摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. ABSTRACTS OF PAPERS ON ORGANIC CHEMISTRY. H. BRERETON BAKER M.A. D.Sc. HORACE T. BROWN LL.I). F.R.S. J. N. COLLIE Ph.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. F. G. DONNAN M.A Ph.D. F.R.S. BPRNARD DYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F. R. S. F. R. S. P. F. FRANKLAND Ph.D. LL.D. C. E. GROVES F.R.S. A. MCKENZIE M.A. D.Sc. Ph.D. J. C. PHILIP D.Sc. Ph.D. A. SCOTT M.A. D.Sc. F.R.S. S. SMILES D.Sc. F. R. 8. mitor Sab- @bitor .J. C. CAIN D.Sc. Ph. D. A. J. GREENAWAY. $bsfrafars E. F. ARMSTRONG Ph.D. D.Sc. F. BARROW M.Sc. Ph.D. R. J. CALDWELL D.Sc. W. A. DAVIS R.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCII D.Sc. Ph.D. W. H. GLOVER Ph.D. W. GODDEN B.Sc. E. GOULDING D.Sc. W. D. HALLIRURTON M.D. F.R.S. T. A. HENRY D.Sc. H. B. HUTCHINSON P1i.D. L. DE KONINOH. G. D. LANDER D.Sc. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. Ph.D. E. J. RUSSELL D.Sc. 8. B. SCHRYVER D.Sc. Ph.D. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc. F. SODDY M.A. F.R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. D. F. TWISS D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. C. WITHERS Ph.D. W. 0. WOOTTON B.Sc. H. WREN M.A. D.Sc. Ph.D. W. J. YOUNG M.Sc. D.Sc. 1912. Vol. CII. Part I. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 1912.RICHARD CLAY & SONS LIMlTED. PRUNbWICK STREET STI?ME”ORD STREET S.E. AND BUNGAY. SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91202FP001

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

J O U R N A L A. JAMIESON WALKER Ph. D. J. C. WITHERS Ph.D. OF THE CHEMICAL SOCIETY ~ ABSTRACTS O F PAPERS OX PHYSICAL INORGANIC MINERALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. AND Gommittee of &&litation H. BRERETON BAKER hI.A. D.Sc. HORACE T. BROWS LL.D. F.R.S. J. N. COLLIE Ph.D. F.R.S. A. W. CROSSLEY n.Sc. Ph.D. F.R.S. F. G. DONSAN M.A. Ph.D. F.R.S. BERNARD DYER D.Sc. a!. 0. FOHSTER D.k. Ph.D. F.R.S. F.R.S. P. C. A. J. A. S. F. FRANKLAND Ph.D. LL.D. F. R. S. E. GROVER F.B.S. bICKENZIE M.A. D.Sc. Ph.D. C. PHILIP D.Sc. Ph.D. Scow hl. A. D.Sc. F.R.S. SMILES D.Sc. cEbifor J. C. CAIS D.Sc. Ph. D. Bnb-Qbifar A. J. GREENAWAY. ~Cbatrmtora - E. F. AKMSTKONG Ph.D. D.Sc. F. BARROW M.Sc. Ph.D. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWNOX Ph.D. D.Sc. C. H. DERCH D.Sc. Ph.D. W. H. GLOVER Ph.D. W. GODDEN R.Sc. E. GOULDIXQ D.Sc. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY DSc. H. B. HUTCRINSON Ph.D. L. DE KONINQH. G. D. L A ~ D E R D.Sc. F. M. G. MICKLETHWAIT. N.H. J. MILLER P1I.D. T. H. POYE B.Sc. 7'. SLAWR PRICE D.Sc. Ph.D E. J. RUSSELL D.Sc. S. €3. SCHRYVER D.Sc. Ph.D. G. SENTER Ph.D. B.Sc. I W. P. SKERTCHLY. ' C. SYITH D.Sc. F. SODDY M.A. F. R.S. J. F. SPENCER D.Sc. Ph.D. 1912. Vol. CII. Part 11. B.A. LONDON 1912. GURNEY &JACKSON 33 PATERNOSTER ROW E.C.RICEAHD CLAY 8; SONS LIXITED HXUNBWICK STREET ST.kDlFORD STRBHT S.L. AND BUNGAY PUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91202FP003

