solution of sodium arsenate until a potassium ferro- or ferri-cyanide test-paper is turned bliie; the mixture is then diluted with four volumes of water so that it contains about 0.2% of ferrous arsenate VOL. XCVI. ii. 1s262 ABSTRACTS OF CHEMICAL PAPERS. and is used as a spray. It is much less toxic to plants than the alkali arsenates and adheres better than Scheele’s or Schweinfurth’s green. G. B.

ISSN:0368-1769    

DOI:10.1039/CA9099605255

出版商:RSC    

年代:1909

数据来源: RSC