出版商:RSC    

年代:1912

数据来源: RSC

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INORGANIC CHEi’vTI WRY. Inorganic Chemistry. ii. 39 The Hydrogen Ion Concentration of Sea-water. SVEN PALITZSCII (Biochenz. Zeitsch. 19 11 37 11 6-1 30).-By means of Sorensen’s indicator method with the use of phenolphthalein and a-naphtholphthalein the concentration of the hydrogen ions was determined in sea-water taken in different parts of the North Sea Mediterranean and Black Sea during a voyage of investigation. The variations (with the exception of certain measurements made with water from the Black Sea) lay between pri = 7.95 and p = 8.35. HANS KAPPELER (Ber. 1911 44 3496-3501).-The author has prepared the compounds usually denoted as IloOIn and I6OI3 according to the details given by their discoverers (Millon J. pr. Chem. 1845 34 321 ; Kammerer ibid. 1861 83 65 72) and finds that they are identical with basic iodine iodate 1204.Tho analysis was carried out by decomposing them with water into iodine and iodic acid and determining the ratio of the iodine t o the iodic acid. By the action of concentrated nitric acid (D=1.52) on finely powdered iodine at the ordinary temperature a voluminous yellow powder is produced which can be collected and dried on a porous plate. It rapidly decomposes on exposure to light or moisture. Analysis by decomposition with water and estimation of the free iodine and iodic acid showed it to be an iodine nitrate either I(N03)3 or IO(N0,); the decision between these two formulae could not be made. If in the oxidation of iodine or in the reduction of iodic acid water is excluded as much as possible the reaction ceases as soon as the stage I,O is reached and salts of tervalent iodine are produced; thus oxidation of iodine (1) with ozone gives I(1O3) (Fichter and Rohner Abstr.1909 ii 991) (2) with nitric acid gives iodine nitrate ; reduc- tion of iodic acid by heating with concentrated sulphuric acid gives an iodine sulphate ( 10),S04,$H20 whilst reduction with sulphur dioxide gives a similar sulphate or else a sulphite. Exposure of the iodine salts of volatile or deliquescent acids to moist air brings about slow decomposition. Hydrolysis takos place and the residual oxide I,O or the hydroxide I(OH) decomposes into hydriodic acid and iodic acid or into iodine and iodic acid 15I(OH) = 5H1+ 10HI0 + 15H,O = 31 + 9HI0 + 18H,O. This decomposition takes place so slowly with the sulphate nitrate and sulphite that the resulting iodic acid can react to some extent with part of the undecomposed salt forming insoluble basic iodine iodate I,O for example according to the equation (IO),SO + 2HI0 = 2(IO)IO3 + H2S04 ; the free iodine volatilises.With iodine acetate (Schiitzenberger Compt. rend. 1861 52 135; 1862 54 1026) and the iodine iodate I,O the decomposi- tion with water is too rapid for the formation of the basic iodine iodate to take place. S. B. S. The Iodine Oxides 16013 and IloO19 and Iodine Nitrate. T. S. P.ii. 40 ABSTRACTS OF CHEMJCAL PAPERS. Action of Hydrogen Peroxide on Iodine Compounds Con- taining Oxygen. VICTOR AUGER (Compt. ?-end. 19 1 1 153 1005-1007. Compare Abstr. 1911 ii 386 ; Tanatar Abstr. 1899 ii 414 ; PQchnrd i3id. ii 477).-The salt Na2H,T0 is very slowly decomposed by hydrogen peroxide with formation of sodium iodate and liberation of a larger amount of oxygen than corresporrds with the equation this being due t o catdytio decomposition of the peroxide.With periodic acid the results vary con*ideral~ly accm ding to conditions. I n dilute solutions the acid is rapidly and completely reduced to iodic acid only a trace of iodine being liberated whilst i n concentrated sdutions the reaction is incomplete and much iodine is formed. Cold solutions of hydrogen peroxide slon ly decompose iodic acid in solutions containing less than Oms% iodine being set free. If the concentration of acid exceeds O%% however the solution remains colourless owing to the fact that the reaction J 2 + 5H,O = 2H10 + 4H,O proceeds more rapidly than the reaction ZHIO + 5H,o = I + 6H,O + 50,.w. 0. w. Production of Solid Oxygen by the Evaporation of the Liquid. SIR JAME~ DEWAR (Proc. Roy. Soc. 1911 85 A 589-597).- By the use of charcoal as a gaseous condensing agent a t low temperatures combined with the employment of suitable vacuum vessels the change from liquid oxygen into the solid can be easily effected. Pare liquid oxygen contained in a properly isoIated vessel is subjected to the exhaust produced by a qnantity of charcoal kept at about the temperature of boiling oxygen ; the pressure is thereby lowered sufficiently to produce solidification to a transparent jelly. The pressure a t which Solidification took place was determined by connecting a McLeod gauge to the vessel containing the solid oxygen and from the results obtained and the application of the Rankine or Willard Gibbs vapour-tension equation the melting point is calciilated to be 53-55'abs.a t a vapour pressure of 1.12 mm. Actual measure- ment with a hydrogen gas thermometer gave the value 54' abs. (compare Onnes aiid Crommelin Abstr. 1911 ii 854). T. S. P. The Formation of Ozone. ANTON KAILAN (Zeitsch. Elektrochem. 1911 1'7 966-367).-In the residues obtained in the fractionation of a gas containing a very high percentage of ozone Harries found that there was a discrepancy between the iodometric and gravimetric estimations of the ozone and came to the conclusion tbat t h i s was caused by the presence of a constituent 0 (compare ibid.1'7 629). The author points that if tho molecule 0 contains two available oxygen &toms (0 = 0 + 0 -+ 0) as assumed by Harries both the iodometric and gravimetric estimations mill give the same result for a mixture of 0 and 0 so that the observations of Harries cannot be used in support of the existence of the molecule 0 ; they must be due to some as yet unknown cause. T. S. P. The SyBtem Sulphur. ANDEEAS SMITS and H. L. DE LEEUW (Proc. K. Akatl. Wetensch. Amsterdam 191 1 14 461-468. Compare Abstr. 1910 ii 400).-An account is given of experiments to deter-INORGANIC CHEMISTRY. ii. 41 mine the influence of the percentage of Sp present on (u) the transition point of monoclinic to rhombic sulphur; (6) the freezing point of sulphur with the formation of the monoclinic modi6cation.The tran- sition point may be lowered as mnch as lo' and in some cases freezing- point terriperatuies as low as 108' mere obtainetl care boing taken to avoid supercooling. The apparent separation of liquid sulphur into two ph:ises is brought about by t h e differences in temperature which arise in R column of the liquid owing to the bad conduction of heat Tn reality there is no formation of two phases the differences in colour being accounted for by the differences in temperature. T. S. P. The Electrolytic Preparation of Persulphates. A. BLUMER (Zeitsch. Elektvochern. 191 1 17 965-966).-A platinum mire anode is described which is beld together by a g1:iss frame of such shape that it forms a cage round the porous cell containing the cstholyte; the frame fits into a glass cylinder containing the anolyte.The whole apparatus is cooled by surrounding it with a jacket through which water flows continuously. The anode had a total length of 96 cm. the wire being 0.15 mm. in diameter and current densities of 9.5-4.9 amperes per sq cm. could be used,without the temperature of the anolyte rising above 28-29' (compare Levi Abstr. 1903 ii 474). Lead cathodes did not give Satisfactory results but with nickel cathodes keeping the electrolyte strongly acid by addition of sulphuric acid from time to time yields of persulphate varying from 51-81% were obtained without a diaphragm and 95-97&% yields with a diaphragm. (The particular persulphate obtained is not stated ; presumably it was ammonium persulphate.) The claims of the Ger.Pat. 205067-8 (Abstr. 1909 ii 312) with respect t o the effect of the addition of ferrocyanides on the yield of ammonium persulphate were verified yields as high as 93.5% being obtained. The addition of aluminium sulphate did not give such good results (50-62% yield); with cobalt sulphate a 60% yield wits obtained. T. s. P. The Oxidation of Nitrogen by the Electric Discharge in the Presence of Ozone. VIKTOR EHRLICR and FRANZ Russ (Monalsh. 1911 32 917-996).-By the action of the silent electric discharge on still mixtures of nitrogen and oxygen the authors have been able t o obt'ain high percentage oxidation of the nitrogen in accordance with the following table Original % (vol.) of oxygen in the blrLxiinum % (rol.) of nitric oxide in mixture .......................................'5 20-8 50 75 91.5% terms of the final volume of gas ...... 0.2 4 ' 1 13.2 18'0 21% The high percentage of nitric oxide thus obtained is not due to an equilibrium attained under the influence of the electrical discharge but to a conpling of electrical and chemical processes. Ozone in excess oxidises the nitric oxide formed to nitrogen pentoxide thus causing the further formation of nitric oxide. The formation of nitric oxide is oneii. 42 ABSTRACTS OF CHEMICAL PAPERS. of zero order and takes place so long as ozone is in excess; when all the ozone has been used up further discharge decomposes the nitrogen pentoxide with the formation of nitrogen tetroxide. This then further decomposes almost completely giving a new equilibrium which is con- ditioned by the nitric oxide equilibrium under the conditions of experi- ment and by the velocity of formittion of ozone.The available ozone increases with increasing concentrations of oxygen in the initial mixture and consequently also the maximum amount of nitric oxide formed until all the nitrogen has been oxidised. Above this limiting concentration a stationary condition is attained which is dependent on the ozone and nitrogen pentoxide. Under given electrical conditions the velocity of formation of nitric oxide is independent within wide limits of the composition of the initial mixture whereas the velocity of ozone formation increases with the oxygen content of the original mixture. However when the gaseoiis mixtures are poor in nitrogen there is some retardation in the velocity probably because of diminished conductivity.Variation in the electrical conditions for a given mixture has no effect on the course of reaction since the velocities of formation of nitric oxide and ozone are affected in the same direction ; there are however effects on the relative velocities of these reactiom so that the maximum amount of nitric oxide formed is altered. For example increase in the electrical energy or diminished gas pressure gives lower values for the maximum amount of nitric oxide produced. The increased velocity of decomposition of ozone caused by the presence of nitrogen pentoxide is independent of the concentration of the ozone within certain limits T. S. P. Thiophosphates and Thiophosphites.FRITZ EPHRAIN and REBECCA STEIN (Ber. 1911 44 3405-3413. Compare Glatzel Abstr. 1905 ii 31 8).-In aqueous solution the tetrathiophosphates are subject to a kind of hydrolysis whereby the sulphur is either com- pletely or partly replaced by oxygen. It is probable that sodium tetrathiopbosphate for example gives rise to the equilibrium 2Na,PS4 ZZ 3Na2S + P,S and that the phosphorus pentasulphide then undergoes decomposition with evolution of hydrogen sulphide whereby the equilibrium is disturbed. A consideration of this equilibrium equation shows that the tetrathiophosphates would probably exist in the presence of excess of the alkali sulphide and the authors have succeeded in preparing a number of such salts by the interaction of phosphorus pentasulphide and excess of alkali sulphide. When tetra- phosphorus trisulphide or heptasulphide is used in place of the pen tasulphide the thiophosphites are formed.Potussium tetrathiophosphate K3PS4,H,0 is prepared by heating an intimate mixture of 100 grams of crystallised potassium sulphide and 7.5 grams of phosphorus pentasulphide until the former compound melts in its water of crystallisation. Before fusion is complete 30 C.C. of water are added and after the whole mass has become liquid it is filtered through a hot water funnel. On cooling the filtrate deposits microscopic crystals of the required salt in the form of quadratic rods. The yield is only 0.4 gram the main quantity of the salt remainingINORGANIC CHEMISTRY. ii. 43 in solution from which it is impossible to obtain it free from potassium sulphide.The crystals are fairly stable in the air and can be pre- served unchanged for weeks over concentrated sulphuric acid excepb for gradual loss of water of crystallisation ; they undergo dehydration at 90’. The preparation of other thiophosphates is similar in principle to that of the potassium salt. forms thin rhombic leaflets or else thick prismg which can he dried in the air without loss of ammonia. The yield is better than that ob- tained with the potassium salt. Barium tetrathiophosphate Bn,(PS,),,aq. forms microscopic needles as also does strontium trithiophosphate Sr,H&PS,O),,aq. ; the sulphur content of the latter compound varies with small changes in the conditions in one case R compound of the composition Sr3H6(PS3.50,,.5)4 being obtained.Calcium and aluminium thiophosphates could not be prepared. The thiophosphites are prepared similarly to the thiophosphates as indicated above ; phosphorus hydrides are however evolved to some extent showing t h a t tbe reactmion is not purely one of addition of the components. Sodiuin trith,iopTtosphite Wn,PS,,aq. forms rectangular plates which are very soluble in water ; the crystals are stable in dry air and do not lose their glance. Barium trithiop?iospl&e Brig( Pd,)2,aq. forms white microscopic rhombic prisms whilst burium oxythio- phosphite Ba,(PS,,,0,,,)2,8H20 forms microscopic flat crystals. Amntoniurn tetrut~iio;uiios;lil~clts (NH,),P% T. 5. P. Arsenic Tri-iodide. ERW. RICHTER (Chem. Zentr. 19 11 82 ii 935 ; from Apotl~ Zeit.26 728-730 742-743).-The product obtained by keeping a mixture of arsenious acid (10 grams) with iodine (5 grams) is extracted with carbon disulphide and the solvent allowed t o evaporate when garnet-:to scarlet-red hexagonal crystals of arsenic tri-iodide eeparate and may be dried at 50-70°. This leaves 8-9% of residue when t.reated with water and rather more Then water containing alcohol is used. A 1% solution in water or in water containing 5-10% of alcohol is stable. ‘The product may be assayed by titration first with N/lO-potassium hydroxide and then with N/lO- iodine. Commercial preparatims should contain 97% of real iodide. T. A. H. Proper ties and Preparation of Boron. EZECHIEL WEINTRAUB (J. Ind. Bng. Chern. 1911 3 299-301).-h description of the pro- perties of boron when isolated in the pure fused condition an account OF the methods used in its preparation with a discussion on t h e agree- ment of these propert ics with its position in the periodic classification and the possibilities of its future industrial employment.Boron has a curved conchoidsl fracture is very hard scratching all known substances except diamond; the surface is very shiny black and takes a beautiful polish but as at present prepared it lacks tough- ness. The m. p. lies between 2000 and 2500° and i t is somewhat volatile exhibiting an appreciable vapour-tension at 1200O. The electrical properties are entirely unexpected when cold boron is a very poor conductor its specific resistance being about 1OI2 timesii. 44 ABSTRACTS OF CHEMICAL PAPERS.that of copper; this resistance drops as the temperature rises and between room temperature and about 400' this drop is in the approxi- mate ratio of 2 x lo6 to 1. Its bebaviour is more like that of a spark gap or arc than that of a solid conductor there existing a '' break down" voltage in the cnse of boron as in that of an air gap; this relationship between temperature and resistance has been studied up t o red heat. Two methods of preparation are employed in the first boric nnhydride is reduced hy means of magnesium and the impure boron so obtained then heated t o almost its melting point when magnesium and nitrogen volatilise in the elemental form and oxygen is eliminated as boric anhydride. The second method is based on the decomposition of boron chloride by hydrogen at a red heat and is carried out in two ways (u) in an arc discharge taking place between two boron or (water-cooled) copper electrodas iu an atmosphere of boron chloride and hydrogen ; ( b ) by deposition on a hot graphite tube heated by a current passing through it when if the conditions are properly adjusted there is practically no combination between the graphite and boron.Boron chloride is best obtained by passing chlorine over boron carbide which may be prepared in the electric furnace from boric anhydride and carbon. F. M. G. 3%. Silicon Hydride at Low Temperatures. KAROL ADWENTOWSKI and EDWARD DROZDOWSEI (Bull. Acad. Sci. Cmcow 19 11 A 330-344). -Pure silicon hydride can only be obtained after repeated fractionatiori of the gas prepared either by the method of Friedel and Ladenburg (Annulen 1867 143 123) or t h a t of Moissan and Smiles (Abstr.1902 ii 318). By the latter method (the action of conceutrated hydrochloric acid on magnesium silicide) liquid as well as gaseous fractions were obtained ; the liquid was not a pure substance but probably a mixture of several silicon hydrides. The pure gas is spontaneously inflammable in open vessels where the surface in contact with the air is large; the inflammability is not due to the presence of impurity One litre at Oo and 760 mm. weighs 1.4538 grams. The critical temperature is - 3 * 5 O the critical pressure 47.8 atmospheres and the boiling point - 11 6'/740 mm. The Melting of Carbon by means of the Joule Effect. M. LA ROSA (Ann. Physik 1911 [iv] 36 841-847.* Compare Abstr.1909 ii 399 and Ann. Physzk 1911 [iv] 34 95).-The changes observed by Watts and Mendenhall (Abstr. 191 1 ii 881) in carbon rods subjected t o a strong current are considered to be mainly due to impurities in the carbon. When rods purified by heating for some hours in a current of chlorine are employed deformation is not observed until much higher temperatures are reached. I n opposition to Watts and Mendenhall t h e author main- tains that the structuraI changes found in carbon after the passage of a strong current can only be accounted for satisfactorily on the assumption that a partial liquefaction takes place. * and Nuavo Cim. 1911 [vi] 2 ii 418-424. E. F. A. H. M. D.INORGANIC CHEMISTRY. ii. 45 The Deposition of Carbon in the Form of Diamond.WERNER VON BOLTON (Zeitsch. Elektrochem. 191 1 17 971-972)- I n 1910 the author found that hydrocarbons are decomposed by amalgams for example by sodium amalgam with deposition of carbon which is amorphous for the most part but contains some crystalline particles which are probably diamonds. The amount of these crystals obtained hitherto has been too small for analysis and the author has endeavoured to increase the quantity as follows a 14% sodium amalgam was put in a test-tube and covered with a dilute solution of sodium silicate containing very fine diamond dust in suspension. The test-tube was heated a t 100' for four weeks moist coal gas being passed continually over the surface of the amalgam by means of a tube passing through the sodium silicate solution.The diamond dust used showed a few crystalline particles under a mag- nification of 68 but after the end of the experiment t h e number of such particles had greatly increassd. These particles had the properties of diamonds disappearing completely on heating in a current of oxygen and dissolving in fused sodium carbonate; their amount (less than 1 mg.) way however too small for analysis. The results show that the crystalline particles in the diamond dust act as nuclei for the deposition of carbon in the form of diamond from the hydrocarbons in the coal gas. T. s. P. The Formation of Carbamide by HeatiDg Ammonium Carbamate. FRITZ FICHTER and BERNHARD BECILER (Bela. 191 1 44 3473-3450).-A systematic investigation of the dehydration of ammonium carbarnate to carbamide (compare Basaroff this Joum.1868 21 194 and Bourgeois Abstr. 1898 i 564). Ammonium carbarnate was prepared by the interaction of gaseoiis ammonia and carbon dioxide in a wide glass tube enclosing a water- cooled narrower tube ; the salt deposited on the latter in hard crusts. The results of earlier workers appear to have been vitiated by the presence of traces of alcohol introduced by the method of preparation involving the use of this liquid. For the experiments the substance was enclosed in a small steel bomb lined with tin ; after heating the bomb was reopened and the yield of carbamide estimated. 'l'he results of a series of tests show that under otherwise similar conditions the yield of carbamide rises rapidly from 115' to 135O and then slowly falls again. Experiments performed at 135' indicate that the yield is improved considerably by a closer packing of the substance ; under these optimum conditions 40% of the carbarnate is converted into carbamide in the course of four days whilst the final yield is approached even a t the end of t wenty-f our hours.The investmigation indicates that it is the unvaporised ammonium car bamate which undergoes dehydration to carbamide the diminution in the yield above 135' being due to the larger proportion vaporised. A calculation elicits the fact that at 135O whatever the amount of carbarnate taken an approximately constant percentage (42%) of the unvaporised portion is converted into carbamide. The change is an syuilibrium one and a final mixture of the same compositionii.46 ABSTRACTS OF CHEMICAL PAPERS. is reached whether for example one starts with ammonium carbamate or with a corresponding amount of an equimolecular mixture of carbamide and water. Ammonium rarbouate and hydrogen carbonate likewise give an incomplete change into carbamide the results indicating that of the compounds of ammonia and carbon dioxide only ammonium carbnmabe is stable under pressure at 135". D. F. T. The Gaseous Condensable Compound ExploRive at Low Temperatures Produced from Carbon Disulphide Vapour by the Action of the Silent Electric Discharge. 11. SIR JANES DEWAR and HUMPHREY 0. JONES (Proc. IZog. Xoc. 1911 85 A 574-588).-The explosive properties of the product previously described (now called the " ozoniser product ") (Abutr.1910 ii 408) are not due to the presence of impurities in the carbon disulphide used. The ozoniser product is formed whether the ozonisor is cooled to -SOo or heated t o 220" but the quautity obtained is less than under the ordinary conditions of temperature. No difference in its hehaviour has been traced to variations in the amount of carbon disulphide condensed with it. The interposition of a cotton-wool filter between the ozoniser and the condenser for collecting the ozonised product diminishes the intensity of the phenomena observed in the condenser. to a very con- siderable extent and at the same time increases the rate a t which brown solid is deposited in the ozoniser and leading tubes. At - 210° the ozoniser product collected is perfectly white a t first but even at this temperature it becomes brown after about fifteen minutes.Examinn- tion of the gas after it left the ozoniser by means of a beam of light did not reveal the presence of solid particles indicating that the transformation into the brown solid takes place only in contact with solid surfaces. Tho spectrum of the flash produced during the trans- formation showed the presence of sulphur bands (wave-lengths 384-392) hydrocarbon bands especially that of wave-length 436-443 the cyanogen line (3885) and various other bands. Tnere is practically no electric effect even with the brightest flashes during the transformation. By the passage of the ozoniser product through a U-tube a t - 120" and then into one a t - 1 8 5 O it was found possible t o wpuate it into two parts.A white crystalline deposit collects at - 120° which does not molt uutil the temperature has risen almost to 0'; the hubstance which gives rise to the brown solid is not condensd a t - 120° but is collected at - 186O. The ozoniser product is absorbed destroyed or caused to poIymerise by cocoanut charcoal either at - 7 8 O or ah ZSO" or at the ordinary temperature. When passed over finely shredded rubber some of the carbon disulphide is removed from the gas. The brown solid product and also the material deposited in the ozoniser after removal of free sulphur had a composition agreeing approximately with the formula CS. Tho ozoniser product is destroyed by finely-divided platinum nickel or silver ; ferric oxide (not ignited) yellow mercuric oxide,INORGANIC CHEMISTRY.ii. 47 silver oxide and barium peroxide react with it giving sulphides. Solid potacjsium hydroxide silver nitrate lead acetate and sodium peroxide have little or no action. Nitric acid and concentrated sulphuric acid bring about decomposition. Mixture of carbon disulphide vapour with hydrogen nitrogen ether methyl iodide or chloroform has no effect on the phenomena observed. The vapours of thiocarbonyl chloride ethyl thiocarbonate ethyl dithiocarbonate ethyl trithiocarbonate and thiophen do not give rise to carbon monosulphide. Comparison of t lie properties of the brown substance produced as above and the polymeric form of carbon monosulphide obtained from thiocarbonyl chloride (Abstr. 1910 ii 408) shows that they possibly differ in degree of polymerisation.The product obtained by Sidot (this Journ. 1875 28 1236) is also a polymeric form of carbon monosulphide. The specific heat between 15" and - 1 8 5 O of the polymeric form of carbon monosulphide obtained from thiocarbonyl chloride is 0.1 27 the molecular heat being 5.59 as compared with the calculated value 5.556. The heat of combustion is 178,050 cals. and the heat of formation - 10,000 cals. T. S. P. Ratios of the Rare Gases to One Another and to Nitrogen in Mine Gases. CHARLES MOUREU and ADOLPHE LEPAPE (Corrzpt. rend. 1911 153 1043-1045. Compare Abstr. 1913 ii 808 1087 1134).-The results of new analyses are given. The ratios of the rare gases to one another confirm the conclusions set forth in previous communications. There is evidence that coal exerts a selective action towards the heavier rare gases thus tending to reduce slightly below normal the ratio between argon and the other gases in mixtures occurring in coal mines.w. 0. w. The Thermal Analysis of Binary Mixtures of chlorides of Elements of the Same Valency. CARLO SANDONNINI (Atti R. Accad. Lincei 1911 [v] 20 ii 503-510).-The binary mixtures of chlorides which have been studied by means of thermal analysis are examined in the light of the rules given by Tammann for metallic alloys (Abstr. 1906 ii 346; 1907 ii 857) and by Herrmann for salts (Abstr. 1911 ii 801) and t h e results confirm the latter's conclusions. Of the univalent metals a close similarity occurs between potassium rubidium and thallous chlorides whilst lithium sodium cuproue and silver chlorides also form a group.The bivalent metals are also compared the three sub-groups being calcium strontium and barium chlorides ; cadmium and mercuric chlorides; and stannous lead and manganous chlorides. C. H. D. A Remarkable Case of Isopolymorphism with Salts of the Alkali Metals. FRANB M. JAEGER (Yroo. K. Akad. Wetemch. Amsterdam 19 11 14 35+369).-The author points out that the conclusions drawn by Tuttm from his researches on the sulphates selenates double sulphaters and double Eielenates of the alkali metals are too general since they are not supported by the results obtainedii. 48 ABSTRACTS OF CHEMICAL PAPERS. with other salts of these metals. As a further contribution to the subject the full crystallographic data for various acid trichloro- acetates are given ; these have the general formula CCI 3* CO,M,CCI,* CO,H where M represents a univalent metal and a comparison of them is given in the following table Molec.Salt. Habit. D1"m. vol. Axial ratio. Potassium Tetragonal-trapezohedric 2.005 182.04 a c = 1 0.7808 Ammonium > 7 1.775 193'80 a c = l 0.7678 Rubidium Moiioclinic-prismatic .. 2.150 191.21 a b c=1'4649 1 3.1596 Monoclinic-prismatic a:b:c=1.0434:1 :O 9706 Czsium { (pseudo-tetragonal) } 2'143 214'18{~ b ~ = 0 9 9 3 8 1 0.2538) Thallium Tetiagonal-trapezohedric 2.822 187.74 n c = l 0.7672 Thallium* Monoclinic-prismatic ... 3.923 203'16 a b :c=1*5515 1 3.3007 * Acid thallium tribromoacetatc CBr3*CO2T1 CBr;CO,H. The acid trichloroacetates of the alkali metals thus give an isopolymorphous series ; in all probability it is an isotetramorphous series with three monoclinic and one tetragon:d-trapezohedric modification.The thallium and ammonium salts probably give a continuous series of mixed crystals ; they are undoubtedly isomorphous. From mixtiires of potassium and rubidium salts the first fractions are crystals analogous t o those of the rubidium salt whilst the last fractions contain both monoclinic and tetragonal double pyramids. Mixed crystals of the pot'assium and cesium salts exhibit the form of the rubidium salt. The potassium and ammonium salts give mixed crystal& possessing solely the tetragonal-bipyramidal form. From solutions contaiuiug the rubidium and thallium salts mixed crystals of the form of the rubidium salt alone are obtained.Mixtures of caesium and tballium salt of low thallium content give mixed cryhtals having the form of the rubidium salt ; when the concentration OC the czsium salt is very great there are also found mixed crystals exhibit- ing the form of the first caesium salt. Mixed crystals of the rubidium type appear first from mixtures of the caesium and rubidium salts; with very high concentration of the caesium salt mixed crystals of the casium type are also deposited. The Capacity of Potassium Halides for Forming Solid Solutions in Relation to Temperature. MAHIO AMADOR1 and G. PAMPANINI (Atti N. Accad. Lincei 1911 [v] 20 ii 473-480)- I n the present paper the miscibility of pairs of t h e solid potassium halides at 25' is studied as the first part of a n investigation of the change of miscibility with temperature.The solubility in water is determined at 25" fifteen to twenty days being allowed for the attainment of equilibrium and curves are drawn showing the ratio between the two salts in the crystals and in the solution. Potaasium chloride and potassium bromide are completely miscible in the solid state at 25'. The curve for potassium bromide and iodide is discoutinuous indicating a gap in the miscibility from 25 to 94 mol. % KBr and the curve for potassium chloride and iodide shows a similar gap extending from 7 to 99 mol. % of chloride. T. S. P. C. H. D.INORGANIC CHEMISTRY. ii. 49 Occurrence of Potassium N i t r a t e in Western America. ROBERT STEWART (J. Arner. Chem. Xoc. 1911 33 1952-1954).- Crude potassium nitrate containing some calcium sul phate has been found in sandstone in the State of Utah. It is suggested that the existence of such deposits may have some bearing on the occurrence of excessive quantities of nitrates in some of the agricultural soils of the Western States.E. G. Experiments with Sodium Silicate. W. J. CLUNIES Ross (J. Proc. Roy. Xoc. New South TPules 1910 44 583-592).-Crystals of various salts are dropped into a solution of sodium silicate D 1.08 contained in test-tubes or cylinders. Growths resembling plant shoots are obtained from salts of silver mercury lead copper iron aluminium cobalt nickel manganese zinc cadmium calcium zirconium yttrium and cerium A ntimony uranium tin and bismuth do not yield shoots. The growths are coloured when coloured salts are used but the silicate solution surrounding them does not become coloured except in the case of manganese.The form of the growths is generally character- istic of the metal cadmium giving hair-like filaments and nickel thick fungoid forms. The growths m e probably tubular and act as semi-permeable mem branes. C. H. D. Dimorphism of Rubidium Dichromate. JOSEPH A. LEBEL (Compt. rend. 1911 153 1081).-From acid solutions of rubidium dichromate the red variety alone crystallises whilst in presence of a little alkali only the yellow modification separates. It has usually been supposed that the dimorphism is conditioned by temperature alone and that the solubility of the two forms is the same. This is negatived by the observation that a red crystal placed in a solution from which yellow ones are separating goes completely into solution.w. 0. w. Solubility of Silver Chloride in Chloride Solutions and the Existence of Complex Argentichloride Ions. GEORGE S. FORBES (J. Ame7*. Chem. Xoc. 1911 33 1937-1946).-Determinations have been made of the solubility at 25’ of silver chloride in concentrated solutions of the chlorides of sodium calcium ammonium strontium potassium and barium and also of hydrochloric acid. The temperature- coefficient of the solubility was determined in 3N-potassium and calcium chlorides a t lo 25’ and 35’. The solubility is nearly doubled by an increase of the temperature from Oo to 254 the rate of increase above and below 25’ being nearly logarithmic. The solubility is closely proportional to integral powers of the chloride concentration through- out considerable ranges which is explained by assuming the existence of the complex anions SgCl,”! AgCl,“’ and possibly AgCl,””.No evidence was obtained of the existence of the ionAgC1;. It is shown that the extent of complex formation by mercurous and silver chlorides is not proportional to the activity of the chloride ion in concentrated solutions. The data obtained in this investigation lead to the con- clusion that silver chloride should be least soluble in N/lOO-chloride solutions a fact which is of importance in analytical work. E. a. VOL. CII ii. 4ii. 50 ABSTRACTS OF CHEMICAL PAPERS. Thermal Analysis of Binary Mixtures of Calcium Chloride with Chlorides of Other Bivalent Elements.CARLO SANDONNINL ( A t t i R. Accad. Lincei 1911 [v] 20 ii 496-503).-CaIcium chloride forms a continuous series of solid solutions with strontium cadmium and manganous chlorides the freezing-point curve in each case having a minimum which occurs at 646" 545O and 583' respectively. I n the case of mixtures of calcium chloride with strontium and man- ganous chlorides a developmeut of heat a t lower temperatures is also observed over a certain range of composition indicating a decompositiou of the solid solutions. Mixtures of calcium chloride with barium chloride and with lead chloride form simple eutectiferous series the eutectic points being at 600' and 35 mol. % BaCI and at 468" and 83 mol. % PbCI respectively. C. H. D. The Plasticity of Barium Sulphate. ALBERT ATTEHBEKG (Zeitsch.angew. Chem 1911 24 2355).-Polemical. A reply to Ehrenberg's criticism (Abstr. 1911 ii 972) of the author's paper (ibid. 605). C. H. 1). The Replacement of Metals from' Aqueous Solutions of their Salts by Hydrogen at High Temperatures and Pressures. WLADIMIR IPATIEFF (Be?.. 191 1 44 3452-3459. Compare Abstr. 1911 ii 716)-In the presence of copper N-nitric acid is reduced completely to ammonia by hydrogen under 100 atmos. pressure at 150-160O; in the absence of copper no reduction takes place. In solutions of 2N-copper nitrate a t temperatures of 100-180' and initial pressures of 100 atmos. hydrogen gives rise a t first t o the production of emerald-green crystals of the compound which is identical with the mineral gerhardtite ; nitrous acid is pro- duced at the same time in quantities varying with the experimental conditions.Prolonged reaction produces black hard crystals of cupric oxide and finally a mixture of cupric oxide and copper forms the only product. With N-copper nitrate the above-mentioned complex com- pound is produced only in traces even at 140-160" ; at 100-120' crystallised cuprous oxide is.formed together with traces of metallic copper. Above 120° cupric oxide and copper are deposited the quantity of copper increasing with the time of reaction. A t 155' after forty-eight hours pure copper is the final product a result which could not be obtained with 2N-copper nitrate. A t 1 5 5 O and a n initial hydrogen pressure of 100 atmos. a 2N- solution of cupric chloride gives crystals of cuprous chloride ; under the same conditions and even at 180° a 1CT/S-solutio~i gives rise to a mixture of cuprous chloride and copper.I n a quartz tube at 186-240" and initial pressures of 100 ntmos- pheres hydrogen causes precipitation of nickel from a N/5-solution of nickel sulphate but the precipitation is not complete even after thirty hours; when a glass tube is used complete precipitation of the nickel takes place. From a 2N-solution of nickel sulphate in quartz tubes the compound NiSO,,H,O is produced whether the tube contains CU( NqJ,,3Cu(OH)pINORGANIC CHEMISTRY. ii. 51 hydrogen nitrogen or air under pressure. This compound is green and crystalline insoluble in water and does not lose water at 270"; when hydrogen is used i t is always mixed with traces of nickel. I n the presence of reduced nickel N- and N/lO-eolutions of nitric acid are reduced completely to ammonia by hydrogen under pressure.I n a glass tube a t 200° and initial pressure of 100 atmospheres hydrogen causes the precipitation of a green hydrated nickelous oxide (61*04-61.95% Ni) from a N/5-solution of nickel nitrate. I n a quartz tube metallic nickel is also deposited (at 810°) and a t 230-250O a blackish-grey precipitate of a mixture of nickel and nickelous oxide is formed. A N/5-solution of nickel acetate at 120" gives a precipitate of hydrated nickelous oxide ; nickel is deposited at 168". From a X / 5 - solution of nickel chloride a t 230-240° small quantities of nickel are deposited but the reaction is far frcm complete. T. S. P. Preparation of Colloidal Copper.J. GAUBE DU GERS and W. KOPACZEWSKI (Zeitsch. Chenz. I n d . Kolloide 191 I 9 239-240).- Twenty grams of powdered egg-albumin are treated with 20 C.C. of 15% sodium hydroxide and diluted to a litre. The liquid is then heated to its boiling point filtered from the coagulated albumin again heated to boiling after which a 1% solution of copper sulphate is added drop by drop. The liquid assumes a red colour but this changes to violet and finally to reddish-brown. On dialysing the reddish-brown solution a colloidal solution of copper albuminate is obtained. This solution does not give the reactions for copper unless the complex albuminate is decomposed. It is almost neutral towards litmus can be concentrated on a water-bath and its refractive index at 20' is 1.319. The albuminate is reduced by hydrazine hydrate only after prolonged boiling of the solution.Constitution of Phosphor Bronzes. MARIO LEVI-MALVANO and F. S. ORoFrNo (Gcczzetta 1911 41 ii 297-314).-The study of the system Cu-P has shown the existence of a compound Cu,P (Heyn and Bauer Abstr. 1906 ii 855) whilst in the examination of tbe system Cu-Sn a compound Cu,Su was encountered (Giolitti and Tavanti Abstr. 1905 ii 946). Tho authors have therefore investigated the binary system Cu,P-Cu,Sn and the ternary system Cu-Cu,P-Cu,Sn. The compound Cu3Sn has m. p. 710" (Giolitti and Tavanti found 725") ; its transformation point lies at 630" (Giolitti and Tavanti gave 659"). The diagram of the binary system Cu,P-Cu3Sn is characterisad by the presence of an eutectic corresponding with 650" and (probably) H.M. D. 22% of CU,P. The authors discuss the diagrdm of the ternary system Cu-CUSP-Cu,So as constructed with the aid of those of its three constituent binary systems. The results of the thermal investigation of a number of alloys belonging t o this ternary system are also given and interpreted. The paper is illustrated with a number of photomicrographs. R. V. S. 4-2ii. 52 ABSTRACTS OF CHEMICAL PAPERS. Constitution of Aluminium Brasses. MARIO LEVI-MALVANO and M. MARANTONJO (Gnxxettcc 191 1 41 ii 282-297).-Aluminium brasses contain 58-70% of copper 1-4% of aluminium and zinc. The ternary system Cu-Zn-A1 may be divided into two other systems namely Cu-Cu,Al-Zn and C,u,Al-Al-Zn (compare Gwyer Abstr. 1908 ii 284).The authors have investigated the binary system Cu3Al-Zn and those portions of the ternary system Cu-Zn-Cu3Al which include the aluminium brasses. The fusion and solidificaIion of the alloys was effected in an atmosphere of carbon dioxide. The diagram of the binary system Cu,Al-Zn shows that the temperature falls from the melting point of Cu,M to that of zinc. It exhibits two transformation points and a third lies at 570’. Evidence was obtained of the existence of various solid solutions and corre- sponding with the first two transformation points there are two gaps of miscibility in the solid state which were also demonstrated microscopically. In view of the character of its constituent binary systems the ternary system Cu-Cu3A1-Zn yields various mixed crystals and gaps of miscibility.The ternary alloys in the region examined develop heat at the beginning and a t the end of crystallisation but no heat changes mark the passage over gaps of miscibility. These have therefore been partially explored by microscopic methods. The paper is accompanied by a number of photomicrographs The Solubility of Iron Carbide in y-Iron. N. J. WARK (Metallurgie 1911 8 704-713).-The determination of the form of the curve of solubility of iron carbide in y-iron by thermal methods is uncertain. Better results are obtained by heating steels containing varying quantities of carbon in a salt-bath t o 2100° cooling to a definite temperature maintaining that temperature constant for some time quenching rapidly and examining microscopically.Barium chloride is used for baths above 1000° arid a mixture of sodium and potassium chlopides for lower temperatures. The maximum solubility of carbon in solid y-iron is found to be 1.70%. Equilibrium between the solid solution and the separated carbide (cementite) is rapidly attained being complete after ten minutes a t constant temperature. The highest temperature a t which the separation of cementite occurs and the lowest temperature at which pure martensite is observed are both determined the mean of the two being taken as the temperature of crystallisation of cementite for that alloy. Equilibrium is also reached from the other side by heating quenched specimens in a salt- bath and again quenching. The two series of observations coincide. The solubility curve thus obtained lies somewhat above that determined by the thermal method.The Removal of Rust from Iron in Reinforced Concrete. EDUARD DONATH (Zeitsch. angew. Chem. 1911 24 2355-2356. Compare Abstr. 1911 ii 897).-Rohland’s view that the active agent in the removal of rust is calcium hydrogen carbonate is not confirmed by experiment. Only that part of the ferric iron which is in combina- tion with ferrous oxide is converted into calcium ferrite. R. V. 8. C. H. D. C. H. D.INORGANIC CHEMISTRY. ii. 53 The Removal of Rust from Iron in Reinforced Concrete. PAUL ROHLAND (Zeitsch. angew. Chem. 191 1 24 2356).-Polemical against Donath (preceding abstract). KICOLA PAPPAU~ (Zeitsch. Chem. Ind. Kolloide 1921 9 233-239).-The coagulation of ferric hydroxides by different electrolytes has been examined.The hydroxide was prepared according to Graham’s dialytic method and the con- centration of the added electrolytes was varied. The observations show that the coagulation is brought about by the anions and that the chlorine bromine iodine and nitrate ions are about equally effective whereas the coagulating power of the hydroxyl ion is much greater. For anions of different valency the efficiency increases with the magnitude of the electrical charge. Non-electrolytes even in concentrated solution hRve no action on colloidal solutions of ferric hydroxide. H. M. D. F. DUCELLIEZ (BUZZ. Xoc. chim. 191 1 [iv] 9 1b17-1023).-8 study of these alloys has been made on the lines adopted by Vigoroux and Bourbon for nickel-zinc alloys (Abstr.191 1 ii l095) and a definite compound CoZn4 has been isolated and characterised (compare Lewkonja Abstr. 1908 ii 853). Alloys of these two metals containing more than 81.6% of zinc are non- magnetic and become more brittle as the quantity of zinc diminishes. When powdered and treated with cold 1% hydrochloric acid the acid being frequently renewed they leave a residue having the composition expressed by the formula CoZn ; this compound may also be isolated by treating the alloys with dilute nitric acid. It has DO 7.43 (calc. 7 ~ 1 1 ) ~ is nonmagnetic oxidises in the air is attacked slightly by boiliug water feebly by 1% hydrochloric acid and more strongly by 1% sulphuric acid. In these acids the residue slowly becomes magnetic due to deposition of cobalt from the solution.The com- pound also becomes magnetic when placed in aqueous solution of cobalt sulphate or chloride due to solution of the zinc but not in a solution of cobalt nitrate. When heated to a red heat it burns in oxygen air or chlorine. Alloys containing less than 81.6% of zinc are all magnetic and are attacked by acids without having any characteristic residue. The results of determinations of the E. M.E developed by a series of the alloys opposed to a pole of zinc in a solu- tion of zinc sulphate are plotted in the original and the curve shows a break when the amount of zinc in the alloy reaches 81% and corresponds with the formation of CoZn,. The analyses were made by dissolving the alloy in nitric acid adding excess of hydrochloric acid evaporating t o dryness re-dissolving in water containing a few drops of hydrochloric acid and precipitating the zinc as sulphide.A little sulphuric acid was added to the filtrate which was then evaporated to dryness and the cobalt weighed as sulphate. T. A. H. Preparation of Stannic Iodide and its Solubility in Certain Organic Solvents. F. ALEX. MCDERMOTT (J. Amer. Cl~em. Xoc. 1911 33 1963-1965).-8 method is described for the preparation of C. H. D. Coagulation of Ferric Hydroxide. Cobalt-Zinc Alloys.ii. 54 ABSTRACTS OF CHEMICAL PAPERS. stannic iodide by heating tin and iodine with carbon tetrachloride. The salt is much more soluble in the solvent at the b. p. than at the ordinary temperature and therefore separates on cooling. Stannic bromide can be prepared by adding bromine dissolved in carbon tetra- chloride in small quantities a t a time through the open end of the condenser to which the flask containing the tin and carbon tetra- chloride is attached.Sufficient heat is generated spontaneously to effect the reaction. In carbon tetrachloride a t 22.4" 8.35 grams per 100 C.C. of solution or 5.25 grams per 100 grams of solution ; at 50*0° 20.47 grams per 100 C.C. or 12-50 grams per 100 grams. I n chloroform at 28*0° 12.32 grams per 100 C.C. or 8-21 grams per 100 grams. I n benzene a t 2 0 * 2 O 12.02 grams per 100 C.C. or 12-65 grams per 100 grams The following solubilities of stannic iodide are recorded. E. G . Bismuthides and Inter-metallic Compounds. ALEXANDER C. VOURNASOS (Bey. 1911 44 3266-3271).-To prepare for example sodium bismuthide the author proceeds as follows.One hundred grams of sodium free from crust are added to an excess of pure anhydrous paraffin (b. p. 375-400") the mixture cdrefully heated on the sand-bath until the sodium melts and then the temperature raised to 300-310'. Sticks of pure bismuth (30 grams) are then gradually immersed in the paraffin ; as the bismuth melts the drops fall on to the sodiurri and combine with it crystals of the bismuthide immediately separating. The hest of reaction is so great that the paraffin is heated to the boiling point. The crystals are taken out with a perforated spoon washed with benzene or light petroleum and if necessary treated with amyl alcohol or liquid ammonia t o remove any free alkali metal ; this latter process is seldom necessary.Other cornpouods are prepared similarly. Sodium bismuthide Na,Bi forms small dark grey crystalline lamina? m. p. approx. 776". POtaSBiUm bisrnutlde K,Bi forms small shirring crystals. These bismuthides are readily oxidised on exposure to the air and are decomposed by moisture The compounds Ka,Pb (m. p. 405") and Na,Sn (m. p. 477") were also obtained. When potassium bismuthide is heated at 380-400' in a current of dry 11) drogen gas is absorbed producing a pyrophoric substance. On fuvther heating to 700° potassium vaporises away and a grey attioi ptious powder is left containing hydrogen and bismuth approxi- iiial elg in the proportions corresponding with the compound BiH,. This substance is being further investigated. ANDREW GUHDON FRENCH (Chem. News 1911 104 283).-The new element to which the name canadiurn is given was discovered by the author in the dyke rocks in the Nelson district of British Columbia running in quantities from a few penny-weights up to three ounces to the ton. It occurs pure in semi-crystalline grains and in short rods about half a millimetre in length by one-tenth of a millimetre in thickness. It is also found in metallic particles in the form of scales in platinum- bearing ores. These particles which have a bluish-white colour con- T. S. P. A New Element Probably of the Platinum Group.MlN ERALOGICAL CHEMISTRY. ii. 55 tain the metal alloyed with a volatile substance which may be osmium as it is dispelled by the blowpipe flame leaving a brilliant bead of cttnadium which is white. It is not platinum ruthenium palladium or osmium. It is much softer than these and is quite easily melted by the blowpipe. The new metal does not become tarnished by lengthened exposure to moisture and it is not oxidised by continued heating in the blow- pipe oxidising flame. It is soluble in nit& and Fydrochloric acids and in aqua regb without residue and its solution in nitric acid yields no precipitate with sodium chloride solution. It is not blackened by lengthened exposure to moist hydrogen sulphide or to alkali sulphides nor is it blackened by iodine; its nitrate solution is not precipitated by potassium iodide. Its melting point is somewhat lower than that of fine gold and silver and very much lower than that of palladium. It is electro-negative t o silver in dilute acid solution. T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9120205039

出版商:RSC    

年代:1912

数据来源: RSC

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MlN ERALOGICAL CHEMISTRY. ii. 55 Miner a l o g i c a1 C h emi stry. Determination of the Density of Minerals by means of Rohrbach's Solution of Standard Refractive Index. H. E. MERWIN (Amer. J. Sci. 1911 [iv] 32 425-428).-The density of rriineral grains may be determined by measuring the refractive index of a heavy liquid in which they remain suspended. The liquid with the suspended grains is contained in the small glass cell of a refracto- meter. A table is given showing the variation of the refractive index with the density for Rohrbach's solution (barium-mercuric iodide) at 20° ranging from D 3.449 and 12 1.7686 to D 2-067 and 1.1 1.5148. L. J. 8. Quartz and Fluorite as Standards of Density and Refractive Index. H. E. MERWIN (Amer. J. Sci. 1911 [iv] 32 429-432).-The use of these minerals as standards for checking the accuracy and adjustment of instruments is recommended since for material from different localities the constants named vary but slightly.Clear colourless quartz in twelve specimens from various localities was found to have DiO 2.6495 L- 0.0010 and (in five specimens) oD 1.54425 ? 0.00005. Clear pale-coloured fluorite from different localities has D;" 3.180 k 0.001 and nD 1.4338 + <0-0001. L. J. S. Lignite. 11. Volatile Constituents. GEORGE B. FRANKFORTER and ANDREW P. PETERSON (J. Amer. Chem. Soc. 191 1,33,1954-1963). -Analyses have been made of samples of lignite from North Dakota Canada and Alaska. It has been shown by Frankforter (J. Amer Chem. Soc. 1907 29 148s) that the lignites vary widely in the amount of moisture they contain samples from the Southii.56 ABSTRACTS OF CHEMICAL PAPERS. containing more than those from more northern districts. It has been found that the total amount of volatile constituents is greater in the latter. The composition of the volatile constituents varies t o some extent but not in any regular order. The amount of carbon monoxide is nearly constant and that of methane shows but little variation. The quantity of hydrogen however is greater the further north the locality from which the lignite is obtained. E. G. Some Minerals from Beaver County Utah. B. S. BUTLER and WALDEMAR T. SCRALLER (Amer. J. Xci. 1911 [iv] 32 418-424). -In the Horn Silver mine near Frisco the sulphide ores of lead zinc copper silver and iron give place in the upper levels to a large variety of secondary minerals consisting of oxides sulphates carbonates chlorides and silicates of the same metals.Beauerite described as a new species is one of these secondary minerals being a hydrous sulphate of copper lead and ferric iron. It occurs in some quantity as canary-yellow earthy and friable masses intermixed with other secondary lead and copper minerals. Under the microscope i t is seen to be minutely crystallised in bexagonal plates. Anal. I agrees with the formula CuO,PbO,( Fe A1),0,,2S0,,4H20. None of the water is expelled below 250' Fe,O,. Al,O,. PbO. CuO. ZnO. (E,Na),O. SO,. H,O. Insol. Total. II. 42'11 - 18-32 - 0.30 0.13 27-59 9.16 2'64 100.25 Plumbojarosite (Abstr. 1910 ii 966) occurs abundantly together with jarosite and alunite in the same mine and it has also been observed in several other mines iu Beaver Co.It forms dark brown micaceous masses and under the microscope shows golden-yellow hexagonal plates which are optically uniaxial and negative ; D 3.60. Anal. I1 agrees with the usual formula Pb0,3Fe,0,,4SO3,6H2O. The associated jarosite and plumboj arosite can only be distinguished by chemical tests. The rare mineral corkite a hydrous phosphate and sulphate of lead and ferric iron [differing from beudantite in containing phosphate in place of arsenate'] was found in two mines as a light yellowish-green earthy and friable material which under the microscope shows minute crystals. It is readily soluble in hot hydrochloric acid and contains a trace of copper but no arsenic.Wurtzite (hexagonal zinc sulphide) occurs in considerable abundance in the Horn Silver mine and when struck with a pick it phosphoresces ; crystals are described. Thortveitite a New Mineral. I. 17'28 3.64 29.44 9.70 - - 21.32 9.02 10.05 100.45 L. J. S. J. SCHETELIG (Centr. Min. 19 11 721-726).-This new mineral remarkable in containing scandium as an essential constituent occurb together with euxenite monazite beryl etc. in pegmatite new Iveland in Saetersdalen Norway. It forms radiating groups of large prismatic crystals (up to 25 cm. in length and 4 cm. in thickness) somewhat resembling epidote in appearance. The crystals are orthorhombic with a b c =PHYSIOLOGICAL CHEMISTRY. ii. 57 0.7456 1 1.4912 and are always twinned on the prism (llO) this being also a direction of good cleavage. The mineral is transparent to tranducent with a greyish-green colour and bright vitreous to adamantine lustre It is extremely brittle and the crystals are much tissured; H=6$; D 3.57.It is fusible only with difficulty and is partly decomposed by hot concentrated sulphuric acid. Partial and preliminary analyses gave SiO 42.86 ; R2”’OQ 57.67 (including about 3% Fe,O,) ; CaO,MgO traces ; loss on ignition 0.44 = 100-97. The oxides R;’O have mol. wt. 157.1 and consist mainly of scandia (about 37% SC,~,) with yttria dysprosia and erbia (about 17%) but no cerium earths The mineral is essentially a scandium silicate (Sc,Y),O 2Si0,. L. J. S. Minerals from the Deposits of Tiriolo (Catanzaro). U. PANICHI (Atti R. Accad. Lincei 1911 [v] 20 ii 518-523).-A pink fibrous zeolite has the composition of mesolite (I). Brandish (11) is found as white lamellar masses almost without action on polarised light. Crystals of fassaite are found and have been characterised by crystallographic measurements. These minerals are associated with calcite spinel idiocrase and garnet SiO,. Al,08. Fe,O,. CaO. MgO. Na,O. HzO. Loss. Total. I. 45.08 24.86 - 8.76 - 6’02 14’25 - 98.97 11. 22.83 48-20 5.38 2-53 21.78 - - 3.29 99.01 C. H. D.

ISSN:0368-1769    

DOI:10.1039/CA9120205055

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. ii. 57 The Influence of Moderate Changes of Temperature of the Surrounding Atmosphere on the Respiratory Exchanges of Infants. ARTHUR SCHLOSSNANN and HANS MURSCHHAUSER (Biochem. Zeitsch. 191 1 37 1-22).-The methods of investigation employed were the same as those used in the earlier experiments of the authors. It was found that moderate changes of temperature exert practically no influence on the respiratory exchanges. Even in earliest years man is capable of regulating the temperature of the body so as to be more or less independent of the changes in the surrounding atmosphere. S. B. S. TheInfluence of Crying on the Respiratory Exchanges of Infants. ARTHUR SCHLOSSMANN and HANS M URSCHHAUSER (Biochem. Zeitsch. 1911 37 23-29).-The respiratory exchanges of infants in a calorimeter during periods of rest and crying were investigated.It was found that the consumption of oxygen increased 44% and the production of carbon dioxide increased 59.4% during a period of crying as compared with the period of rest in the case of the infant which was used as the subject of investigation. S. B. S.ii. 58 ABSTRACTS OF CHEMICAL PAPERS. The Temperature-coefflcient of the Rate of Reproduction of Paramoecium Aurelia. LORANDE Loss WOODRUFF and GEORGE ALFRED BAITSELL (Amer. J. Physiol. 191 1 29 147-155).-The optimum temperature for the culture of Parccnaoeciunz aurelia is between 24' and 28.5'. Continued subjection to temperatures below 21.5' and over 31.5' is sooner or latar fatal. The temperature-coefficient of the average rate of reproduction is approximately 2.7 and therefore the rate of cell-division is influenced by temperature a t a velocity similar to that for a chemical reaction.W. D. H. The Effect of Organ Extracts on Blood-pressure. JOSEPH L. MILLER and E. M. MILLER (J. PhysioZ. 1911 43 24%-246).-111- trnvenous injection in dogs of saline extracts of pwathyroid thymus cerebrum cerebellum spinal cord liver kidney pancreas prostate ovary and testis always lowers arterial blood-pressure without affect- ing the heart. Saline extracts of spleen always pi oduced a rise usually followed by a fall i n pressure. Aqueous extracts of spleen always produced a fall of pressure. Alcoholic extracts redissolved in normal saline solution were without effect in the case of the liver kidney pancreas spleen parathyroid thyroid thymus prostate ovary testis and anterior lobe of the pituitary body.Alcoholic extracts of nervous tissue contained a depressor substance. Prolonged heating destroved the demessor substance in brain and anterior lobe of the pituitiry but didlnot materially affect that in the posterior lobe W. n. H. Inter-relation of the Ammonia and Carbon Dioxide of the Blood. RALPH HOPKINS and W. DENIS (J. Biol. Chem. 1911 10 407-41 5).-Asphyxiation of unfed animals by increasing the carbon dioxide of the blood causes a decrease in the ammonia present in that fluid. Artificial respiration of unfed dogs causing a decrease of the carbon dioxide leads to an increase of ammonia ; inhalation of oxygen has the same effect.Curare slightly increases the ammonia in unfed dogs ; low blood-pressure decreases oxidation and so decreases the ammonia of the blood in unfed dogs. Asphyxiation of dogs in full digestion increases the ammonia in the blood. W. D. H. The Distribution of Reducing Substances in Mammalian Blood. LEONOR MICHAELTS and PETER RONA (Bioclbem. Zeitsch. 1911 37 47-49).-The authors reply t o the criticisms of J,ytt.kens and Sandgren (Abstr. 191 1 ii 994) maintaining their previous results as to the distribution of sugar between the serum and corpuscles and quote similar resulbs by other authors in support. s. B. s. Viscometric and Cryoscopic Changes in the Blood Produced by Antipyrin Phenacetin and Antifebrin. GUIDO M. PICCININI (Chew. Zentr. 1911 ii 1468 ; from Arch fawn.speriw. 12 193-209).-All three drugs given in doses of 2-5 grams in dogs increase the viscosity and the lowering of the freezing point of the serum. This is attributed to changes in the serum proteins. The cryoscopic change may be related t o an increase of alkalinityPHYSIOLOGICAL CHEMISTRY. ii. 59 which occurs. Antifebrin and phenacetin act in the same way on the defibrinated blood p-mbably because they are haemolytic. Antipyriu on the other hand diminishes the viscosity of defibrinated blood ; this is attributed to changes in the corpuscles which leads to increase of oxygen and alkali. W. D. H. The Removal of the Blood-pigment from Corpuscles Under the Influence of Carbon Monoxide. F. BUBANOVI~ (Biochem. Zeitsch. 191 1 37 139-14l).-Blood treated with coal-gas lost pigment when treated with 0.60% sodium chloride whereas the con- trol normal blood lost pigment in 0.65% saline.I n the latter case the degree of hiemolysis was greater. A weaker saline solution than required by the normal was also necessary to csuse the exit of the pigment when the blood had been treated only with air. I n b3th cases the result is ascribed to the. expulsion of carbon dioxide from hsemoglobin which is then more readily able to take up water. S. B. S. The Changes in the Blood-clotting Produced by Loss of Blood in an Animal. HEINRICH STROMBERQ (Biochem. Zeitsch. 191 1 37 218-237).-Numerous experiments were carried out on the time required for the blood to clot which had been withdrawn from animals (rabbits) after successive losses of definite quantities of blood.Although the blood was found as a rule to clot inore rapidly after loss of blood by the animal no definite relationships between the clottiug time and the toss of blood could be discovered. The results s. B. s. obtained were generally irregular. The Methods of Investigation and Characters of the Blood-clotting Process. HEINRICH STROMBERB (Biochem. Zeitsch. 191 1 37 l77-~17).-Wohlgemuth’s method of estimating the fibrin ferment which consists in determining the uuaximum amount of dilution in which i t is just possible to coagulate a definite fibrinogen solution within twenty-four hours at O” mas subjected to a critical examination and the results were compared with those obtained in a parallel investigation in which the time durations were determined in which varying dilutions of the ferment solution produced clotting.The conclusion was drawn that Wohlgemuth’s method does not; give a real quantitative estimation of the amount of tibrin ferment in blood. It was found that as a rule those sera which in undiluted form produced a clot in the shortest interval gave the largest values for the quantities of fibrin ferment by Wohlgernuth’s method. This was however by no means always the case and considerable caution must be used in drawing conclusions as to the amount of thrombin present when both the Wohlgemuth and the time methods are employed in investigations. It would seem advisable to generally employ both methods but in the present state of knowledge no very definite conclusions can be drawn from either.Numerous experiments were also carried out on the quantitative relationship between the fibrinogen and the thrombin and the relative quantities necessary t’o produce a complete clot It was found that for this purpose there is a definiteii. 60 ABSTRACTS OF CHEMICAL PAPERS quantitative relationship detween the interacting substances a fact which is not in accord with the conception of the -ferment-like character of the thrombin. I n this respect the author’s conclusions are in accord with those of Arthus. DAMEL DAVIS (Amer. J . Physiol. 1911 29 160-164).-1n four experiments on two dogs one rabbit and one cat the injection of thrombin into the circulation within the limits of 20 to 36 mg. per kilo. of animal did not cause intravascular coagulation ; in fact the coagulation time of the shed blood was slightly lengthened ; the effect soon passed off.The injec- tion of thrombin no doubt excites the rapid formation of antithrombin the agent which normally prevents intravascular cloiting. s. H. s. Intravenoue Injection of Thrombin. W. D. H. Preparation of Thromboplastic Extracts (Thromboplastin) from Tissues. H. L. CECIL (Amer. J. Physiol. 1911 29 156-159). -Aqueous or saline extracts of many tissues accelerate blood coagula- tion ; such extracts (thromboplastic) are best tested with ‘( peptone ” plasma. Witte’s peptone was often found to be ineffective for the purpose of obtaining peptone plasma. This is intelligible if Pick and Spiro’s view is accepted that the agent in Witte’s peptone is not peptone or proteose but the unknown substance peptozym.Instead of Witte’s peptone a crude preparation of peptozym which worked excellently was prepared by digesting fibrin with 0.4% hydrochloric acid at 38” for several days. The solution was boiled filtered and evaporated to dryness ; the residue was powdered dissolved in boiling water neutralised with sodium carbonate filtered and again evaporated to dryness on a water-bath. The residue thus obtained was used for injection ; it was dissolved by boiling in physiological saline solution ; the solution was filtered before injection and used in the proportion 0.3 gram per kilo The plasma obtained was clotted by extracts of muscle liver lung spleen thymus lymph glmd and salivary glands. Extracts from pancreas and intestine were inactive.Glycerol was found to be an excellent vehicle for dissolving out the thromboplastic substance ; such extracts keep well. The R61e of Antithrombin and Thromboplastin in the Coagulation of Blood. WILLIAM H. HOWELL (Amev. J. Physiol. 1911 29 187-209).-By the use of solutions of pure fibriuogen and thrombin it is shown that an antithrombin is present in normal mammalian plasma in birds’ plasma and in “ peptone ” plasma. This is neutralised by thromboplastin. Circulating blood contains all the necessary fibrin factors fibrinogen prothrombin and calcium. These substances are prevented from reacting and the blood remains fluid because antithrombin is also present which prevents the calcium from activating prothrombin to thrombin. In shed blood the restraining effect of antithrombin by thrombnplastin is furnished by the tissue elements.I n mammalian blood this is derived in the first place from the elements of the blood itself (blood-platelets). I n the lower vertebrates W. D. H. the supply of thromboplastin cou& from the external tissues. W D. H.PHYSIOLOGICAL CHEMISTRY. ii. 61 Reaction of the Blood-serum of Some Mammals Studied by the Electrometric Method. G. QUAQLIARIELLO (Atti R. Accad. Lincei 1911 [v] 20 ii 418-420. Compare Abstr. 1911 ii 1114; Michaelis and Rona Abstr. 1909 ii 68O).-The values obtained for the concentrations of hydrogen and hydroxyl ions in the blood-serum of the dog and rabbit are in agreement with those of previous in- vestigators. The blood-serum of the fowl has C,. 0.214 x CoH 2.98 x 10-7.I n the case of human blood-serum C,. varied from 0*096-0*171 x 10-7 Coat from 3.41-6-72 x 10-7. This degree of alkalinity is somewhat higher than that found by most other authors. A New Viscometer and Its Application to Viscosity Measurement of Blood and Serum. GEORGE F. WHITE (Bioohem. Zeitsch. 1911 3'7 482-489).-The apparatus which is figured is a modification of the viscometer of Thorpe and Rodger and is provided with a valve by means of which the volume of the liquid which is to pass through the capillary tube is kept constant. Dog-fish blood a t 0' was found to be 3.S96 times as viscous as water at the same temperature. Between 30' and 52' the time of passage of the blood through the capillary was found to be a linear function of the temperature. Above this point there is a fall in the curve owing to separation of the fibrinogen which had been kept in solution by the blood salts.The rate of coagulation can be measured by viscosity determinations at different temperatures. S. B. S. Relation of the Pancreas t o the Serum and Lymph Diastases. L. K. GOULD and ANTON J. CARLSON (Amer. J. Physiol. 19 11 29 165-1 81).-Ligature of both pancreatic ducts and of all the pancreatic tissue along the duodenum in dogs causes a great rise of diastatic power in the blood-serum within twenty-four hours. This is probably due to absorption of amylopsin from the gland; the condition returns to normal and then occurs a second rise ; later there may be a third rise. A considerable atrophy of the pancreas is not followed by a corresponding decrease in the diastatic power of the serum but a marked decrease follows removal of the atrophied pancreas.Almost complete removal of the pancreas in pigs does not cause a decline in the diastatic power of the serum until a considerable time alter the operation ; in dogs the decline is usually rapid but it may be delayed for eight days. I n pigs the depression when it does appear is slight. Serous exudations rich in leucocytes obtained by the injection of aleuronat into the pleural cavity have much less diastatic power than the serum. The pancreas or leucocytes are therefore not the main seat of the production of the blood diastases. The pancreas probably acts indirectly by its internal secretion ; the decrease in diastatic power that follows extirpation of that organ is regarded as due to a depression of all the tissue cells pFrticularly the liver cells which results in the decreased output of diastase into the body fluids.W. D. H. The R6le of the Kidneys in the Regulation of the Con- centration of the Serum Diastases. J. VAN DE ERVE (Amar. J. Physiol. 1311 ZS 182-186).-1n dogs ligature of the renal arteries R. V. S.ii. 62 ABSTRACTS OF CHEMICAL PAPERS. produces no change in the serum diastase. Diuresis caused by cutting the renal nerves has also no effect; but if the diuresis is due to ingestion of excess of salt solution the dilution of the blood so produced is accompanied by a diminution of the diastatic power of the serum. The polyuria which follows complete extirpation of the pancreas is therefore not an important factor i n the great diminution of this power which is observed after the operation.W. D. H. Physiology of Lymph. XVIII. The Relation of the Pancreas to the Lipase of the Blood and the Lymphs. C. L. VON HESS (J. Biol. Chem. 1911 10 381-398).-Extirpation of the pancreas in dogs does not alter the concentration of lipase in the serum ; irk rabbits there may be a temporary fall. The same negative results in dogs follow ligature of the pancreatic ducts. Partial atrophy of the pancreas in dogs and almost complete atrophy in rabbits produces no change in sero-lipase. Ligature of the renal arteries in dogs may sometimes cause a fall in the amouut of sero- lipase ; this result is independent of pancreatic lesions. Bile salts do not activate sero-lipase.Aleuronat injected into the pleural cavity gives a serous exudation teeming with leucocytes with a smaller lipolytic power t h a n the serum. Hyper and hypo-thyroidism has no effect. The pancreas and thyroid are thus not the main sources of the lipase of the serum. Ether anzesthesia has no effect. W. D. H. Comparative Proteolysis Experiments with Trypsin. GEORGE F. WHITE and .,WILLIAM CROZIER (J. Amer. Chem. Xoc. 19 11 33 2042-2048).-The work hitherto done on the artificial digestion of proteins with reference to their relative food value is of limited importance as the extent to which the soluble products had been hydrolysed was not ascertained. van Slyke (Abstr. 1911 ii 779) has devised a method for estimating the amino-nitrogen in proteins and their hydrolytic products and this has now been applied t o a study of the comparative digestibility by trypsin of boiled beef cod and dog-fish. The time of digestion the soluble and insoluble nitrogen and the amino-nitrogen before and after complete hydrolysis with hydrochloric acid are stated in tabular form.Cod is the most readily converted into the soluble form and its soluble proteins are shown to be more easily hydrolysed than those of beef or dog-fish as they yield more amino-nitrogen. Beef is the least easily soluble but the hydrolysis of its soluble proteins lies between that of the cod and the dog-fiab. The results agree with those of the metabolism experiments of van Slyke and White (Abstr. 1911 ii 623) in which dogs were fed with beef and cod and indicate that dog-fish would be digested slowly in the organism and would be more capable of maintaining nitrogenous equilibrium than either beef or cod. The flesh of the dog-fish contains 0.84% of carbamide (compare van Slyke and White Abstr.1911 ii 624). Dog-fish is recommended as a valuable food. E. G.PHYSIOLOGICAL CHEMISTRY. ii. 63 The Nature of the Repair Processes in Protein Metabolism. E. V. MCCOLLUM (Amer. J. Physiol. 1911 29 215-237).-Michaud states that when a starving dog is fed on dog’s flesh in amount equiva- lent to its daily loss of nitrogen the whole of the protein so given is used for repair purposes. In the present experiments pigs were used. They were fed on different vegetable proteins in quantity equivalent to the lowest possible level of protein metabolism ; the results do not indicate a s wide differences in the nutritive values of the proteins of wheat oat and maize as mould be expected from the known chemical differences between these proteins.Zein and gelatin are for instance ‘‘ incomplete proteins.” But the pig can utiliee the nitrogen of zein very efficiently for the repair of losses due t o endogenous metabolism ; about SO% was so used. The figure for gelatin was 50-60%; but there was no evidence of the formation of additional body tissue. On the other hand feeding with casein as the only protein given resulted in increases of the body protein of 20-25%. Repair processes are of a different character from those of growth ; probably in cell kata- bolism and repair the processes do not involve the destruction and re-synthesis of a n entire protein molecule.Studies in Nutrition. 111. The Utilisation of the Proteins of Corn. LAFAYETTE B. MENDEL and MORRIS S. FINE ( J . Biol. Chem. 1911 10 345-352. Compare Abstr. 1911 ii 1109).-Tbe proteins of maize (usually culled corn in America) partly purified were somewhat less thoroughly utilised than meat. The small differ- ence may in great part be attributed to cell residues remaining in the preparation employed. W. D. H. Biological Importance of Caseinogen Phosphorus for the Growing Organism. ALEXANDER LIPSCH~TZ (Pfliiger’s Avclhiv 191 1 143 99-1 OS).-According to Bayliss and Plimmer the phosphorus of caseinogen is converted into inorganic phosphate before absorption. This opens up the question whether feeding on the milk proteins has from the phosphorus point of view any special advantage in growth. The experiments recorded are not regarded as absolutely conclusive but so f a r as tbey go they show that in pliosphorus metabolism the inorganic phosphates are equally beneficial ; and if organic phosphor- ised materials are given the phosphorus enters the blood-stream as inorganic phosphate.W. D. H. ALEXANDER LIPSCHUTZ (P’uge~*’s Archizs 191 1 143 91-9S).-Liebig’s law of minimums does not hold in animal life for iron or calcium ; on diets poor in these substances growth continues. It is now shown that this is true also for phosphorus; bony groffths show certain changes but the total iiicrease in the weight of growing animals is squally great on diets poor in phoaphorns as on those rich in that element.The meaning and possible explanations of the observed data are discussed. W. D. H. Physiology of Phosphorus Hunger in Growth. W. D. H. The Physiological Utilisation of the Phosphorus Compounds in Fodders by Ruminants. GUSTAV FINGERLING (Biochem. Zeitsch. 191 1 37,266-271).1-When various phosphorus compounds (phytb,ii. 64 ABSTRACTS OF CHEMICAL PAPERS. lecithin nuclein sodium nucleate and inorganic phosphorus com- pounds) were added to certain phosphorus poor diets and fed to lambs and goats in milk the phosphorus was not utilised to much more than the extent of 50% whereas in other diets including oats sesame oil and linseed oil cakes the phosphorus was utilised to the extent of 90%. Furthermore in a certain grass the phosphorus compounds were utilised to the extent of 91% whereas in the hay made from the same grass they mere onIy utilised to the ex.tent of 53.4%.The author draws the conclusion that the differences are due to the differences in the physical characters of the fodders the cell-walls of the food material being in certain cases relatively indiff usible to the phosphorus compounds which are therefore prevented from being resorbed. S. B. S. The Protective Action of the Bran of Padi in a Diet of White Rice. L. BRI~AUDAT (J. Pharm. Chim. 1911 [vii] 4 447-45 l).-Polyneuritis of fowls which is produced by an exclusive diet of white rice is prevented if the diet contains 25-30% of rice bran. This protective action is not due t o the glutinous matter fatty matter carbohydrates or inorganic salts of the bran since these sub- stances extracted from bran had no protective action either singly or together.The protective constituent may be extracted from the bran by water. This aqueous extract contains only a very small proportion of the nitrogen of the bran so its protective action is not to be attributed merely to a supplementing of the nitrogen of the rice. Water Drinking. VIII. Utilisation of Ingested Fat under the Influence of Copious and Moderate Water Drinking with Meals. H. A. MATTILL and PHILIP B. HAWK (J. Amer. Chem. SOC. 1911 33 1978-1998).-Experiments are described in which men living on a uniform diet ingested small quantities of water with their meals for a preliminary period then large quantities for a period and finally returned to small quantities.When an additional litre of water was taken with each meal the amount of fat excreted was con- siderably reduced and this diminution was usually evident for several days after the return to a normal quantity of water. A slight gain in weight accompanied the water drinking and was not subsequently lost. After several months of drinking moderate quantities with meals a marked improvement in the digestion of fat was observed the utilisation having increased from 94.3 to 96.5%. The-factors t o which the better absorption and more complete utilisation of the fats are probably due are discussed. W. J. Y. E. G. Water Drinking. IX. Distribution of Bacterial and Other Forms of Fzecal Nitrogen and the Utilisation of Ingested Protein under t h e Influence of Copious and Moderate Water Drinking with Meals.H. A. MATTILL and PHILIP B. HAWK (J. Amer. Chem. SOC. 19 1 1 33 1999 -20 19).-Experiments were carried out on the same lines as those described in the previous paper (pre- ceding abstract). The ingestion of a litre of wahr with meals resultedPHYSIOLOGICAL CHEMISTRY. ii. 65 in a more complete utilisation of the proteins of the food as mas indicated by a decrease in all forms OF nitrogen in the faeces but when only 500 C.C. mere taken no significant changes could be observed. The beneficial results were more or less permanent and no indication was obtained of any detrimental effect even when more than four litres of water were drunk daily. H. G. Water Drinking. X. Faecal Output and its Carbohydrate Content under the Influence of Copious and Moderate Water Drinking with Meals.H. A. MATTILL and PHILIP B. HAWK (J. dmer. Chena. Soc. 191 1 33 2019-2033).-The experiments were conducted on t h e same lines as those already described (preceding abstracts). The ingestion of a litre of water with meals caused a decrease in the amount of faecal matter excreted as well as of the carbohydrates. The improved utilisation o€ the food lasted for some time after the water drinking had been discontinued. The ingestion of 500 C.C. of water with meals caused a similar but smaller reduction in the amount of carbohydrate excreted. The average daily amount of dry bacterial substance in the fzleces w:ts 8.27 grams. The causes of tho beneficial effect of water driuking 0x1 the utilisation of carbo- hydrates are discussed.Many desirable and no undesirable effects were obtained by the use of water with meals and in general the greater the amount of water taken the greater were the benefits. E. G. Fasting Studies. V. Studies on Water Drinking. XI. The Influence of Excessive Water Ingestion on a Dog after a Prolonged Fast. PAUL E. HOWE H. A. MATTILL and PHILIP €3. HAWK (J. Uiol. Chem. 1911 10 417-432).-The details given of the various nitrogenous substances in the urine are believed to substantiate the hypothesis that the increased nitrogen output associated with increased water ingestion is due to a true stimulation of protein katabolism rather than to a flushing of the tissnes. W. D. H. The Effect of Substances which Diesolve in Fat on the Mobility of Phagocytes and Other Cells.HAKTOG; J. HAMBURGER and J. DE HAAN (Proc. K. Akcd Wetensch. Amsterdam 1911 14 314-324).-The acceleration of phagocytosis by substances dissolving fats is attributed to a weakening of the fatty surface layer and this facilitates amaboid movement. Alcohol butyric acid propionic acid and Peruvian balsam act in this may ; this explains why Peruvian balsam has a good effect on infected wounds. The acceleration of phagocytosis is parallel to the solubility of the substances used in fat. Among animals cells which show increased mobility must be rackoned riot only phagocytes but nerve-cells eggs oE lower marine animals and ciliated epithelium. The germination of wheat grains is accelerated by chloroform 1 in 100,000 but delayed by 1 in 1000 as the latter strength paralyses the protoplasm of the cells.W. D. H. VOL. CII. ii. 5ii. 66 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Baees on the Development and Oxidative Processes in the Eggs of the Sea-urchin (Arbacia). JACQUES LOEB and HARDOLPH WASTENEYS (Biochem. Zeitsch. 19 11 37 4 10-42q.- The bifurcation and oxygen corisumption of recently fertilised eggs of Aybucia in solutions of sodium potassium and calcium chlorides in which the hydroxyl ion concentration was varied by means of sodium hydroxide and hydrogen chloride were invest>iga ted. It was found that change of C from 10-lO to corresponded with an increased oxygen consumption of only 20%. After t h i s the oxygen consumption rapidly increased a change of C from to 8.10-4 increasing the amount of oxygen utilised two-fold.The inhibition of bifurcation by sodium hydroxide in higher concentra- tions previously noted by Loeb and Warburg does not depend only on the increase in oxidative processes for if this increase is produced by rise of temperature only there is a quicker bifurcation rather than inhibition. The differences in tho previously observed toxicity effects produced by the3 addition of sodium hydroxide t o sodium and potassium chloride solut,ion on the one hand and sodium arid calcium chloride solution on the other cannot i t was found be ascribed to differences in the oxidation rates in the two solutions. I n view of the fact that amruoiium hydroxide produces about the same effect as sodium hydroxide in the same relative concentration the con- clusion is drawn that the action of the latter cannot be ascribed merely to the concentration of the hydroxyl ions.S. B. S. The Organic Bases in the Flesh of Wild Rabbits. KIYOHISA YOSHIMURA (Biochem. Eeitsch. 191 1 37 477-481).-The only bases which the author has succeeded in isolating from the flesh of wild rabbits were creatine hypoxanthine xanthine and carnosine. The usual methods were employed. s. B. s. The Imbibition and the Loss of Water by Resting and S t i m u l a t e d Frogs’ MuaclerJ when Immersed in Isotonic Saline Solution. CARL SCHWAHZ (Biochem. Zeitsch. 191 1 37 34-46).- von Fiirth and Lenk (Abstr. 1911 ii 750) have shown that the muscies in isotonic saline solution firfit of all take up water until a maximum is reached and then lose water. The first stage is an imbibi- tion process which is accelerated by the presence of lactic acid.The ioss of water is due to a gradual coagulation of the muscle proteins. The action of isotonic saline on resting and stimulated muscles is similar but the btage of maximum imbibition and subsequent loss of water is reached sooner in the case of the stimulated than in that of the resting muscles. This result can be readily explained by the presence of larger quantities of lactic acid in the stimulated muscles. I n the case of the resting muscles the lactic acid is only formed slowly post-mortem. The results confirm generally therefore the theories of von Fiirth and Lenk. The rate of imbibition and loss of water in slightly hyper- and hypo-tonic solutions was also investigated and the results obtained were those which would from the theory of osmosis be expected.S. B. S.PHYSIOLOGICAL CHEMISTRY. ii. 67 The Potassium Sodium and Chlorine Content of Plain and Striated Muscles from Various Animals. A. COSTANTINO (Biochenz. Zeitsch 1511 37 52-77).-A large number of analyses made by a met-ashing method of different kinds of muscular tissue from various mammals fowls and turkeys mere made and are tabulated by the author. No very definite generalisations as to the distribution of potassium sodium or chlorine in the various materials examined can be drawn from the results. S. B. S. The Alleged Formation of Lactic Acid in Muscle during Autolysis and in Pos t-survival Periods. W. M. FLETCHER (J. Physiol. 1911 43 286-312).-The production of lactic acid in excised mammalian and amphibian muscle is accelerated by mechanical injury.The rate of production varies with the tempera- ture and a t body temperature reaches its maximum within an hour. If the muscle is destroyed by heating production of lactic acid ceases. After the msximnm is once reached no further production of lactic acid occurs during autolysis. No glycolytic enzyme leading to the prodiictiou of lactic acid from added dextrose is present. If bacterial infection occurs the result depends on the specific action of the bacteria ; tho d-lactic acid is commonly diminished. W. D. H. The Innervation of the Coronary Vessels. THOMAS GREGO~~ BRODIE and WINIFRED C. CULLIS (J. P?ysioZ. 1911 43 313-324).- Adrenaline in great dilution causes a temporary contraction of the vessels which supply the heart.This is followed by dilatation. This is considered to prove the existence of both vxso-constrictor and vaso-dilator nerves in the coronary vessels but a secondary cause of the dilatation is the action of metabolites particularly carbou dioxide. Earlier observers have failed to detect the primary constric- tion because the solutions of adrenaline used have been too strong so that the first effect is masked by the second. W. D. H. The Action of Homologous Alcohols and Aldehydes on the Tortoise Heart. HORACE 3'1. VERNON (J. Yhysiol. 1911 43 325-348).-When the tortoise heart is perfused with oxygenated Ringer's solution containing alcohol the beats are depressed to a definite level. On washing out with fresh Ringer's solution the heart completely and rapidly recov~rs.The toxicity of the alcohols increases with their moledular weights the order being the same as t h a t f o u i d by Overton for the narcotieation of tadpoles. It also corresponds with their capacity for laking red corpuscles. Aldehydes also depress cardiac action to a constant level b u t recovery with fresh Ringer's solution is not so complete as with the alcohols. These relative toxicities are propaldehyde 1 -0 acetaldehyde 1.2 formaldehyde 40 that is there is no relationship to molecular weights. W. D. H. Comparative Histological and Chemical Investigations of the Fat Contents of Organs. NAQAMICHI SHIBATA and SHIGEKIYO ENDO (Bioclbern. Zeitsch. 191 1 37 399-409).-The organs (liver and 5-2ii.68 ABSTRACTS OF CHEMICAL PAPERS. kidneys) from individuals who had died from various diseases were examined histologically with the use of the ordinary fat-staining reagents and chemically by the Kumagawa-Suto method. It was found that with few exceptions those organs which appeared to be histologically rich in fats did actually contain relative large amounts as determined by the chemical procoss. Fatty Infiltration [into the Liver] a f t e r Phosphorus Poison- ing and the Origin of Fat in the Animal Body. NAQAMICHI SRIBATA (Biochem. Zeitsch. 191 1 37 345-398).-The experiments were carried out on mice and frogs and the fat and nitrogen distribu- tion between the liver and the remainder of the body in normal and poisoned animals was determined and compared the Kumagawa-Suto method being employed for the estimation of the fat.The main conclusion drawn is that there is no evidence of the synthesis of f a t from proteins. Phosphorus poisoning causes a marked diminution in hhe amount of total body fat but an increase in the fat of the liver. The fat diminution is however less after phosphorus poisoning in starving animals than it is in normal starving mice. Whereas in bhe normal starving animals the diminution of fat amounted to 50% in phosphorus- poisoned starving animals it mas from 50 to 65% of the iiornial value when the poisoned and control animals had been deprived of food for the same period. The results were somewhat similar but not so defiuite in the case of frogs. I n the case of both mice and frogs there mas loss of nitrogen which mas not however as great as that which occurs during fasting.The fat in the livers of the animals poisoned by phosphorus is derived from the subcutaneous fat depbts. This fact was determined by injection of foreign fats and the estimation of the iodine-numbers of the liver fat. Very marked mas the fat diminu- tion after phosphorus poisoning when the mice were fed with a bread diet. Whereas after simple fasting phosphorus poisoning caused a fat diminution of SO% after feeding with bread under otherwise similar conditions the fat sank to 84% of the normal. The f a t content of the liver had sunk from 15 to 30%. The energy consumed both by the normal and phosphorus-poisoned animals on a bread diet was the same (about 33 cal. per kilo. body-weight per hour).It appears according to the author that the administration of glycogen-forming substances causes a n oxidation of the infiltered fat in the liver of phosphorus-poisoned animals and that therefore on a carbohydrate- rich diet there is no fatty liver but even the fat is less than normal. The results leave according to the author no donbt as to the fact that the f a t in the livers of phosphorus-poisoned animals is due to infiltration and is not derived from proteins. Kumagawa’s theory as to the action of phosphorus on the liver cells aud the metabolism of fat and carbohydrates in the liver is given in brief outline. S. B. S. Inhibition of Post-mortem Production of Sugar in the Liver and of Certain Forms of Glycosuria by the Intravenous Injection of Dilute Solutions of Sodium Carbonate.FREDERICK W. PAVY and WILLIAM GODDEN (Proc. Physiol. SOC. 1911 vii-x; J. Physiol. 43)-Pavy and Bywaters (Abstr. 1910 ii 1098) have S. B. S.PHYSIOLOGICAL CHEMISTRY. ii. 69 previously shown that acids activate inverting and diastatic enzymes. In the case of liver-diastase the post-mortem production of sugar can be inhibited by previous injection of a 2% solution of sodium carbonate. Some forms of glycosuria are dependent on sugar being thrown into the circulation by the liver ; this occurs €or instance in the glycosuria produced by chloroform inhalation; this in the cat can be reduced and even completely inhibited by injection of sodium carbonate ; the injection of normal saline or Ringer’s solution has no such effect W.D. H. The Influence of Iodine on Autolysis LEON KEPINOW (Biochem. Zeitsch. 191 1 3’7 338-248).-‘The addition of iodine accelerates the autolysis of the liver whereas that of potassium iodide does not. The injection of Lugol’s solution also increases the liver autolysis when the organ is removed from the animal within six t o twenty-four hours after the injection. The injection OF potassium iodide produces a similar effect. Long-continued injections of the iodide produce a still more marked effect. The serum of animals which had been subjected t o a long-continued treatment also produced an accelerating effect. Iodine did not accelerate the action of pancreatin on heated liver tissue. The injection of both iodine and potassium iodide increased the anti-tryptic index. S.B. S. Ingestion of Acids by a Dog after Partial Extirpation of the Pancreas. HENRI LABBE and L. VIOLLE (Compt. Yend. 1911 153 1085-1087).-A dog from which six-sevenths of the pancreas had been removed was given a considerable amount of hydrochloric acid with its food. Contrary to expectation the operation did not dimiuish the capacity of the organism to prevent intoxication by an increased out- put of nitrogenous bases. Nevertheless the effort necessary to resist the action of the acid was apparent from the animal’s loss in weight and by a fall in the coetticient of nitrogenous equilibrium. No such changes were produced by the acid in healthy animals neither was the proportion of amino-nitrogen in the urine altered. Removal of the pancreas appears to lead t o an increased destruction of amino-acids.w. 0. w The Enzymes of the Spleen. TAMIO TANAKA (Biochem Xeitsch. 1911 3’7 249-261).-The dried powder of pig’s spleen contains the following enzymes catalase oxydase starch aud glycogen-splitting diastase inulase invertase lipase urease and enzymes of the type of pepsin trypsin and erepsin. The following enzymes were absent lactase deamidase and glycolytic enzymes. S. B. S. The Vesicular Fluid of the Hedgehog. F. GOWLAXD HOPKINS (J. PI~ysioZ. 1911 43 259-260).-The secretion of the vesiculze seminales is a glairy milky slightly alkaline fluid which contains a crystalloid substance in suspension that can be removed by the centrifuge. The crystals look like ill-formed crystals of edestin ; it gives the protein colour tests and contains phosphorus.Prolonged boiling with water and prolonged action of alcohol do not affect theii. 70 ABSTRACTS OF CHEMICAL PAPERS. form or transparency of the crystals. It differs also from other phospho-proteins in its comparative resistance t o the solvent action of alkalis. Its solution in sodium hydroxide gives an amorphous pre- cipitate on acidifying and evolution of hydrogen sulphide. The crystals are soluble in dilute hydrochloric acid and this solution reduces Fehling's solution. I n the clear residual fluid obtained by removing the crystals small quantities of albumin and globulin are present. W. D. H. The Enzymes of Bull's Testes. SHINJI MIHARA (Zeitsch. physiol. Chm. 191 1 '75 443-455).-An enzyme was found which is capable of fiplitting arginine into ornithine and urea.The intensity of action of the deamidase contained in the extract of the testes varies largely according to tho amino-compounds employed. Asparagine is readily decomposed into ammonia whilst glycine is only slightly attacked and urea remains unchanged. It is not clear from the present stage of the investigations whether or not specific enzymes are required for the decomposition of various amino-compounds. Nuclease is present and also an enzyme acting on salicin but not on amygdalin. The Relation between the Corpus Luteum and the Growth of the Mammary Gland. CHARLES H. O'DONOGHUE (Proc. physiol. Soc. 192 1 xvi-xvii ; J. Physiol. 43).-Experiments and observa- tions are adduced which shorn that in the marsupial Dusyur2c8 the corpus luteum of the ovary is a ductless gland which produces an internal secretion which is the inciting cause of the growth of the mammary glands.W. D. H. Formation of Glycine in the Body. I. ALBERT A. EPSTEIN and SAMUEL BOOKMAN (J. Biol. Chem. 1911 10 353-371).-The production of glycine in the body is progressive depending t o a certain extent on the amount of benzoic acid present in the circulation ; no reserve store of glycine exists. Benzoic acid does not cause a massive decomposition of protein but its action is selective ; it combines with glycine or with other groups which can be changed into glycine. This occurs independently of the rest of protein metabolism. Cooking and Composition of Some English Fish. KATHEBINE I. WILLIAMS (Chem. News 1911 104 271-274.Compare Trans. 1897 71 649).-Results of analyses are given showing the quantities of water ash protein fat reducing gubstances (as dextrose) etc. yielded by some twenty-five different kinds of fish after these had been cooked by boiling. The loss in weight of the fish during the cooking is recorded and attention is drawn to the phosphorus-content of fish ; the quantities of phosphoric anhydride found on tho analysis of the mineral constituents of the different kinds of fish show that as a rule fish does not contain a larger quantity of phosphorus compounds than The Effects of Asphyxia Hyperpnoea and Sensory Stimula- tion on Adrenal Secretion. WALTER B. CANNON and R. G. HOSKINS (Anzer. J. Physiol. 1911,!2@ 27$-279).-The method used for testing H. B. M. W. D. H.is present in the flesh of animals. w. P. s.PHYSLOLOGICAL CHEMISTRY. ii. i I for adrenaline in blood was Hoskins' namely a strip of intestine is placed in oxygenated Ringer's solution and then transferred t o the blood; the amount of inhibition of the contractions indicates the amount of adrenaline in the blood. Cats were used. Asphyxia was found to result in increased secretion from the adrenal bodies. H y p e r p e a does not lead to this result. Stimulation of large sensory nerves (and probably therefore surgical shock) causes increased adrenal secretion ; adrenal fatigue may therefore be a factor in shock. W. D. H. Isolation of Choleic Acid Stearic Acid and Cholesterol from Ox Gall-atones. HANS FISCHER and P. MEYER (Zeitsch. phpsiol. Cheni. 1'31 1 76 95-98).-Pomdered ox gall-stones when extracted with ether yield to the extract choleic and stearic acids and cholesterol.The choleic*acid obtained m. p. 185-18So [a]. + 4S*2' was t'asteless. E. F. A. The Influence of Colloids on Diuresis. FRANK P. KNOWLTON (J. Phys'iol. 191 1 43 219-231).-Colloids which possess an osmotic pressure such us gelatin and gum acacir inhibit in rabbits the diriresis produced by normal saline solution or by hypertonic solutions of sodium chloride but are largely ineffective on the diuresis caused by sodium salphate. The diriresis produced by the latter salt is accorn- panied by an increased oxygen-consumption by the kidney ; that produced by sodium chloride is apparently mechanical or a t leilst is not accompanied by detectable increase of metabolic activity.The colloids given cause no alteration in the blood-flow through the kidney and do not affect its gaseous metabolism. Change in the coucentrution and therefore in the osmotic pressure of the blood colloids is thus a factor in the production of urine in the glomeruli. Colloids possessing no osmotic pressure have no such action. W. D. H. The Influence of Hydrocyanic Acid on the Excretion of Sulphur in the Urine. R. MAQNANIMI (Chem. Zentr. 1911 ii 1467-1468 ; from Arch. farm. sperrirn. 12 210-216).-Sub-lethal doses depress oxidative chamges in the body and as would be expected therefore cause an increase in the " neutral sulphur " of the urine. I n rabbits the effect is a lessened secretion of uiirie and a percentage increase of sulphnr. The total sulphur is slightly raised but the increase is not in the neutral sulphur.This shows that other factors than mere oxidation have to be reckoned with. W. D. H. Influence of Phloridzin on the Distribution of Nitrogen in the Urine of S t a r v e d Rabbits. JUNZI YOSHIKAWA (Zeitach. physiol. Chem. 191 1 75 475-487).-Following the injection of phloridzin into starved sabbite there is an immediate marked increase in the output of amino-acids capable of being titrated by t h e form- aldehyde method which more than keeps pace proportionally with the total output of nitrogen. The absolute amount of carbamide excreted is parallel t o the total nitrogen. A remarkable absolute and relative increase in the excretion of ammonia takes place shortly before death,ii. 72 ABSTRACTS OF CHEMICAL PAPERS.The increased protein decomposition under the influence of the poison is confirmed. I n parallel cases of exposure to extreme hunger without the administration of phloridzin the separation of total nitrogen carbamide and ammonia slowly increased their relative proportions being the same as in the phloridzin experiments. An increased excretion of amino-acids mas only observed just before death. Phloridzin accordingly exerts a specific action in causing the excretion of amino- acids. E. F. A. The Occurrence of Lysine in the Urine in Cystinuria. DANRWART ACKERMANN and FRIEDRICH KUTSCHEK (ZeitscA. Biol. 1911 5’7 355-359).-In cystinuria t,here is a met’abolic condition in which the breakdown of amino-acids is inhibited. I n numerous cases leucine tyrosine as well as cadaverine and putrescine have been found in the urine.To this list it is now necessary to add 1 ysine. W. D. H. The Action of Alanine on the Excretion of Acetone. GUNNAR FORSSNER (Chern. Zentr. 191 1 ii 7 049-1050 ; from Xkund. Arch. Physiol. 1911 25 338-342).-On a customary diet and muscular work a slight acetonuria occurs lasting about tweIve hours (0.06 gram per hour). The addition of alanine diminishes t h i s considerably. The “anti-ketogenic” action of alanine is thus considered to be proved. W. D. H. Creatinine Excretion of the Pig. E. V. MCCOLLUM (Amer. J. Physiol. 1911 29 210-214).-Most pigs will take a sufficient amount of starch solution containing the necessary salts t o meet all the energy requirements day after day with no evidence of anorexia and no appreciable loss of weight.Under such conditions exogenous protein metabolism mould vanish and the .ratio of crestinine-nitrogen t o total nitrogen should be constantl. I n six animals i t averaged 18.5. No creatine was present To determine endogenous protein metabolism in the pig i t is necessary to determine the creatinine-nitrogen in the About 60% of the total nitrogen was in the form of urea. urine whsn the diet is ii-ee from nitrogen and multiply by 5.5. W. D. €1. Action of Certain Lipoids in Producing Caseation. H. GAEHLINGER and A. TILMANT (Compt. rend. 1911 153 982-983).- Animals treated with subcutaneous injections of hepatic lipoids develop tumours consibting of a fibrous envelope enclosing a casein-like magma. Similar results have been obtained by Lefebvre (Th2ssis Lille 19 1 1 ) using a meconium culture and by Auclair who emplojed a toxin from tubercle bacilli These three ninterials all .contain a considerable amount of cholesterol with fatty acids and these are supposed to be the active agents in producing the substance resembling casein. w.0. w. Emotional Glycosuria. WALTER B. CANNON A. T. SHOHL and W. G. WRIGHT (Amer. J. Physiol. 1911 29 280-287).-Pright or rage in a cat leads to glycosuria. Thia does not occur after removal ofPEYSIOLOGIICAL CHEMISTRY. ii. ’13 the adrenals. Emotional glycosuria is possibly useful ; fear and anger in wild life are likely to be followed by muscular struggles and a mobilisation of sugar in the blood may be of service t o the labouring muscles.W. D. H. The Action of Phosphoryl Chloride on the Body of Man and of Animals. ROBERT MULLER (ClLeni. Zentr. 1911 ii 41-42 ; from Zeitsch. exp. Pnth. Ther. 1911 9 103-125).-Clinical experiences obtained on the human subject in cases of phosphorus poisoning and poisoning after chloroforiii narcosis are discussed and amplified by direct experiments on rats. Inhalation experiments on the latter in a Dreser inhalation apparatus with solutions of phosphoryl chloride in benzene were carried out. The effects of tho benzene could be readily distinguished from those of the phosphoryl chloride. The effects of the latter were found to depend far more on the concentra- tion in the inhaled air and the time of action than on the absolute quantities in the animal organism.In an atmosphere of phosphoryl chloride containing 0*05-0*2 vol. % of the gas the animals die within a few hours with serious lesions whereas they can withstand several inha-lations and live for a long time when it is only 0.0123 vol. %. The histopathological effects were also investigated. By oral ingestion of the aqueous solution intense local irritant action was observed. The coefficient of division of phosphoryl chloride between water and benzene was found to be 0.764 0.736. s. B. s. [Phyeiological Action ofJ Electrically Prepared Colloidal Rhodium. ANDRE LANCIEN (C0772pt. rend. 191 1 153 1088-1090. Compare Gutbier Abstr. 1905 ii 396 533).-Colloidal rhodium has been obtained by Bredig’s method in the form of an unstable solution containing 0.002 gram per litre.This solution is toxic towards patho- genic organisms but is without poisonous action on fish frogs and dogs unless employed in very large doses. When rendered isotonic to blood by means of sodium chloride and stable by the addition of a trace of sodium glycocholate it was found to have a very beneficial effect in cases of pneumonia typhoid peritonitis enteritis post- operative septiczemia and in tuberculosis during febrile periods. The injections were painless arid in fever reduced the temperature to normal. The patient’s urine showed an increase in chlorine and uric acid but a marked diminution in urobilin and in scntole and indole The Influence of Guaiacol Derivatives on the Excretion of Glycuronic Acid. TH. KNAPP (Cheni. Zentv. 1911 ii 41 ; from SC~LWG~Z.Wocl.. Chem. Yhwm. 1911 40 229-231).-The amounts of guaiacol derivatives excreted after ingestion in combination with glycuronic and sulphuric acids were estimated. The glycuronic acid was estimated by Tollens’ method. After ingestion of potassium guaiacolsulphonate the glyciironic acid increased above the normal only after large doses ( 3 grams). The increase of conjugated acids after administration of guaiacol glycerol ether is due not only to the preaence of paired acids with guaiacol but also to conjugated acids of a non-volatile derivative. derivatives. Leucocytosis was increased. w. 0. w. S. B. S.ii. 74 ABSTRACTS OF CHEMICAL PAPERS. The Action of Choline and Neurine. J. PAL (Chin. Zentr. 191 1 ii 1253-1254; from Zeitsch. exp. Path. Ther. 1911 9 191-206).- Synthetically prepared choline when intravenously injected acts either as a depressor or pressor substance and the effect is largely deter- mined by the state of narcosis.After protracted ether narcosis or the use of some kinds of curare the pressor effect comes out. Sub- cntaneously injected it has but little toxic action. The effect of neiirine hydrochloride is much more powerful and very minute doses raise the blood pressure; it produces the same effect when given hypodermically. The effect of choline on the heart is incoustant but there is usually a primary weakening of its action followed by an increase. W. D. H. The Behaviour of Betaine Trigonelline and 1-Methyl- pyridinium Hydroxide in the Animal Organism. ARNT KOHLRAUSCH (Zeitsch,. Biol. 191 1 57 273-308).-1f betaine is given to an animal much of i t passes unchanged into the urine; the amount 80 unaffected in its passage through the body is greater in herbivora than in carnivora.This occurs whether it is given by the mouth or injected hypodermically. Some is broken down to trimethylarnine. Trigonelline and methylpyridinium hydroxide are excreted completely as such. In mm during abstinence from nicotine and caffeine no pyridine derivatives occur in the urine. Betaine chloride acts on the isolated heart and en blood pressure as Waller Plimmer and Miss Sowton stated Trigonelline acts in a similar way. Methyl- pyridinium hydroxide however increases the arterial pressure and diminishes pulmonary ventilation. Strychnine Reversal. A. G. W. OWEN and CHARLES S.SHERRINQTON (J. Physiol. 191 1 43 232-.241).-Under the influence of strychnine certain inhibitory reflex phenomena i n skeletal muscles are converted into excitatory reflex effects. The possible explanations are discussed but no definite decision arrived at. Some Iodine Compounds and Preparations in Common Therapeutic Use. EDUARDO FILIPPI (AYcIL. Farm. sper. Sci. 19 1 l? 12. Reprint 22 pp.).-The catalases of the blood and of the liver readily absorb iodine for instance from an alcoholic iodine solution. The product obtained may contain lO-ZO% of adsorbed iodine and when the iodocatalase is administered to an animal the elimination of the iodine is very slow. The iodocatalases do not affect the progress of peptic digestion and their own catalytic activity is not sensibly less than that of the non-iodised catalases.The author discusses t h e probable mode of attachment of the iodine in several preparations intcnded for use as drugs. Some are adsorption products others true iodine compounds in which the iodine is linked either to carbon or oxygen ; mauy so-called organic iodiue compounds are really derivatives of hydriodic acid. The Physiological Action of Extracts of the Pineal Body. €3. E. JORDAN and J. A. E. EYSTER (Amer. J. Physiol. 1911 29 115-123).-The effect of injecting extracts of the pineal body W. D. H. W. D. H. R. V. S.VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 7 5 intravascularly in cats is small and unimportant as stated hy Dixon and Halliburton; in dogs the fall of blood-pressure is more marked and is associated with vaso-dilatation in the intestinal area. The beat of the isolated cat’s heart is slightly improved by the addition of the extract ; transitory diriresis associated with glycosuria occurred in about 80% of the cases. Physiological Action of At ox yl (p-Aminophenylarsin ic Acid). MAXIMILIAN NIERENSTEIN (Ber. 1.91 1 44 3563).-A claim for priority. Bertheim (Abstr. 191 1 i 1055) has attributed to Ehrlich the suggestion that the amino-group in atoxyl plays the same r81e as the chromogenic group in a dye. It was made previously by Breinl and Nierenstein (Abstr. 1909 ii 509). Bio-chemical Investigations of Aromatic Mercury Com- pounds. WALTHER SCH HAUTH and WALTER SCHOELLER (Biochem. Xeitsch. 191 1 3’7 51 0-511).-Further reply to Blumenthal (Abstr. 1911 ii 1017). Narcosis and Want of Oxygen. IV. ELISABETH HAMBURGER (P’iiger’s Archiv 19 1 1 143 186-1 88).-Various narcotics of the f a t t y series dissolved in olive oil diminish its capacity to absorb oxygen. Sulphonal and t.riona1 act most and tetronal among the narcotics tested least strongly. W. D. H. E. F. A. 8. B. S. W. D. H. Action of an Oxazine (3 5 9-Triaminophenoxazoaium Chloride) and of Acridine on Trypanosomes. A. LAVERAN and D. ROUDSKY (Conzpt. rend. 1911 153 916-919. Compare Abstr. 1911 ii 91 I).-When the centrosomes of trypanosowes (Tr. czwnnsi) from tbe blood of mice have been caused to disappear by administra- tion of a n oxazine as described in a n earlier communication i t is possible t o produce a similar condition in untreated mice by inoculating them with such modified trypanosomes. Acridine has a similar action on the centrosomes. The action is attributed to autoxidation eince snbstanceP such as alkaloids or potassium cyanide which diminish oxidation also prevent absorption of the dyes by the centrosomes. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9120205057

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

i. 65 Organic Chemist rg. Three Normal T e t r a t r i a c o n t a n e Saturated Hydrocarbons Triacontane and Hexatriacontane. ALBERT GASCARD (Conapt. rend. 19 12 154 1484-1487).-Pentadecyl alcohol (Simonini Abstr. 1892 1301) was converted into pentudecgZ iodide brilliant scales m. p. 24.5'. This was boiled with xylene and sodium for twelve hours when n-triacontane C30H62 was obtained as brilliant scales m. p. 65*2-65*5O isomeric if not identical with the hydro- carbons isolated from plants by Elobb (Abstr. 1910 ii l l O O ) and from the products of electrolysis of potassium palmitate by Petersen (Abstr. 1906 i 331). Heptadecyl stearate was prepared by heating silver stearate with iodine. The compound crystallises in silky lamellae m. p. 64*7O and on hydrolysis yields n-heptudecyl ulcohol pearly scales m.p. 54'. Heptudecyl iodide brilliant lamellze m. p 33&6O when treated with sodium gives n-tetratriacontane C34H70 occurring as very brilliant scales m. p. 73.2". Similarly octadecyl iodide m. p. 33.5' has been converted into n-hexat?-iacontccne C36H74 a substance cry s t a l k i n g in brilliant lttmellae m. p. 76'. w. 0. w. Catalytic Action. V. Friedel and Crafts' Reaction. JACOB B~ESEKEN (Rec. trccv. chim. 1911 30 381-391. Compare Abstr. 1910 i 152).-In continuation of the previous work it is shown that disaociable chlorides such as sulphuryl chloride pentachloroethane and chloral act as a mixture of the non-decomposed molecule in which the chlorine atoms are activated and of its products of decomposition. The first-named chloride has been tried with benzene toluene and anisole.With the two former the products of reaction are those of the condensation of the non-dissociated molecule as well as those of the products of dissociation. The latter are i n excess since the equilibrium SO,Cl Trr SO,+Cl is displaced to the right by the catalyst. In the case of anisole the reaction only yields the sub- stances formed from the products of dissociation probably owing to the fact t h a t the anisole is attacked so energetically by these products. With pentachloroethane i t is only t h e activated chlorine in the undecomposed molecule which attacks benzene although at the same time some of the pentachloroethane is decomposed into tetrachloro- ethylene and hydrogen chloride. Chloral and benzene give a very complex reaction a large number of substances being formed owing to the fact that the products of decomposition of the chloral can re-combine t o form other Substances.W. G. Autoxidation of Trichloroethylene. ERNST ERDMANN (J. pr. Chem. 1912 [ii] 85 78-89).-Trichloroethylene was prepared by VOL. CII. 1. fi. 66 ABSTRACTS OF CHEMICAL PAPERS the action of alcoholic potash on tetrachloroethane; i t has b. p. 85*8-86.0"/741.6 mm. m. p. - 8 3 O Dp 1.4649 D:" 1.4695. I n contact with air this liquid undergoes autoxidntion ; at elevated temperatures and increased pressure for example in an autoclave the reactions are complex a mixture of halogen compounds boiling between 100 and 240' being obtained due to polyrnerisations and secondary actions; at the ordinary pressure and below 60° the process is much simpler the final products being hydrogen chloride carbon monoxide carbonyl chloride and dichloroacetyl chloride the latter being the only liquid product.I n order to obtain measurable quantities of the products the experiment may have to extend over several weeks; the rate of reaction varies as the ratio of trichloroethylene to oxygen. With excess of oxygen after twenty-eight days the amount of oxygen removed is between 1 and 2 atoms for each molecule of trichloro- ethylene originally present thus indicating the simultaneous reactions CHCl:CCl + 0 = CHCl,*COCl and CHCl:CCI + 0 = CO + HCl + COCI,. On passing ozonised oxygen through trichloroethylene hydrogen chloride carbonyl chloride and carbon monoxide are formed but no dichloroacetyl chloride.By using a solution of trichloroeth ylene in hexahydrotoluene at -79" the increase in weight due to ozonide formation could be directly determined and indicated an addition of one molecule of ozoiie t o each molecule of trichloroethylene ; the ozonide which was too unstable and explosive to be examined in a pure C H Cl $XI state is therefore formulated I . The gases from an explosion 0-0:0 of the ozonide contained carbon monoxide carbonyl chloride hydrogen chloride and an oxide of chlorine ; the decomposition can be moderated by solution in chloroform or liexahydrotoluene but the product's are the same with the exclusion of the oxide of chlorine. I n decornpositioti in the presence of water hydrogen peroxide is formed. The spon- taneous decomposition of the ozonide in a dilute solution (for example excess of trichloroethylene) in the absence of water indicates that an atom of oxygen is first removed being chemically absorhed by the solvent and after removal of excess of trichloroethylene i n a vacuurn a pungent oil remains to which is attributed the formula it rapidly decomposes giving carbon monoxide hydrogen chloride and carbonyl chloride the first two of which can be regarded as the decom- position products of the intermediate formyl chloride.No indication of dichloroacetyl chloride was detected in any decomposition of the ozonide. The author therefore suggests an explanation of the sutoxidation of trichloroethylene described by the formulae ?HCl-$JCI 0-0 ; CHCl:CCl -+ CHCl*CCl -+ CHCl*CCI -+ CHCl,*COCl.\O/ \O/ .. 0 + O (1.) (11.) (111.) (IT. 1 The method of formation of the dichloroacetyl chloride is thus The nascent oxygen formed at (111) together with ordinary explained.ORGANIC CHEMISTRY i. 67 oxygen then attacks another molecule of t,richloroethylehe like a molecule of ozone giving tho ozonide which then decomposw a s described above. The possibility of autoxidation is not restricted t o unsymmetrical substituted ethylenes (compare Demola Abstr. 1878 847 ; Demole and Durr Abstr. 1878 846; Anschutz Abstr. 1880 98). The action of other oxidising agents on trichloroethylene was also investigated ; anhydrous ferric chloride attacks the substance in a sealed tube first at 8 5 O the former being reduced to the ferrous salt whilst the latter gives pentachloroethane ; a t higher temperatures the last substance loses a molecule of hydrogen chloride and the resultant tetrachloroethglene becomes further 'converted into hexachloroethane. D.F. T. The Distillation of Methyl Alcohol. GUSTAV BIRSTEIN H. DENNELER and ALFRED HEIDUSCRKA (Zeitsch. nngew. Chem. 1911 24 2429-2430).-Two series of experiments on the volatility of solutions of methyl alcohol have been carried out. In the first series in which the solutions were distilled under constant pressure it was shown that even dilute solutions of methyl alcohol yielded distillates comparatively rich in methyl alcohol. I n the second series in which the temperature was kept approximately constant and air drawn through the solution the concentration of alcohol in the distillate was found to be invariably slightly greater than in the original solution.The bearing of these results on the commercial preparation of formaldehyde is discussed. H. W. Action of Potassium Hydroxide on Primary Alcohols ; Preparation of the Corresponding Acids. MABCEL GUEHBET (Cornpt. rend. 1912 154 1487-1489 ; J. Phurm. Chim. 1912 [vii] 5 58-64).-Dumas and Stas (Ann. Chim. Phys. 1840 [2] 73 113) found that potassium hydroxide acts on methyl ethyl and amyl alcohols a t 200-230" transforming them into the corresponding acids with liberation of hydrogen. It is now shown that in the case of the lower alcohols dehydration also occurs with formation of ethylenic hydrocarbons. The higher alcohols however form only hydrogen and the potassium salt of the acid.This method of oxidation is very advantageons for alcohols above the C terms since i t is unnecessary to employ sealed tubes and the yield is practically theoretical. P-Methylpentanol gives a 95% yield of the corresponding acid which was characterised by conversion into its umide tn. p. 85O. B-Heptylhexoarnide CH; [ CH,],* CH(C7H15) *CH,-CO*NH has m. p. 108O. w. 0. w. Calcium Ethoxides. ROBERT DE FORCRAND (Compt. rend. 191 2 154 1441-1444. Compare Abstr. 1895 i 259; Doby Abstr. 1903 i 546 ; Chablay this vol. i 3).-Calcium ethoxide Ca(OEt),,ZEtOH when allowed to remain over concentrated sulphuric acid slowly loses alcohol. A specimen prepared in 1905 now approximates in com- f 2i. 68 ABSTRACTS OF CHEMICAL PAPERS. position to the formula 3Ca0 EtOH,2H20 or Ch(OEt),,5Ca0,5H,O.The suggestion is put forward that a process of catalytic decom- position occurs calcium oxide the active agent behaving as the thorium dioxide in Sabatier and Mailhe's experiments (Abstr. 1910 i 294). Calcium ethoxide is analogous to the hypothetical compound ThO(OEt) losing ethylene or ether like this substance but having greater stability a t the ordinary temperature. w 0. w. The Crystallographic Distinctions of Nitroglycerol. SIGURD NAUCKHOFF (Zeitsch. Scheiss. Spreoigstoflw. 191 1 6 124-125).-The paper contains sketches and measurements of two forms of nitro- glycerol crystals; they are of the bipyramidal class of the rhombic system but when obtained from supercooled nitroglycerol have a flattened tabular habit whilst those deposited from saturated ethereal solution are of rhombic character; their optical properties are also described.The author discusses the work of Kast (Atti V I Cong. Internax. chim. appZ. IlIb) and considers that the m. p. of nitroglycerol is - 12*5O instead of - 13.5' (Kast). F. M. G. M. Transformations of Thio- and Seleno-phosphoric Esters. P. PISTSCHIMUKA (J. p. Chcm. 1911 [ii] 84 746-760 ; from Mern. Inst. agr. forest. Now0 Alexandria 191 1 1-148).-Tloe esters of thiophosphoric acid should exist in two isomeric forms PO(0R);SR and PS(OR) but hitherto only the latter series have been prepared. It is found that the esters of this series combine with a large number of metallic salts yielding additive compounds which undergo decom- position either a t the ordinary temperature or when heated with the formation of derivat.ives of isothiophosphoric acid PO( OH),*SH ; thus the additive compounds of the alkyl esters with silver nitrate PS(OR)3,AgN0 readily lose one molecule of alkyl nitrate and form salts of the composition PO(OR),*SAg.The isomeric esters are obtained from these salts by the action of alkyl iodides. A similar transformation into derivatives of the isomeric acid is mused by alkalis alkyloxides alkyl halides and ammonia although the formation of intermediate additive products with these compounds could not be observed. The transformation is however not confined t o esters of monothiophosphoric acid but is common to all esters of the type PS(XK),*OR (where X = O or S) derivatives of PO(XH),*SH being produced.Esters of selenophosphoric acid PSe(OR) have also been prepared and converted into the isomeric forms by methods similar t o those employed in the case of the thiophosphates. The alkyl thiophosphates of the type PS(OR) were prepared by the method described pipeviously (Abstr. 1909 i 5) ; the ethyl ester has b. p. 106O/20 mm. D! 1.0944; the pvopyl ester b. p. 133-134O/ 20 mm D 1.0409 ; the isobutyl ester b. p. 155°/20 mm. Dt 0.9907 On treatment with nitric acid they yield esters of phosphoric acid and are converted by sodium into the corresponding alkyl phosphites. The compound PSCl,* SEt obtained by heating the acid chloride,ORGANIC CHEMISTRY. i. 69 PCl,*SEt with sulphur has b. p. 92.110 mm. Di 1.4453; i t reacts with sodium ethoxide yielding ethyl dithiopliosphate PS( OEt),*SEt b.p. 130°/20 mm. D 1,1340. Ethyl trithiophosphate obtained from the chloride PSCI,*OEt and sodium ethylmercaptide is a liquid b. p. 155'/20 mm. D,3 1.1716. The following additive compounds with mercuric chloride were prepared PS(OMe),,ZHgCI transparent needles melting a t 1 0 2 O and simultaneously losing methyl chloride forming the compound PO(OMe),*SHgCl,HgCl which passes a t 150' into the cornpound SHgCl*Pu(OMe)*OHgCI ; SHgC1.PO(OEt),,HgC12 forms stout trans- parent prisms m. p. 6 6 O which a t 85" yield the conapuund SHgCl*PO(OE t)-OHgCl; P S ( O P I - ~ ) ~ ~ H ~ C J ~ ; PS(OCH2Prfi),,2HgC1 ; PS(SEt),.0Et,2HgC12 white needles m. p. 81'; PS(SEt),,BNgCI m. p. 84'. All additive compounds of the type PS( XR),*OR,2HgC12 lose one molecule of alkyl chloride a t a relatively low temperature.The esters of thiophosphoric acid form with ferric chloride additive compounds of the general formula 3PS(OR),,2 FeCI which lose three molecules of alkyl chloride when heated ; the methyl compound forms large yellow prisms m. p. 125' ; the ethyl compound is crystalline ; the propyl and isobutyl compounds are oils. The ethyl esters of di- and tri-thiophosphoric acid yield with ferric chloride oily additive compounds having a similar composition. Compounds of the same type are formed with ferric bromide but only the methyl compound 3PS(OMe),,2FeBr3 m. p. 9 9 O is crystalline Ethyl thiophosphate combines with platinic chloride yielding the compound 3PS(OEt)3,2PtCl orange-yellow needles m. p. 103'. The crystalline compound of methyl thiophosphate and auric chloride has m.p. 110'. Silver nitrate dissolves in methyl thiophosphate yielding methyl nitrate and the silver salt PO(OMe),*SAg and in ethyl thiophosphate t o form the additive compound PS(OEt) AgNO which decomposes slowly a t the ordinary temperature into ethyl nitrate and the silver salt PO(OEt);SAg m. p. 8 2 O . Similar compounds are formed by the propyl and isobutyl esters. The phenyl ester reacts with silver nitrate yielding o-nitrophenol and the compound PO(OPh),*SAg. The behaviour of silver nitrite resembles that of the nitrate. Mercuric iodide combines with the alkyl thiophosphates PS(OR) t o form additive compounds which are derivatives of the isomeric ester PO(OR),*SR. Thus ethyl thiophosphate when heated with mercuric iodide a t 1 80" yields the cornpound PO(OEt),*SEt,2Hg12.Similar compounds are formed by the esters of di- and tri-thio- phosphoric acid. The interaction of alcoholic ammonia and ethyl thiophosphate yields ethylamine and the cornpound NH,*PO(OEt),. Sodium hydroxide sodium ethylmercaptide and sodium a1 kyl- oxides react with the d k y l thiophosphates to form sodium salts of the composition PO(0R);SNa. The action of sodium hydroxide and sodium alkyloxides on the esters of di- and tri-thiophospboric acids leads to the formation of a mercaptan or alkyl sulpbide togetheri. 70 ABSTRACTS OF CHEMICAL PAPERS. with sodium salts containing a smaller number of atoms in the molecule. Sodium ethylmercaptide on the other hand gives rise to the sodium salts SNa*PO(SEt)*OEt and PO(SEt),*SNa.The isomeric thiophosphoric esters of the type PO(OR),*SR are obtained by the action of alkyl iodide on the above-mentioned silver salts PO(OR),*SAg in alcoholic solution. The methyl ester has b. p. 107'/20 mm. D! 1.2685; the ethyl ester b. p. 122'/20 mm. D! 1,1245; the propyl ester b. p. 156'/20 mm. D! 1.0532; the isobutyl ester b. p. 170'/20 mm. D! 1.0102. The esters of selenophosphoric acid of the formula PSe(OR) are formed by the combination of gcmolecular" selenium and esters of phosphorous acid; the methyl ester is a liquid b. p. 95'/20 mm. DE 1.5387 ; the ethyl ester has b. p. 117'/20 mm. D 1.3189. The following additive compounds were prepared PSe(OMe),,HgCI ; PSe(OEt),,HgCI ; PSe(OMe),,HgI m. p. 66O and is simultaneously transformed into its isomeride PO( OBle),*SeMe,HgI ; PSe(OEt),,HgI large yellow prisms m.p. 32' which pass at 75' into the isomeride PO(OEt),*SeEt,HgI m. p. 95O and when warmed under diminished pressure lose ethyl iodide yielding the compound PO(OEt),*SeHgI. Ethyl selenophosphate and sodium ethyl mercaptide react to form the sodium salt PO(OEtj,*SeNa m. p. 196'; the corresponding lend salt is unstable and yields with ethyl iodide the ester PO(OEt),*SeEt a liquid b. p. 140°/20 mm. D 1.3593. Esters of the type PS(XR),*OR are transformed by prolonged heating with an excess of alkyl iodide into their isornerides. Thus ethyl thiophosphate PS(OEt) is converted by ethyl iodide into its isomeride PO(OEt),*SEt and by isobutyl iodide into the estey PO( OEt),*S*CH,Pr?.With respect to the mechanism of the above-mentioned transforma- tions the author considers that in all cases additive compounds containing either a quadrivalent or sexavalent sulphur or selenium atom are first produced and that these subsequently undergo tautomeric change and decomposition ; the action of sodium ethoxide on ethyl dithiophosphate is represented as follows PS(OEt),*SEt NaS*S(OEt):P(OEt),*SEt -+ NaS*S*P(OEt),*SEt -+ NaS*PO(OEt) + Et,S. F. B. Complex Compounds of Platinous Bromide with Organic Sulphides LEO A. TSCHUCIAEFF and (Mlle.) D. PRAENKEL (Compt. rend. 1912 154 33-35. Compare Abstr. 1910 i 354).-When an aqueous solution of potassium platinobromide is treated with ethylene- dithioglycol ether the compound [PtZC,H,(SEt),]PtBr separates as a grey microcrystalline precipitate m.p. 157". At looo this substance changes into a yellow isomeride having the same m. p. but a greater solubility in water and chloroform. The above constitution is assigned to the substance on the ground t h a t it unites with Reiset's bromide forming the salt [Pt4NH,]PtBr4 together with a yellow cornpound in. p. 157-158'. The latter has the constitution [C,H+(SF:t),],PtBr since it can also be prepared by mixing the grey salt with ethylenedi-ORGANIC CHEMISTRY. i. 71 thioglycol ether and potassium platinobrornide in equimolecular proportions Potassium platinobromide reacts with methyl sulphide giving an unstable grey compound [PtPMe,S]PtEr m. p. 160'. On crystal- lisation from chloroform this changes into Blomstrand's salt ( Me,S),PtBr,.Platinoiodides do not form derivatives with organic sulphides. w. 0. w. Intramolecular Rearrangements of Aliphatic Sulphoxides. THonrAs P. HILDITCH (Ber. 191 1,44 3583-3589).-By treatment with alcoholic hydrogen chloride or with boiling acetic anhydride diisoan?yI- sulphoxide is converted into isoamyl mercaptan and isovaleraldehyde ; by the former reagent thionyldiacetic acid is decomposed into thioglycollic and glyoxylic acids. SO( CMe,*CO,H) m. p. 186" is unchanged by alcoholic hydrogen chloride. a-T?~ionyldiisobzctyric acid An explanation of these decompositions is given which assumes the intermediate formation of thionium compounds. c. s. Complex Compounds of Platinum with Organic Selenides. I. E. FRITZMANN (Zeitech. anory. Chem. 1911 73 239-255).- The isomerism of the compounds of platinous chloride with organic sulphides has been discussed by Tschugaeff and Subbotin (Abstr.1910 i 354). The corresponding selenium compounds have not been examined with the exception of those derived from ethyl selenide (Petren Zeitsch. anorg. Chem. 1899 20 62). The isomerism observed is similar to that of the sulphur compounds. The a-componnds are more soluble than the P-compounds and are darker in colour. The former are to be regarded in accordance with Werner's views as &-modifications and the latter as trans- modifications. The y-compounds are less stable than those of sulphur. A 4% solution of potassium platinochloride (1 mol.) is shaken with the alkyl selenide (2 mols.) until decolorised. The a-compound is then chiefly obtained. I n order to prepare the P-compound 4 mols.of selenide are used and the mixture is digested at 70-75" in a closed vessel until all is dissolved. The cooled solution is evaporated in a vacuum over calcium chloride and solid paraffin or rubber and potassium chloride is then removed by washing. For analysis the compound is decomposed with sulphuric acid and heated in hydrogen t o remove selenium the residual platinum being weighed. Selenium is estimated by boiling with aqua regia in a quartz vessel evaporating and precipitating the slightly acid solution with a hot saturated solu- tion of hydrazine sulphate. The precipitated mixture of platinum and selenium is collected dried at loo" and weighed and the selenium is then removed by heating in hydrogen.Methyl selennide pZc&nous chloride PtC1,,2Me2Se has m. p. 163-1 63.5". The a-form is partly converted into the p-form by repeated crystallisa- ticm from chloroform arsd the reverse change is also observed. At ai. '72 ABSTRACTS OF CHEMICAL PAPERS. low temperature it is possible t o obtained the y-modification but it can only be isolated in the form of the green Magnus salt ( Pt,4Me2Se)C1 by t h e addition of a solution of Reiset's salt (Pt,4NH,)C12. Meth,yl selenide platinous bromide PtBr2,2Me2Se is red and has m. p. 171' (decornp.). Propyl selenide forms the compound PtC12,2Pr,Se m. p. 42.5-43'; only the a-modification has been obtained. n-Butyl selenide only yields an oily product. isoAmxl selenide yields a n a-compound PtCI2,2(C,H,,),Se m. p. 97 - 975O and rz P-compound m.p. 115-116'. The phenyl selenide a-compound has in. p. 180° and the fl-compound m. p. 178-1 79'. Piethyl trimethylene diselenide forms an a- and a P-compound 2PtCI2,2CH,(CH2*SeEt) both of which have m. p. 176-176.5". A y-modification has been recognised by conversion into the Magnus salt. C. H. D. Chemico-crystallographic Notes. L. WAGNER (Zeitsch. Xryst. Min. 191 1 50 47-56).-Phosphonium iodide PH,I ; tetragonal D 2.860. Tetramethylphosphonium iodide ; tetragonal a c = 1 0.7310 D 1.746. Calcium formate C:t(CHO,) ; orthorhombic (bipyramidal) [a b c = 0.7599 1 0.9363 (Plathan)] D 2.023. Strontium formate 8r(CH0,)2 ; orthorhombic (bisphenoidal) a b c = 0.7846 1 0.8292 D 2.693. Mixed crystals of calcium and strontium formate resemble those of either one or other of the simple salts but they also show an intermediate tetragonal form ; the two salts are therefore isotri- morphous.Strontium formate forms the hydrate Sr(CH0,),,2H2V D 2.259 ; but calcium formate forms no hydrate. Anhydrous oxalic acid; orthorhombic a b c = 0-8301 1 0.7678 D 1.900. Nitrobenzene; monoclinic (domatic?) a b c = 1.280 1 '3. ; p = 117'21' m. p. 3.8'. L. J. S. Direct Synthesis of the Glycerides. GIUSEPPE GIANOLI (Atti R. Accad. Lincei 1911 [v] 20 ii 653-654. Compare Abstr. 1911 i 349 ; Bellucci and Manzetti ibid. i 259).-Polemical. R. V. S. Formation of Cork. MAX VON SCHMIDT (J. pr. Chem. 19 11 [ii] 84 830-832).-A reply t o Zeisel's criticism (Abstr. 1911 i 768) of previous work of the author (Abstr. 1910 i 540).F. B. Derivatives of Tetrolaldehyde and its Acetal [ Diethoxy- butinene]. PAUL L. VIGUIER (Compt. rend. 1911 153 1231-1233. Compare Abstr. 1909 i 69 1).-On treating diethoxybutinene with aniline hydrochloride the hydrochloTide NHPh-CMe:CH*CH:NPh,HCI is obtained as yellow crystals decomposing at 160". No definite com- pound was obtained from aniline and phenylmethylpyrazole was the only definite product with phenylhydrazine. Urethane combines with the acetnl in presence of hydrogen chloride giving the compound CMeiC.CH(NH*CO,Et) slender needles m. p. 188-189". The acetal unites with alcohol in presence of scdiuur ethoxide formingORGANIC CHEMISTRY. i. 73 aay-triethoxy-A8-butyi?ene OEt*CMe:CH*CH(OEt) b. p. 190-1 95‘ under ordinary pressure 82-86”/15 mm.DZ1 0.908 !n,g 1.430. Exposure to air converts triethoxybutylene into /3-ethoxycrotonic acid. On hydrolysis i t appears to form acetoacetaldehyde but t b i s rapidly polymerises to triacetylbenzene. When treated with semi- carbazide hydrochloride i t yields a compound m. p. 127- 128’ w 0. w. 7 H CMe N-CO*NH,. CH-N> having the constitution Action of Monochlorocarbamide on Ketones. AUGUSTE R ~ H A L and A. DETCEUF (Compt. rend. 1911 153 1289-1231. Com- pare Ahstr. 191 1 i 957).-On allowing chlorocarbamide to act on the caIculated amount of an aliphatic ketone in aqueous solutions for three t o five days a n excellent yield of a monochloro-ketone is obtained. Symmetrical ketones give the halogen derivative in which the chlorine is next t o the carbonyl group whilst unsymmetrical ketones give two halogen derivatives the secondary one pre- dominating.On boiIing the semicarbazones of chloro-ketones with water hydrogen chloride is eliminated and a ketol formed; thus the semicarbazone of P-chloropropane-y-orre gives P-hydroxypropane-y-one. Chlorocarbamide and methyl hexyl ketone give a chloro-octanone m. p. - 25O b. p. 104-108”/20 mm. D 1.0034; the semicacrbaxone has m. p. 133”. Acetophenone forms only o-chloroacetophenone ; cyclic ketones also undergo chlorination. w. 0. w. Action of Dilute Nitric Acid on Starch and on Dextrin. WILLIAM OECHSNER DE CONINCK and ALBERT RAYNAUD (Rev. yen. Chim. pure appZ. 1910 14 169-l‘iO).-An investigation on the action of dilute nitric acid on dextrin and starch. The dilution of the nitric acid varied from 1 to 5 C.C.of acid (36OB8) in 50 C.C. water and the results indicated t h a t the amounts of dextrose formed during the same interval of time increased with the concentration of the acid but that this increase was less rapid with dextrin than with starch. With low concentrations more dextrin than starch underwent hydrolysis .but a t the highest concentration dextrin yielded 87.7% dextrose as compared with 90% from starch indicating that in the former oxidation had t o some extent interfered with saccharification. F. M. G. M. Modiflcations Undergone by Nitrated Celluloses and Powders Derived from them,under the Influence of Heat. R. FRIC (Compt. rend. 1912 154 31-32).-The changes produced in nitrated celluloses by heat can be followed by measuring the viscosity of a n acetone solution in the usual way.The effect of beating the solid a t 110’ is t o diminish the viscosity of the solution. w. 0. w. The ‘gCause’’ of the Beckmann Rearrangement. PIETER J . MONTAGNE (Cliem. VeekbZad 191 1 8 968-476. Compare Abstr. 1910 i 623).-In the author’s opinion the Eeckmann rearrangementi. 74 ABSTRACTS OF CHEMICAL PAPERS. is a simple exchange of position between the alkyl group attached to carbon and that attached to nitrogen. The assumption of the inter- mediate formation of an oxime-ester is a t variance with the experimental facts. A. J. W. New Compounds of the Choline Type. G. A. MENCIE (J. .BioZ. Chem. 191 1 10 399-406).-The chloride of a - methylchoZine NClMe,*CHMe*CH,*OH has been prepared as follows ally1 chloride was converted into the chlorohydrin and then into the corresponding acetate ; this by treatment with hydrochloric acid was converted into the acetate -chloride and saponified t o give the desired chlorohydrin CHMeCL*CH,*OH. On heating at 100' in a sealed tube with trimethylamine dissolved in alcohol the choline was obtained as a viscous yellow oil from which a hygroscopic colourless solid separated on cooling.The yellow platinichloride decomposes a t 254-255' ; the aurichloride is definitely crystalline it sinters above 180° m. p. 198-1 99 -5". By condensing monochloroacetone with magnesium alkyl halides the chlorohydrins of P-methylpropylene ap-glycol and P-methyl- butylene up-glycol are obtained. With trimethylamine these yield P-disubstituted cholines. P-Dimethylcholime cldoride NClMe,*CH,*CMe,-OH is obtained as a colourless hygroscopic solid.The platinichloride crystallises in yellow short individual prisms or foliated clusters which blacken at 240' decomp. 245'. P-Meth?lZ-P-eth?llcholine chloride NClMe,*CH,*CMeEt*OH forms a platinichloride which sinters a t 240° m. p. 242-243' (decomp. ). E. P. A. Stereoisomeric Cobalt Compounds. ALFRED WERNER (Annalen 1911 386 1-272).-The author's investigations on the stereo- isomeric cobalt compounds have now reached such a stage that stringent proofs have been obtained for the s tereochemical conceptions and methods which are free from objections have been devised for the determination of the configurations of the various isomerides. A summary of the methods used and of the results obtained is given in the present paper the greater part of the work consisting of hitherto unpublished investigations.The general results arrived at may be briefly summarised as follows The investigation of inorganic compounds containing the complex radicle CoA has shown that in all these compounds the six groups A are in direct connexion with the central cobalt atom. Any space formula used to represent these compounds must be such t h a t positions occupied by the groups A are all equivalent ; this follows from the fact that no stereoisomerides are known having the formula [Co i s ] . It has hitherto been impossible to prepare more I- _J than two stereoisomerides of the formula so that the groupsOKOANIC CHEMISTRY. i . 75 Aand B must occupy the corners of an octahedron the cobalt atom being in the centre ; the plane formula and prism formula would each give three possible isomerides.The groups B in the stereoisomerides [ c o 21 must consequently occupy the cis- and trans-positions. Investigation has shown that in all cases when t h e two groups B are replaced by a bivalent group giving three- four- five- or six-membered rings the same compound results no matter whether the cis- or trans- isomeride was used in the preparation. It appears therefore that there is only one position in the complex (the cis-position) favaurable t o the formation of such rings this being in accordance with the octahedral arrangement of the groups and in analogy with the forma- tion and non-formation of anhydrides from organic cis- and trans- isomerides.Use has been made of this result in the determination of the configuration of the various stereoisomerides but great caution is necessary in drawing conclusions owing to the ready transformation of one isomeride into the other Diaquo-salts H2° Co en X,.-The ois-isomerides have been characterised by their preparation from the carbonato-salts as also from the hexol- and diol-dicobaltic salts. The cis-compounds only are known in the tetrammine series whereas both cis- and trans-compounds of the ethylenediamine series have been prepared. The configuration of Ho Co en X is deduced from that of the the h~droxo-ccquo-salts diayuo-salts because of their formation from the latter by loss of a molecule of acid. Dihatogeno-salts [X Co en,]X,.-The two stereoisomeric dichloro- salts are known both in the tetrammine and diethylenediammine series. The cis-isomeride (violeo-salt) is the first product of the action of concentrated hydrochloric acid on the carbonato-salt ; it readily changes into the trans-isomeride (praseo-salt) under the influence of concentrated hydrochloric acid. The cis-dibromotetra- ammine salts are not known.Stereoisomeric hcdogeno-apuo-salts Co en,lX are not known ; in all cases +he cis-isomeride is [H,O 1 L a 2 0 I Both cis- and trans-isomerides are known. L A alone formed,' lfulogeno-isothiocyanato-salts rst co en,lX. - Stereoisomeric I- J chloro- and bromo-isothiocyanato-salts are known. Their configuration has to be decided chiefly by their colour (see later) since they so readily undergo transformation.The isothiocyanate group deepens the colour of the cobaltammines and it follows that the violet chloro-salts and indigo- blue bromo-salts are t h e trans-isomerides the cis-isomerides being red and bluish-red respectively. Similar results hold for the isothiocy anato-a puo-salts co en,]x the violet salts forming the trans- and the orange the cis-isomerides. The configuration of the I~~.ccZogeno-amnLin~d~t~yZ~n~~iu~?a~n~ salts [H,$ co en,& has been determined by oxidation of the corresponding halogeno-isothio-i. 76 ABSTRACTS OF CHEMICAL PAPERS cyanato-salts with hydrogen peroxide ; both the chloro- and bromo- salts have been prepared. The constitution of t h e apuo-ammine- diethglenediamine salts [:$ Co en,]X is determined by their transformation into the halogeno-ammine-salts by interaction with the halogen acids.The stereoisomeric diisothiocyanato-sai ts Co en,]X have already been described (Abstr. 1900 i S6) but the wrong configuration given t o them. The cis-isomerides are those which were formerly characterised as dithiocyanato-salts as may be deduced by their oxidation with hydrogen peroxide and subsequent evaporation with hydrochloric acid whereby the cis-chloro- ammine salts are formed. The trans-isomerides on oxidation with chlorine yield trans-diamminediethylenediaminecobaltic sal ts and were formerly characterised as diisothiocyanato-sal ts. The configuration of the diamminrzdiethylenediamine salts [:$ c o en,]^ was determined by their solubilities the cis- being more readily soluble than the trans-isomerides (compare below).The configuration previously ascribed to them (Abstr. 1907 i 290) is incorrect. Oxidation of the isoth ioc yanatoamminediethylenediamine salts [p; co en2]X2 with hydrogen peroxide giv’es rise to the diammine salts whereby the structure of the former salts is ascertained. The configuration of the nitroamminedieth&nedlamine salts [$3i co en,]^ follows from their formation from the isomeric aquo-ammine salts or from their transformation into the chloro-ammine salts. On oxidation of the isothiocyanatonitrodiethyZenediarnine salts [SCN Co en,]X with hydrogen peroxide nitroammine-salts are formed whereby the configuration of the former salts can be ascertained. Of the dinitro- diethylenediamine salts [(NO,) Co en,]X the croceo-salts are the trans- whilst the flavo-salts are the cis-isouerides.This is ascertained by their formation from the stereoisomeric diaquo-salts by the action of nitrous acid the dinitrito-salts first formed transforming into the dinitro-salts. The configuration of the chloronitro-salts [o, Co en2]X is ascertained by their transformation into the dinitro-salts by interaction with sodium nitrite. Influence of the Constitution of the Complex Radicle Co 4 on the Existence of Steveoisorneric Co6alt Ammonias.-The cis-compounds of the ammonia series are less readily produced than those of the diethylene- diamine series and transform much more readily into the trans- isomerides. cis-Dichloro-compounds of the trimethylenediamine series cannot be prepared all methods of preparation giving the green trans-isomerides. The nature of the halogen has an effect in that although cis- and trans-isomerides have been prepared in the dichloro- and di bromo-diethylenediamine series no cis-dibromo-compounds have been obtained in the ammonia series; in neither series eould iodo- O2N [ &IORGANIC CEEMISTRY.i. 77 compounds be obbained. The influence of the bivalent group Z in the salts [Z Go en,]X is shown by the fact that although sulphito- carbonato- oxalato- and malonato-salts have been prepared no com- pounds derived from succinic malic and tartaric acids have been obtaiaed. The formation of a seven-ring does not therefore take place which is in accordance with the results obtained with the alkyldiamines (compare Abstr.1907 ii 161). Ionisation 1somerides.-A full list of such compounds is given ; for example the cis- and trans-isomerides of the chloronitrothiocyanate nitroisothiocyanato-chloride and chloroisothiocyaiiato-nitrite in the diethylenediamine series. their Con- stitution and Conjguration.-The cis-isomerides are ge uerally more soluble than the trans-isomerides. There are exceptions as for example with the dinitrodiethylenediaminecobaltic iodides. It is pro- bable also that the solubility of the salt increases with the number of ionogenic radicles. Relation between the Colour of the Cobalt Ammonias and their Constitution and Configuration.-The chief influence on the colour is exerted by the radicles directly connected with the cobalt atom and is the only one considered here.No colourless cobalt compounds are known. The inflnence of the element directly attached t o the cobalt atom is shown by the series C N S 0 C1 Br I the elements being arranged in the order of their bathochromic action. This series can be extended as follows when the various radicles are taken into account CN CO; NO en NH NCS; SO,; OH O*NO 0-Acyl O H ; C1 Br I; thus the least-coloured compounds of cobalt are the pale yellow cyanocobaltammonias [Co(CN),]k,. Amines for example ethylenediamine propylenediamine hydroxylamine and pyridine have the same effect as ammonia. It is noteworthy that substitution in the trans-position has a much greater bathochromic effect than substitution i n the cis-position. Dareerences i n the Reactions of Stereoisomeric Cobalt A~nmnias.- Radicles which are in the cis-position with respect to each other are not so firmly combined as those in the tram-position and enter into reaction much more readily; for example by the action of hydro- chloric acid on cis-dinitrotetramminecobaltic salts both nitro-groups are replaced by chlorine with the formation of the trans-dichloro-salts whereas when the trans-dinitro-salts are heated with hydrochloric acid only one nitro-group is replaced the tvans-chloronitro-salts being formed.Differences of this kind have caused many difficulties in the determinations of the configuration of the stereoisomerides. These difficulties are especially marked in the case of the isothiocyanato-salts a full discussion of which compounds is given. Differences also occur in additive reactions ; for example the trans-chloroemurinediethylene- diamine salts readilv give the diammine salts when dissolved in liauid Relation between the L?olubiZiiy of the Cobalt Ammonias t ammonia [(I) ciCi en2]C12 + NH = [E Co en2 t6)H,N cis-compounds are unacted on even after keeping for hours dissolved - - in liquid ammonia.Intramolecular Reactions with the Cobult Ammonicm-The variousi. 78 ABSTRACTS OF CHEMICAL PAPERS. cases are summarised in which there occurs (a) Intramolecular reactions with expulsion of ammonia or water; for example the chlorides bromides and sulphates of chloro-aquo- and bromo-aquo-. diethylenecliaminecobaltic salts are stable whilst the nitrites on keeping change in accordance with the equation .-I roo Co en21N0 + H,O.( b ) Intramolecular reactions in which inter- ;hinge of thgacid-residues takes place; for example when a drop of water is added to the pure green tlrans-dichlorodiethylenediamine- cobaltic nitrite [CI Co en,]NO it immediately changes into the yellowish-red chloronitrodiethylenediamine chloride LO2 c o en,J CI. (c) Transformation of stereoisomerides into each other. Direct transformations have hitherto been observed in comparatively few cases and even then i t is probable that intermediate products are formed which have not so f a r been isolated. Additive Compounds of the Cobalt Ammonias.-A full discussion is given of cases such as the following By the addition of silver nitrate to a solution of the intensely-red coloured salt .I [[;; g c o en,]S2069 golden-yellow prisms of the composition I L:s Co en,lS,O,,AgNO,are obtained.this compound point to its having the constitution The change in colour observed Lnd the va&us reactions of [*qg Go e n 2 ] 3 2 6 that is it is a silver thiocyanatoamminediethylenedinminecobaltic salt. The study of such compounds is of great service in elucidating the mechanism of the various reactions of the cobalt ammonias. Spatial Change of Position during Reuctions of the Stereoisomeric Cobalt Ammonias.-(Compare Abstr. 191 1 i 494.) [With Jos. ~~~~~~~~.]-~arbonatodiethy~enediaminecoba~tic salts YX where Y=[CO,Coen,] are prepared from any dichloro- or dibromo-salt by the action of sodium or potassium carbonate. The mixture with water is boiled until the solution becomes an intense blue colour when the reaction is complete. The chloride YCl,H20 is thus obtained from 1 6-dichlorodiethylenediaminecobaltic chloride by interaction with sodium carbonate.The hot filtrate from undissolved salt deposits on cooling dark red flat columnar crystals which become anhydrous at 70-80°. It may also be obtained from a concentrated solution of the bromide by shaking with silver chloride. The bromide YBr,H,O is obtained from the chloride by precipitation with potassium bromide. On recrystallisation it deposits partly as hydrated and partly as anhydrous salt. The hydrated salt forms large dark red hexagonal efflorescent columns the anhydrous salt being brownish-red in colour. One gram of the salt dissolves in 30 C.C. of water at 50". The iodide YI is obtained similarly to the bromide and forms shining dark red flat prisms which are soluble in water to the extent of 1 gram in 70 C.C.of water at 80'. The nitrate YNO,,H,O,ORGANIC CHEMISTRY. i. 79 results from the interaction of the bromide and silver nitrate; it crystallises in dark bluish-red shining flat needles. Twenty C.C. of water dissolve 1 gram a t 60". The tlJiocyanate YSCN the dithionate Y,S,0G,2H,0 and the sulphccte Y2S0,,5H,O were also obtained by.reactions involving doubleidecomposition. They crystallise respectively in red hexagonal prisms or needles long dark red prisms and reddish-black flat prisms. [With R. H~~~~u~~.]-O~alatodiethylenediaminecoba~~~c salts [C,O Coen,]X have been known for some time (compare Abstr. 1899 ii S S O ) and an attempt has now been made t o introduce ammonia into the radicle to find out if a spatial transformation takes place.As a matter of fact ammonia does enter into the inner sphere but cis-diamminediethyknediamin,ecobaltic salts Y,(C,0,)X4 are alone formed where Y = [ Co \::3)2]. Four grams of the oxalato- diethylenediamine salt are heated with 15 C.C. of saturated ammonia solution for two hours in a bomb-tube at 1 1 0 O ; the contents of the tube are taken up with water the solution concentrated and potassium iodide added. The sparingly soluble oxalatodiethylene- diaminecobaltic iodide is first precipitated and from the mother liquor brown monoclir,ic columnar crystals of the iodide oxalate Y2(C20,)I are obtained. By interaction with silver chloride irregular light yellow crystalline aggregates of the chloride oxalate Y,(C,O,)Cl are obtained.I n contradistinction to the aqueous ammonia liquid ammonia has no action on the oxalato-chloride. Y = [C,H20 Co en,]. -Thehydrogen malonate Y C3H304 is obtained from carbonatodiethylene- diaminecobaltic bromide by first preparing the hydroxide by shaking the solution with freshly precipitated silver oxide. Malonic acid (2 mols.) is added to the filtrate from the silver bromide and on con- centrating carmine-red crystals of the desired salt are obtained. By double decomposition with potassium nitrate and ammonium thio- cyanate respectively red shining leaflets of the nitrate Y NO and thiocyanate YSCN are obtained. Attempts to prepare corresponding salts by using succinic malic or tartaric acids were unsuccessful.[With MARIE ~oKRows~~.]-~u~ph~tod~eth~y~ened~am~necobn~t~c salts YX where Y = [SO Co en2].-The chloride YCl,&H,O is obtained by boiling down a solution of sodium sulphite (10 grams) with trans- dichlorodiethylenediaminecobaltic chloride (1 0 grams free from hydrochloric acid) in 50 C.C. of water to half its bulk. After filtering dark brown crystals of indefinite shape are deposited. The same results are obtained if the cis-dichloro-chloride is used in the prepara- tion. The sulphito-group is co-ordinately connected with the cobalt in the cis-position since on heating with concentrated hydrochloric acid cis-dichlorodiethylenediaminecobaltic chloride is produced. Moreover the brown colour of the salt shows that the SO,-radicle is linked up with the cobalt by means of a sulphur valency thus The sulphate loses 5H,O at 100'.Mnlonatodiethylenediaminecobultic salts YX wherei. 80 ABSTRACTS OF CNEMlCAL PAPERS. since if i t were linked through two oxygen atoms it would be red in colour. On triturating the semihydrate with hydrochloric acid a reddish-brown solution is formed from which orange-brown shinirig scales of the trihydrate YC1,3H20 can be obtained. The solution gives characteristic precipitates with potassium iodide acetic acid and sodium nitrite and with chloroplatinic acid. On trituration with fuming hydrobromic acid and subsequent gentle warming green crystals of tvans-dibromodiethylenediaminecobaltic homide are obtained. Both hydrates can be dehydrated at 105'. By double decomposition with potassium thiocyanate brownit-h-yellow shining needles or scales of the thiocyanate YSCN,ZH,O are obtained.The pkatinichloride Y2PtC1,,4H,O forms brown star-shaped crystals ; the aurichloride YAuC1,,3H20 crystallises in thin yellowish-brown shining scales. [With K. R. LANGE.]-Di~quodietiyler~ed~a~~~ecobakt~c salts YX where Y = H2° Co en2].-The salts of the cis-series are all much more soluble than the tmns-isomerides. The latter are remarkable in that by precipitation of their aqueous solutions with potassium iodide the tyans-hydroxoaquo-iodide is formed and not the diaquo- iodide which shows that in aqueous solutions the diaquo-salts are hydrolysed in accordance with the equation L 2 O [(H20) Co en,]X [< Co en2 X,+HX. 1 A number of salts have been prepared in addition t o those previously described (compare Abstr.1907 i 188). The cis-nitrate Y(N0,)B,H20 was obtained from ci.s-d1aquodiethylenediaminecobaltic bromide by the action of concentrated nitric acid at a low temperature. It forms red glistening plates and can bs dehydrated over calcium chloride. The cis-subhate Y2(S04) was prepared from the bromide by inter- action with silver sulphate and crystallises in red glistening needles. Other cis-salts could not be obtained. New methods of preparation of the cis-bromide are as follows (1) 10 grams of carbonatodiethylenediaminecobaltic bromide are mixed with 18 C.C. of cold water and 5 C.C. of concentrated nitric acid added drop by drop. The solution is neutralised with potassium hydroxide half as much again of the hydroxide added and then precipitated with sodium bromide (23 grams).(2) The hydroxo- aquobromide is triturated with a little concentrated hydrobromic acid and then washed with alcohol and ether. The dry product is dissolved in cold water containing a little hydrobromic acid saturated (at 0') hydrobromic acid added and the solution allowed to crystallise in a freezing mixture. The trans-?bitrate Y(NO,) was prepared from the tmw-bromide by a method similar to that used for the cis-salt. It could also be obtained by interaction with silver nitrate. It forms brownish-red needles. The trans-sulphate Y2(S0,) was obtained from the bromide by interaction with sulphuric acid as brownish-red leaflets. The trans- dithionnate Y2(S2O,) and the trans-thiocyanate Y( SCN),,& H 20 crys- tallise respectively as slender brownish-red needles and as dark brown plates. The iodide could not be obtained for the reason already given.ORCtANLC CHEMIH'I'RY.i. 81 Au account is given of the transformatioil of the diaquodiethylenc- diaminecobaltic halogenides into dihalogeoodiethylenediaminecobaltic salts on keeping for some time or on heating a t 105-115'. A number of h ydroxoaquodieth ylenedimiineco baltic salts YX [H,O Co en2 have been previously described (Abstr. where Y = 1907 i 189). They have been further studied because the different stereoisomerides may be obtained from the same starting material under conditions of reaction which are only slightly different from each other; thus in the former paper the cis-bromide was prepared from cis-dichloro-chloride (violeo-chloride) but i t is now shown that when the latter compound is dissolved in concentrated aqueous ammonia and the solution triturated with solid sodium bromide the trans-bromide YBr is formed.The trans- thiocpnate is reddish-brown in colour. When dichlorovioleo-chloride (5 grams) is dissolved in concentrated ammonia (25 c.c.) by heating on a water-bath the-solution then kept in a vacuum over phosphoric oxide until the odour of ammonia has disappeared and then precipitated with sodium bromide a bluish-red precipitate of cis-chloroammiizediethylenediamis~ecobaltic bromide Ho 1 [.,".' Go en,]Br is formed. The production of this compound is not due to the inter- mediate formation of the diaquo-bromide since this salt when dissolved in concentrated ammonia gives rise to the hydroxoaquo-bromide only.The trans-bromide may also be prepared by carefully heating the trans-nitrate with dilute ammonia (1 1) until crystals begin to form on the side of the dish. [ bTith R. B o s s n ~ ~ ~ . ] - T h e formation of carbonatodiethylenedi- aminecobaltic salts from the stereoisomeric hydroxoaquo-salts has been studied. I n all cases one and the same series of carbonato-salts was formed it being impossible to prepare stereoisomerides. The carbonato-salts were prepared by the actiori of carbon dioxide either on alkaline solutions or on aqueous solutions of the hydroxoaquo- salts. Dichlorotetramminecobaltic salts YX where Y = [Cl Co(NH?)J.- The constitution of the silver and bismuth salts described previous1 y (Abstr.1897 ii 264) must be altered to Co(NH,),-/U12and [:: CO(NH,),ICI,. A new method of preparation of the cis-chloride is given. Carbonatotetramminecobalt chloride is shaken up with a saturated (at 0') solution of hydrogen chloride in absolute alcohol until the evolution of carbon dioxide ceases. The greyish-blue reaction product which is a mixture of the cis- and trans-dichloro-salts after being washed free from acid with alcohol and dried is ext,racted with a small quantity of ice-cold water the cis-isomeride going into solution. The filtrate is immediately precipitated with sodium dithionate in order to obtain the violeo-dithionate from which the chloride and other salts can be obtained in the manner previously described (Abstr. 1908 ii 42). There is always a considerable loss of violeo- VOL. c11.i. 9i. 82 ABSTRACTS OF CHEMICAL PAPERS. salt owing to its ready transformation in aqueous solution into chloroaquo-salt. The preparation by means of aqueous hydrochloric acid cooled with liquid air was by no means so satisfactory. DichZorocliethyZenedia??ainecobccEtic salts YX where Y = [C12 Co eo2]X. -A new method of preparation of the riormai trccns-chloride is t o precipitate an aqueous solution of the acid chloride with solid lithium chloride. The trans-nitrite YNO is obtained as small green crystals by precipitation of an aqueous solution of the chloride acidified with acetic acid with sodium nitrite. When sulphuric acid is used as the precipitant green crystals of the trans-hydroyen sulphate YHSO are obtained.The addition of silver nitrate to a solution of the chloride cooled with a freezing mixture gives a precipitate consisting of greenish-white glistening leaflets having the composition [ "g;; co en ]2(:$)2.H2Q New methods of preparation of cis-dichlorodietbylenediaminecobaltic salts from carbonatodiethylenediarninecobalt chloride are given ; they are similar to those already described for the corresponding tetrammirie salts except that the product of reaction is washed with cold water to free i t from impuritiee than which the cis-dichloro-salt is less soluble. A characteristic cis-sulphate Y2S0,,2H20 is described ; it crystallises in small reddish-violet needles. [With L. GERB S. LORIE and Jos. RAP] POKT.] -Dibromodiethylene- cliaminecobaltic salts YBr where Y = [Br Co en2.]-Only the trans- isomerides have hitherto been prepared (by Jorgensen) for which new methods of preparation are now given,as follows ( a ) a solution of cobalt bromide in 10% ethylenediamine is oxidised by leading air t.hrough it and then evaporated to dryness.The residue is then repeatedly treated with hydrobromic acid and evaporated until a uniform green salt remains which consists of the acid bromide. On treatment with a little water the trans-bromide is obtained. (6) Carbonatodiethylene- diaminecobalt bromide is heated on the water-bath with a solution of hydrobromic acid (D= 1.49) until the solution is green. On cooling the acid bromide separates from which the normal bromide is best obtained by heating at 110" until it no longer gives an acid solution.The trans-thiocyanate Y SCN is precipitated as a canary- green crystalline salt by the addition of potassium thiocyanate to a solution of the trccns-bromide. The methods for the preparation of the cis-bromide YBr are as follows (1) a solution of the trans-bromide is evaporated on the water-bat'h several times to a syrupy consistency. On keeping in a vacuum desiccator black crystals are then obtained which give a greyish-violet powder ; they consist chiefly of the cis-isomeride mixed with a little of the trans-isomeride. The latter can be extracted with a small quantity of water leaving the cis-form which can be purified by solution in water and precipitation with sodium bromide. (2) By fission of tetraethylenediaminedioldicobaltic bromide with concentrated hydrobromic acid into diaquo- bromideand therequireddibromo-bromide. The diaquo-salt is removed from the mixture by solution in absolute alcohol.(3) From carbonatodiethylenediaminecobaltic bromide by treatment with an alcoholic or aqueous solution of hydrogen bromideORGANIC CHEMISTRY. i. 83 by a method similar to that described for the correspouding dichloru- salts. The cis-bromide YBr forms scaly crystals possessing a colour. and glance similar to that of graphite. By double decomposition with the appropriate salts of the alkali metals the following compounds were prepared. The cis-iodide YI is similar in appearance t o the bromide ; the cis-nitrate YNO forms small gi eyish-viole t crystals as also does the cis-thiocyanate PSCN,H,O; the crystals of the cis- dithionute Y,S,O are somewhat lighter in colour than those of the other salts.Ch ZorobrorrLocliet?~.1/lenediu~i~~ecobctltic sul ts. Y X. where Y Y = rB c1 co enJX. L _I -Both the cis. and trans isomerides have been prepared ; the former are readily obtained pure the latter only with difficulty since they are generally mixed with trans-dibromo-salts. Two methods of pre- paration are given ( 1 ) Two grams of chloroayuodiethylenediamine- cobaltic bromide are covered with 2 C.C. of concentrated hydrobroulic acid and the mixture heated until complete solution takes place. On cooling a mixture of the green aod violet salt is obtained which is washed with alcohol and ether dried and then treated with a srriall quantity of water to dissolve out the green salt. The violet salt (cis-isomeride) is collected washed with water and alcohol and dried.The green filtrate gives precipitates kith metallic salts which give aualytical results corresponding with a mixture of dibromo- and chlorobromo-salts. (2) Chloroaquodiethylenediaminecobaltic bromide is heated for two hours a t l l O o whereby a ruixture of the cis- and tmns-chlorobromo-bromides is produced. This is separated as in (l) the trans-nitrate being precipitated from the green filtrate by ammonium nitrate. The trans-nitrate YNO forms small light green glistening leaflets. The trans-dithionate Y2S,0,. and trans-tJhiocyunute Y SCN are prepared from the green filtrate mentioned above by double decom- position with the appropriate alkali salts ; they form respectively glistening green flat crystals and a light green precipitate.The cis-bromide Y Br,H,O is a greyish-violet microcrystalline salt ; the cis-nitrate YNO forms dark violet needles and the cis-dithionate Y,S,O small violet leaflets. When the cis-bromide is gently warmed with concentrated hydro- bromic acid until a solution is formed i t is changed into trans- di bromodie t by I enediaminecobal tic bromide which is deposited on cooling in cauary-green crystals. [., c o en2 ~ . - - ~ n l y €IuZogenoaquodiethyZenediunainecobaltic sal ts the cis-isomerides have so far been obtained ; t h e cold aqueous solu- tions are fairly stable but on heating complicated changes take place. By the action of concentrated aqueous ammonia on the chloro- aquo- and bromoaquo-bromides hydroxochloro- and hydroxobromo- bromides are Obtained.1 cis-OhZoroaqzcodietrllylenediami?L~cobaZtic salts YX where Y = [H20 co en2 . Ii. 84 ABSTRACTS OF CHEMlCAL PAPERS. -The sulphude YS04,1$H,0 is prepared by heating 20 grams of trans- dichlorodiethglenediaminecobaltic chloride with 20 C.C. of water until a deep blue solution is obtained. After cooling and keeping for one hour ammonium sulphate (10 grams) is added ; on keeping for a further twelve hours bluish-red crystals of the sulphate are deposited mixed with some green crystals which can be removed by shaking with a little cold water. The sulphate dissolves in concentrated ammonia and the solution gives a bluish-red precipitate of chloro- amrninediethylenediamifiecobaltic bromide with concentrated hydro- bromic acid.The chloride YCI and the bromide YBr,,H,O are obtained from the sulphate by interaction,with the respective halogen acids. The former is microcrystalline and the latter forms small crystalline leaflets ; both are reddish-violet in colour. The bromide- nitrate YBrN03 prepared from the bromide and lithium nitrate is reddish-brown in colour. The mitrite Y(NO,) from the chloride and sodium nitrite gives dark violet micro-crystals. It is unstable changing to cis-chloronitrodiethylenediaminecobaltic nitrite. [With R. ~ ~ ~ ~ 1 1 ) ~ . ] - ~ ~ ~ - ~ r o n z 0 a q w 0 d i e t ~ ~ y ~ e n e d ~ a m ~ n e c o h salts YX where Y = LH$ Co en2].-The following methods are given for the preparation of the 6romide YEr2,H,0. (1) A solution of neutral 1 6-dichlorodiethylenediaminecobaltic chloride containing nitric acid is heated with a concentrated solution of silver nitrate until it assumes a Bordeaux-red colour.After collecting the silver bromide the filtrate is saturated with sodium bromide first filtering off any more silver bromide which may be formed. After a few hours the bromide has deposited as a violet microcrystalline powder. (2) A concentrated solution of the tyans-dibromo-bromide is heated a t 40" until it becomes violet in colour; after cooling it is saturated with sodium bromide. Any green crystals of praseo-bromide which are precipitated with the bromoaquo-bromide are removed by fractional solution in ice-cold water the praseo-bromide being the lesser soluble salt. (3) A solution of trans- di bromonitrate is treated similarly to t h e dibromo-bromide except that it is heated over the bare flame.(4) The carbonato- chloride or bromide is treated with concentrated hydrobromic acid (D i= 1.4). The bromoaquo-bromide is separated from the less soluble cis-dibromo-bromide which is formed at the same time by fractional solution. ( 5 ) cis-Diaquo-bromide is heated at 40' with j u s t enough water to give complete solution until a violet-coloured solution is obtained ; the bromoaquo-salt is then precipitated with sodium bromide. The bromide forms dark violet leaf-like crystals. By double decomposition with sodium nitrate and sodium nitrite respectively i t gives the nitrate Y(NO,),,H,(? and nitrite Y( NU,) as bluish-violet crystalline powders. it gives a yellowish-green tetranitrodiarnminecobalt compound.When triturated with Erdmann's salt H3)21 H49 Bydroxohalogeno-salts rHg Co A41 X.- I~y3roxochZorotetrccmmirne- L -I cobccltic drthiorbate [H Co (NHJ4] S206 is precipitatetlas a violet-blue 2ORGANIC CHEMISTRY. i. 85 salt when solid chloroaquotetramminecobal tic chloride is dissolved in a saturated solution of sodium dithionate in concentrated ammonia ammonium dithionate remaining in solution. The colour corresponds with that of the cis-dichlorotetrammine salts. The corresponding hydroxocr3Llorodiethylenetliccminecobalt~c bromide rH2 Co en Br is obtained as a brownish-violet crystalline paste when chloroaquo- diethylenediaminecobaltic bromide is treated with concentrated ammonia ; when heated with concentrated hydrogen chloride this salt gives a mixture containing a little 1 6-dichloro- with much 1 2- dichloro-diet h ylenediaminecobal t ic chloride. cis - Hyd~oxo bromodiethyl- eraediurninecobattic bromide ri Co en,]Br is similarly obtained as a brownish-violet salt from the bromoaquo-bromide and ammonia. When warmed with a little water addition takes place with the formation of the cis-hydroxoaquo-bromide ; similarly when triturated with concentrated hydrobromic acid the cis-diaquo-bromide is obtained .I Chloroisothiocyanc~todieth~llenediaminecobaltic salts Y X where Y = rScN c 1 Co en,l.-A few of the trans-isomerides which were howe& impure Gave been described previously (Abbtr. 1900 i 86). The trans-thiocyanate YSCN is obtained by precipitating a solution of 1 6-dichlorodiethylenediaminecobaltic chloride with potassium thio- cyanate. The precipitate consists of a mixture of about two-thirds of the trans- and one-third of the cis-isomeride.By appropriate treatment the pure trans-isomeride is obtained as sparingly soluble violet leaflets. When trituixted with hydrobromic acid it gives glistening bluish- violet crystals of the trans-bromide YBr,2H20. This salt may also be prepared from praseo-chloride (Abstr. 1907 i 291). With sodium dithionate it gives bluish-violet glistening crystals of the trans- dithionate Y2S206 and with perchloric acid violet leaflets of the trans-perchlorate YC10,. The perchlorate may also be obtained directly from the trans-dichlorothiocyanate and perchloric acid. The trans-isomerides dissolve readily in liquid ammonia giving red- dish-yellow solutions which deposit mixtures of the stereoisomeric iso- thiocyanatoammine salts.If the trans-perchlorate is boiled with sodium nitrite in concentrated aqueous solution until a reddish-brown colour is obtaiued the solution cooled and ammonium thiocyanate added an isomorphous mixture of the 1 6-chloroisothiocyanato- and 1 6-nitroisotgiocyanato-thiocyanates is precipitated. If the solution is boiled until brown in colour small quantities of the cis-nitroiso- thiocyanato-salt crystallise ou cooling. On heating a solution of tmns- chloroisothiocyanato-bromide with potassium thiocyanate and cooling needles of the trans-diisothiocyanato-thiocyanate separate and from the mother liquor small quantities of the cis-isomeride can be obtained; oxidation of the trans-salt with hydrogen peroxide gives the ty-ccns- diztmrnine salt.Or1 boiling a concentrated solution of the trans-chloroisothiocyanato- bromide (1 mol.) with silver nitrate (3 mols) filtelring from silver bromide and cooling light violet slender needles of an additive com-i. 86 AI<Sl'RAC'I'S O F CHEMICAL PAPERS. pound [hpSCN C1 Co en,](NO,) are obtained. On hoiling the aqueous solritiori of this salt silver chloride is slowly precipitated. cis-Chloroiso~hiocyanatodiethylenediaminecobaZt~c chloride YCI is obtained in the purification of the trans-thiocyanate in the form of bluish-red needles. It is purified by transformation into the per- chlorate and precipitation of the solution of this salt with concentrated hydrochloric acid.By double decomposition of a solution of the per- chlorate with the appropriate salts of the alkali metalcr the following compounds were obtained cis- Dithionate Y,S,OG,H,O brownish-red needles ; cis-nitrate YNO dark bluish-red needles ; cis-sulphate Y,SO violet-red powder. The cis-bromide Y Br,l-$H,O mas obtained from the chloride by interaction with hydrobromic acid. A method of preparation of the cis-chloride from cis-isothiocyanatonitro-chloride by interaction with hydrochloric acid is also given. The action of hydrogen peroxide liquid ammonia potassium thiocyanate sodium nitrite and silver nitrate on the cis-salts is fully described. Rro~zoisothioc~anatodieth ylencdiccminecoballic salts Y X where Y = LsEg Go en2].-Both series of isomerides are known but the cis- salts are difficult t o isolate since in aqueous solution they are readily trau sformed into aquo-sal ts.The trans-isomerides on oxidation wit b hydrogen peroxide under certain conditions give 1 6-bromoamine s;tlts and under other conditions 1 6-dibromo-salts. Hydrogen peroxide completely oxidises the thiocyannte residue of the cis- isouierides but if the aqueous solution is kept some time before hydrogen peroxide is added a salt of the aquo-series is formed which then gives rise t o the bromoamrnine salt. With ammonia both isomerides give a mixture of cis- and trans-isothiocyanatoammine- diet h ylenediami D ecobaltic salts. The trans-thiocyanate YSCN is prepared from 1 6-dibromo- diethylenediaminecobaltic bromide by precipitation with potassium thiocyanate.The green precipitate and mother liquor are heated until R deep red solution is obtained. On cooling and further addition of potassium thiocyanate green glistening needles of the required salt are obtained. Trituration with concentrated h ydrobromic acid gives dark blue prismatic crystals of the trans-bromide YBr 2H20 and pre- cipitation with perchloric acid the trans-perchlorate YCIO as dark blue almost black slender needles. The trans-dithionats Y2S,0 forms violet-blue leaflets. Three methods of preparation of the cis-bromide YBr are fully described namely from 1 6-dibromodiethylenediaminecobaltic bromide 1 2-aquoisothiocyanatodiethylenediaminecobaltic dithionate and 1 2-nitroisothiocyanatodiethylenediaminecobaltic sulphate. It forms garnet-red .glistening prismatic crystals and is used as a source or' preparation of the other salts by methods involving double decomposition. The cis-nitrate YNO is violet-brown in colour the cis-dithionccte Y,S,O brownish-red whilst the cis-sulphate Y,SO gives reddish-lilac silky thin leaflets.ORGANIC CHEMISTRY. i. 87 isoTliiocyanatoaquodiethylenediamin2ecobaltic salts Y X where L L -Both series of isomerides have been obtained whereas with all other acidoaquo-salts it has been possible to prepare one series only either the cis- or trans-. The salts of the cis-series are yellowish-red t o crimson in colour whilst those of the trans-series are violet; the former are obtained from the stereoisomeric chloroisothiocyanato-salts by the action of concentrated ammonia and the latter from the same salts by the action of potassium hydroxide.The cis-dithionate YS,O,,H,O is prepared by warming 1 6-chloro- isot hiocyao atodie t h y 1 ened iamineco bal tic bromide with concentrated ammonia until a red solution is formed. The cooled solution is then poured into absolute alcohol the precipitate dried on a porous plate dissolved in cold water and glacial acetic acid added to the solution until a precipitate begins to form. On further keeping orange-coloured needles of the dithionate separate. With potassium thiocyanate the solution gives R crimson precipitate of the cis-thiocyanate Y(SCN),. With hydrogen peroxide the dithionate gives a mixture of the cis- and trans-chloroammine salts ; with concentrated hydrochloric acid cis- chloroisothiocyanato-salts ; with nitrous acid cis-nitroisothiocyanato- O N diethglenediaminecobaltic dithionate SbN Co en,1,S2O6 in the form of L slender yellow needles ; with potassium thiozyanate cis-diisothio- cyanato-salts.With silver nitrate and perchloric acid an orange- coloured additive product LAgScN Co en,]gA:)2,2H2O is obtained. The trans-bromide YBr2,2H,0 is prepared as follows 1 6-chloro- isothiocyanatothiocyanate dissolves in potassium hydroxide to a red solution ; on cooling brownish-red leaflets of 1 6-hydroxoisothio- cyanccto-thiocyanat e [sEgCo en,]SCN,H,O separate. These are dis- solved in a little water excess of concentrated hydrobromic acid added and the solution kept over sulphuric acid in a desiccator. After a .few days dark red crystals of the required bromide separate.From this salt by the method of double decomposition the trans-thio- cyanate Y(SCN),,H,O is obtained as a violet precipitate the trans- nitrate Y(NO,),,H,O as bluish-red needles and the trans-nitrite Y(NO,) as dark violet-red crystals. On the addition of excess of silver nitrate to a well-cooled solution of the nitrate bright red H24 - needles of an additive product [Ag,$$ Co en,](NO,),,H,O are deposited. On oxidation with nitric acid or hydrogen peroxide and subsequent evaporation with concentrated hydrochloric acid the trans-aquoiso- thiocyanato-salts give only trans-chloroamrnine salts. When solid sodium nitrite is added to a concentrated solution of 1 6-isothiocyanatoaquo-nitrate acidified with a few drops of acetic acid a bright red precipitate of 1 6-nitritoisothiocyanatodiethyZ~ne- diaminecobdtic nitrite PNO,,H,O where Y = [tzi Co en,] is88 ABSTRACTS OF CHEMICAL PAPERS.produced ; with potassium thiocynnate the solution gives red needles of the 1 6-thiocyanate YSCN. ChloroamminediethyZenediaminecobcLEtic salts YX where Y = LH- Co en,].-The isomerides of this series are best distinguished by means of the dithionates ; the cis-dithionate forms thick crystals whilst the trans-dithionate crystallises in long glistening needles. Both series of salts are bluish-red in colour. The trans-salts react very quickly with liquid ammonia forming diammine salts whereas the cis-isomerides are scarcely acted on. Jorgensen has already prepared a number of the cis-isomerides. The best method of preparation f o r the cis-chloride YCI is the trituration of 1 6-dichlorodiethylenediaminecobaltic chloride with concentrated ammonia. The green salt first dissolves and then a red paste of the required chloride separates.The addition of solid sodium perchlorate t o a solution of the chloride precipitates long red prisms of the cis-chloride-perc72lorale YCl( (310,) ; on recry stallisation from concentrated hydrochloric acid it is transformed into the chloride. The cis-nitrite Y (NO,) forms brick-red crystals. The actions of sodium and silver nitrites of potassium thiocyanate and of liquid ammonia on the cis-chloride are fully described as also the changes which aqueous solutions of the cis-nitrite undergo on warming. To prepare the tram-chloride YCl,,€I,O 1 6-chloroisoLhiocyxnato- diethylenediaminecobaltic thiocyanate is oxidised with hydrogen peroxide in aqueous solution acidified with sulphuric acid. Precipita- tion with hydrochloric acid then gives a chloride-sulphate which is recrystallised from hydrochloric acid several times and the aqueous solution then precipitated with barium chloride to remove the sulphuric acid.It forms bright ruby-red prisms. It may also be prepared from 1 6-nitroammine salts by heating with concentrated hydrochloric acid and from 1 6-dichloro-salts by the action of a methyl-alcohol solution of ammonia. The trans-chloride-perchlorate YCI(ClO,) is prepared from 1 6-chloroisothiocyanatodiethylene- diaminecobaltic perchlorate by a method similar to that used for the chloride; it forms bright red glistening leaflets or flat needles.The trans -chloride hydrogen sulphate Y C1( H SO,) is obtained by repeated evaporation on the water-bath of 1 6-nitroamminedithionate with hydrochloric acid ; it crystallises in thick ruby-red plates. The trans-dithionate YS,O H20 crystallises as bright red slender needles when sodium dithionate is added to a solution of the chloride- perchlorate. The dichomate nitivate and nitvite have also been obtained. The actions of sodium and silver nitrites of potassium thiocyanate and of liquid ammonia on the trans-chloride-perchlorate a r e fully described as also the changes which aqueous solutions of the trans-nitrite undergo on keeping or on warming. Bromonrnminediethylenedi~n~inecobaltic salts YX where Y == Co en2].-Both series of isomerides have been prepared the cis-isomerides being the mom easily obtained.The determination of their configuration depends on the formation of the trans-isomerides from ‘trans-bromoisothiocjanato-sal ts by oxidation with hydrogen IORGANIC CHEMISTRY. i. 89 yaroxide. Both series are very similar i n colour. The cis-dithionate iorms short compact crystals whilst the trans-isomeride gives long slender needles ; also the former E a l t readily dissolves in concentrated hydrobromic acid with the formation of the bromide whereas the latter is unaltered. [With W. E. BoSs.1-The cis-bromide YBr2,2H,0 is obtained when moist 1 6-dibromodiethylenediaminecobaltic bromide is treated at a low temperature with ammonia (1 l) drop by drop until the green colour changes to a dark violet.At higher teu-peratures the diammine- salt is produced owing to the addition of a further molecule of ammonia. When recrystallised from water it forms bundles of reddish-violet glistening needles ; when precipitated from tbe aqueous solution by the addition of concentrated hydrobromic acid the anhydrous salt YBr is obtained as dark brownkh-red prisms or needles. It may also be prepared (1) by the action of ammonium bromide on tetrae thylenediamin ediaquotetrold icobal ticobn 1 tous sulphate and (2) by the action of hydrobromic acid on 1 2-nitroamminediethylene- diamiuecobaltic salts or on 1 2-aquoamminediethylenediaminecobaltic salts. By appropriate double decomposition the following salts were obtained cis-homide-nitrate YBr(N03) as reddish-violet crystals ; the cis-dithionate YS,O as reddish-violet thin leaflets ; the cis- pbatinochloride YPtCl as reddish-brown leaflets.The cis-nitmte Y(NO,) mas obtained from the bromide by trituration with concentrated nitric acid a s dark reddish-violet long rectangular columns. The trans-dithionate YS,O is obtained from 1 6-brornoisothio- cyanatodiethylenediaminecobaltic bromide by oxidation a t 50' with hydrogen peroxide in aqueons solution acidified with acetic acid and subsequent precipitation with sodium dithionate. It forms bluish rose-coloured slender needles. With ammonium iodide the solution gives reddish-brown glistening flat needles of the trans-iodide Y12,H,0. The trans-bromide Y Br,,H,O was prepared from 1 6-aquoamminediethylenediaminecobaltic bromide by evaporation with concentrated hydrobromic acid on the water-bath.It forms large dark reddish-violet prisms and serves as the hource of the trans-nitrate Y(NO,),,H,O and the trans-perchlortcte Y(CIO,) the latter crystallising in violet needles. AqzcoamminediethyEenediamineco6altic salts YX where Y = [g$ co en . I1 -Both series of isomerides have been prepared. They are obtained by the action of potassium hydroxide or of freshly precipitated silver oxide on the. stereoisomeric chloroammine- and bromoammine-diethy he- diaminecobaltic salts. I n every case partial transformation takes place so t h a t a mixture of t h e isomerides is produced. The product of action of the alkali is an hydroxoammine salt the aquoauimine salt being produced when the solution is acidified Potassium hydroxide produces a greater relative transformation than silver oxide ; more trans- isomeride seems t o be produced a t low than at ordinary temperatures. The mixture of the isomerides is separated by taking advantage of the fact that the tmns-aquoammine-bromide iA much less soluble in dilutei.90 ABSTRACTS OF CHEMICAL PAPERS. hydrobromic acid than the cis-isomeride. The isomerides can be dis- tinguished from each other (1) by transformation into the chloro- amminedithionate ( q . ~ . ) by warming with hydrochloric acid and subsequent precipitation with sodium dithionate ; (2) by warming the aqueous solution to which sodium nitrite and R little acetic acid has been added t o 60-70'. A yellow solution is produced which on the addition of sodium dithionate gives an insoluble precipitate if the cis-isomeride is present or a precipitate which can be recrystallised from water if the trarts-isomeride is present.The trans-bromide YBr,,H20 forms pale brick-red needles and is used as the source of other salts methods of double decomposition being employed. The trans-iodide YI,,H,O forms brownish-red flat prismatic crystaIs ; the trans-nityate Y( NO,) crystallises in fire-red glistening prisms ; the trans-platinichloride Y2(PtCl,),,2H,O gives small dark brownish-rcd crystals and the trans-platinochloride Y,( PtCl,)3,2H,0 forms slender light brown crystals. The cis-bromide YBr,,H,O forms clumps of small red crystals. The diisothiocyamatodaethylenediaminacobaltic salts YX where Y = [( SCN) Co en,] bave already been described (compare Brauniich Abstr.1900 i 86). Their true configuration has now been deter- mined as follows. By violent oxidation with concentrated nitric acid and subsequent evaporation with hydrochloric acid the trans-isomerides give mainly trans-chloroammine salts together with some trans- diammine salts ; oxidation with hydrogen peroxide gives only the latter salts. Under the same treatment the cis-isomerides give respectively t?*ans-dichloro-salts together with a little cis-chloro- ammine-salt and cis-chloroammine salt. On oxidation with chlorine the trans-isomerides give trans-diammine salts and the cis-isomerides trans-dichloro-sal t s. [With C. R1x.1-A new method of preparing the cis-salts is as follows 1 2-nitrosoisothiocyanntodiethylenediaminecobaltic thiocyan- ate is evaporated with hydrochloric acid whereby pure cis-diiso- thiocyanatodiethylenediaminecobaltic chloride YCl,$H,O is obtained.The solubilities at 25' of the various salts in grams per 50 C.C. of water containing acetic acid are as follows chloride 0.2766 ; bromide 0.1996 ; iodide (at 24') 0.465 ; nitrate 0.1968 ; thiocyanate 0.1860. Stereoisomeric dinmminediethylemdiamirnecobaltic salts YX where Y = [(NH5) Co en,] have already been described (Abstr. 1907 i 290) but the wrong configuration has been assigned to them; those which were formerly charncterised as cis-compounds are now found to be the trans-isomerides and vice-versa. The evidence for this is based on their relation with the diisothiocyanato- and isothiocyanato-ammine- salts which has already been indicated and on the resolution of the cis-compounds into the optically active isomerides.The trans-salts are sparingly soluble whilst the cis-salts are readily soluble. A new method of preparation is described by the oxidation of the isothio- cyanatoamminediethylenediaminecobaltic salts with hydrogen peroxide in the presence of halogen acid. [With R. SAMANEK.]-M~X~UWS of the two series of salts have also been obtained by the action of liquid ammonia on the following com- pounds 1 6-dichloro- 1 6-dibromo- and 1 2-dibromo-diethylene-ORGANIC CHEMISTRY. i. 91 diaminecobaltic salts; 1 6-chlorormmine- 1 6- and 1 2-brumo- ammine-diethylenediaminecobaltic salts. The separation of the isomerides can be brought about by taking advantage of the fact that the bromide of t h e trans-series is only sparingly soluble in hydrobromic acid whereas the cis-bromide is readily soluble ; or better still by precipitation of concentrated solutions of the salts with sodium dithionate whereby the trans-dithionate is obtained it being practically insoluble in water ; from the mother liquor the cis-periodide is precipitated by the addition of a solution of iodine in hydriodic acid and by trituration of this salt with sodium thiosulphate the cis-iodide is obbained. I n all reactions leading to the formation of diammine salts the cis-isomerides are formed in preponderating amount.If the action of ammonia on the 1 6-dichloro-salts is not sufficiently energetic some 1 2-chloroammine salt is formed.isol’f~iocyanatoamminedietl~ylened~iacmilzecobccItic salts YX where Y = [E? Co en2 .-The two series of isomerides have been obtained and are very important because of their genetic relations with other series in the determination of configurations etc. A mixture of both isomerides is always obtained in their preparation no matter whether 1 2-chloro- 1 2-bromo- or 1 6-chloro- 1 6-bromo-isothiocyanato- diethylenediaminecobaltic salts are used to obtain them by inter- action with liquid ammonia. The relative proportion of the isomerides produced is not independent of the nature of the ionogenic radicle in the salt used. The cis- and trans-thiocyanates Y(SCN) are obtained by dissolv- ing 1 6-chloroisothiocyanatodiethylenediaminecobaltic thiocyanate in liquid ammonia and allowing the solution to evaporate a t the ordinary temperature. The residue is dissolved in water containing acetic acid and on keeping the trans-thiocyanate is deposited as slender glisten- ing reddish-orange needles ; the cis- thiocyanate is precipitated from the mother liquors by the addition of much potassium thiocyanate in the form of reddish-brown crystalline crusts. By appropriate double decomposition the following salts were obtained cis-dithionate YS206 brilliau t orange-red leaflets ; cis-iodide Y I short columnar reddish- brown crjstals ; trans-iodide YI,,H,O small brick-red prisms.The trans-bronzide-dithionate Y,Br,(S20,),2H,0 was prepared by trituratiou of the thiocyanate with hydrobromic acid and subsequent precipitation with sodium dithionate ; it forms brownish-red -prismatic crystals.With silver nitrate the cis-dithionate gives glistening yellow crystals I of an additive product [AgSCN H P Co eni]sg whilst the trans-per- chlorate prepared from the thiocyanate and perchloric acid gives yellow needles of the additive product [ Ag2f$g c0 (No3)4’ A detailed account is given of the amion of oxidising agents and of Botassium thiocvanate on the cis- and trans-isomerides. Nitmtoan~,minediethylencdian2inecobaltic salts Y & where -7i. 92 ABSTRACTS OF CHEMICAL PAPERS. are oh tained by the evaporation ol the stereoisomeric aquoammine- diethylenediaminecobaltic nitrates with concentrated nitric acid. I n the preparation of the trans-isomeride from the 1 6-aquoammine salt some cis-isomeride is formed a t the same time but the two are readily separated by taking advantage of the fact t h a t the cis-dithionate is almost insoluble in water.Their configuration is determined by evaporation with concentrated hjdroctrloric acid whirh gives the corre- sponding chloroarnmice salts. Liquid ammonia gives a mixture of the stereoisomeric diammine salts. The cis-nitrate Y(NO,),. forms small glistening,'orsnge-red crystals ; the cis-dithionate. YS,O H,O is an orange-coloured powder. The trans-dithionate YS,O crystallises in orange-coloured needles. [With W. E. Bo~s].-NitroammirLacliethylelnedia~ainecoballic salts YX where Y = [%3? Co en,].-Both series of isomerides have been prepared and are distinguished from each other by the fact that the cis-salts are much moi e soluble than the trans-salts this difference being especially marked in the dithionates.The configuration is best decided by evaporation of the salt t o dryness with hydrochloric acid solution of the residue in water and precipitation with sodium dithionate of the chloroamminedieth y lenediaminecobal tic di thionat e the cis- and trans-isomerides of which are very characteristic. The cis-bromide YBr,? is obtained by adding an excess of a saturated solution of sodium nitrite t o a saturated (at 25') solution of 1 2-aquoamminediethylen~di~minecobaltic bromide acidifying with acetic acid and warming a t 40' until the solution becomes orange-yellow in colour. After keeping for twenty-four hours a precipitate consisting of a mixture of the bromide and nitrite is deposited ; i t is dissolved in water and the solution saturated st 3 5 O with potassium bromide.On cooling large dark yellow plates of the bromide are obtained. The following salts were obtained from the bromide for the most part by the usual methods of double decomposi- tion. The cis-chloride YCI forms orange-yellow prisms or else a microcrystalline precipitate ; the &iodide Y 12 crystallises in reddish-brown needles ; the cis-nitrate P(NO,) in flat tabular or needle-shaped crystals. The cis-dithionate YS,O forms small golden- yellow leaflets whilst the cis-sulphate YSO crystallises in long radiating light yellow prismatic needles. %he cis-bromide-nitrate YBr(NO,) is prepared by the gradual addition of concentrated nitric acid to a well-cooled solution of the nitrate; i t forms large glistening reddish-brown prisms.The following methods of preparation of the cis-isomerides are also described (1) B y the action of silver nitrite on 1 2-chloroammine- diethylenediauiinecobaltic chloride. (2) By the action of ammonia on 1 6-diuitrodiethylenediaminecobaltic salts. (3) By oxidation of 1 2-nitroisothiocyanatodiethylenediaminecobaltic salts. The trans-nitrate Y (NO,),,&H,O is prepared by dissolving 1 6-nitronitratodiethylenediaminecobaltic nitrate in liquid ammonia and allowing the solution to evaporate spontaneously. The residue is recrj stallised from water whereby 8 mixture of large dark brown plates and small light yellow crystals is obtained which areORGANIC CHEMISTRY. i. 93 mechanwally separated. The latter crystals consist of 1 6 diuitro- nitrate whilst the former asre the required trans-nitrate and after further recrystallisation are obtained a s flat rhombic tablets.By appropriate double decomposition the nitrate yielded the following salts the trans-iodide Y 12,H20 as brown glistening prismatic crystals ; the trans-bromide YBr as thick short columnar or tabular dark brown crystals ; the trans-tl~iocyccszate Y(SCN) as thick glistening bro wnish-yellow plates ; the trans-dithionate as long glistening fluted prisms. This latter salt was also obtained from a solution of the trans-chloride prepared by the interaction of 1 6 - chloronitrodiethyleneditlminecobaltic chloride and liquid ammonia. The solubilities of the various trans-salts expressed in grams of salt per 10 C.C.of water at 27" are nitrate 2.827 ; thiocyanate 1.458; bromide (at 26O) 0.6867 ; iodide 0,7707. Nitroisotl~iocyanatodiethylenediumis~ecobultic salts YX where Y = [,.!$ Co en,].-The salts of the tyans-series are more easily soluble than the cis-isornericles the sulphates showing the greatest difference in solubility. There is also a marked difference in the colour of the salts the cis-compounds being bro wnish-yellow whilst the trans- compounds are dark brown. Hydrogen peroxide partly oxidises the cis-salts to cis-nitroammine-salts and partly oxidises the thiocyanate group completely away ; the tyans-salts under similar conditions give only trans-nitroaquo-salts the thio- cyanate group being split off completely. On heating with concentrated hydrochloric acid the cis-isomerides give the cis-chloroisothiocyanwto- salts whereas the trans-isomerides are not affected by the Bame treat- ment.On oxidation with nitric acid and subsequent evii.poration with hydrochloric acid the cis-salts give 1 6-dichloro-salts whilst the truns-salts give 1 6-chloronitro-salts. [With C. Rrx.]-The cis-chloi-ide YCl,H,O is obtained by intra- molecular transt ormation from 1 2-chloronitrodiethyleuediamine- cobaltic thiocyanate a solution of which in water containing acetic acid is evaporated to half its volume. The red colour changes to brown and on cooling brownish-yello w needles of the cis-chloride deposit contain- ing 2H20 but 1H,O is lost in a desiccator over calcium chloride. The chloride serves for the preparation of the other salts for the most part by the method of double decomposition.The cis-bromide YBr forms light brown nodular crystals ; the cis-iodide YI crystallises in brown prism ; the cis-sulphccte Y2S0 forms yellow glistening scales ; the cis-nitrate YNO forms brown thick crystals ; and the cis-thio- cyanate YSCN crystallises in brown leaflets. The cis-sulphate may also be obtained by heating a solution of cis-chloroisothiocyanato- diethylenediaminecobaltic chloride with sodium nitrite and subsequent precipitation with ammonium sulphate. The cis-thiocyaoate is also prepared by heating a solution of the cis-chloronitro-chloride with potassium thiocyanate. [With N. Gos~~~cs.]-The trans-lhiocyanccte YSCN i b obtained as YS,O,,H,? The following Ieactions are different in tlie two series.i.94 ABSTRACTS OF CHEMICAL PAPERS. brown prismatic crystals lien potahsiurrl thiocyanate ib i t d d d to a solution of 1 6-chloronitrodiethylenediaminecobaltic nitrate. Methods are also described for its preparation by the action of potassium thio- cyanate on nitratonitrocliethylenediaminecobaltic thiocyanate and on 1 6 -nitroa mm ined iet h y lened iam inecobal tic nitrate. The trans- chloride YCl,H,O is obtained as reddish-brown tabular crystals by dissolving the thiocyanate in conceu trated hydrochloric acid and precipitation with alcohol; the other salts are prepared from i t by appropriate double decomposition. The trans-bromide YBr,H20 forms brown tabular crystals ; the trans-iodide YI crgstallises in glistening brown irregular leaflets ; the trans-nitrate YNO,,H,O forms brown plates as also does the trans-nitrite YNO,,H,O.With silver nitrate the trans-nitrate gives long yellow needles of an additive compound rAg\yg c o en2] (NO,),. L Din~trotetram~inecobaltic salts YX where Y = [(N0,)2Co(NH3)4].- [With L. COHN.]-B~ the addition of rubidium nitrate to a solution of the cis-nitrate (flavonitrate) a rubidium double nitrate Y NO,,RbNO is obtained as brown rhombic tabular crystals. It is analogous with the potassium double nitrate already prepared by Jiirgensen. Dinitrodiethy Zenediarnineco baltic salts YX where Y = [(O,”) Co en,]. -A number of the stereoibomerides have been described previously a8 dinitrito-salts (Abstr. 1901,i,511) ; thetruedinitrito-salts wereprepared later (Abstr. 1907 i 291).It has been found that the cis-nitrate is transformed into the tvans-nitrate when its aqueous solution is heated. The cis-thiocyanate YSCM is obtained from the cis-nitrate by precipi- tation with potassium thiocyanate ; i t forms glistening yellowish- brown tabular crystals. The trans-thiocyanute YSCN forms orange- yellow glistening thick crystals. The trans-hydrogen sulphate 3-H SO has been prepared from the iodide by interaction with silver oxide and subsequent neutralisation with sulphuric acid ; it forms glistening yellowish-red needles. Stereoisomeric chloro~zitrodieth~lenediaminecobaltic salts have already been describe$ (kbstr. 1961 i 512). It has since been found that the trans-salts can be exposed t o the action 6f concentrated hydrochloric acid for a long time without effect whilst the cis-salts rapidly give 1 2- and 1 6-dichloro-salts. trans - Nitronitrutodiethylenediaminecobaltic salts YX where Y = [gig Co en2].-Only the nitrate YNO has been obtained.It is prepared by the oxidation of 1 2-dinitrodiethylenediaminecobaltic nitrate with concentrated nitric acid and forms glistening chamois- coloured crystals. By precipitation of the aqueous solution with concentrated nitric acid an ucid nitrute YNO,,HNO is obtained. trans - Nitroaquodiethylenediaminecobaltic salts YY where Y = [22E Co en,].-The sulyiiate YSO is obtained as follows 2.8 grams of solid ammonium sulyhate are added to a solution of 4 gramsORGANIC CHEMISTRY. 1. 95 of 1 6-nitronitl.ato-diethylenrdiaminecobaltic uitr:tte i i i 10 c.c. of water and then alcohol added until no further precipitate forms.It crystallises in orange-coloured needles. No other salts could be obtained owing to their great solubility. DichZoroethyZenedian~inediccmlninecobaltic salts YX where Y = C I C ~ en (NHJ2]. -Both series of stereoisomerides have been obtained. The method of preparation is briefly as follows By warming trinitrotri- amminecobalt with ethylenediamine trinitroethylenediamineammine- cobalt is obtained en (NO,),Co(NH,) + en = (NO,),Co NH + 2NH,. 3 By heating with concentrated hydrochloric acid the latter salt is transformed in to dic hloroaquoe t hy lenediamineamm inecobal tic chloride [gb co en ]GI of which 1 gram is then dissolved in 25% ammonia (34 c.c.). After five minutes 3.5 C.C. of concentrated hydrochloric acid are added to the solution which is then heated until i t becomes greenish-blue in colour.On cooling green crystals of the trans- cldoride YCI,&H,O are deposited from which by the method of double decomposition the following salts were obtained generally as green precipitates trans-nitrate YNO ; trans-iodide Y I ; trans- bromide YBr ; trans-thiocycmate Y SCN ; trans-lqdroge~i sulphate YHSO,,H,O ; trans-dithionate Y,S,O,. The iodide is sensitive to light. The cis-isomerides were prepared from the trans-compounds as follows By heating a solution of the trans-chloride with potassium carbonate until the colour bad changed to red and then cooling garnet- red crystals of carbonatoetlbylenedianzinediamminecobuZtic chloride NH3 p 3 c 0 (BNnHS)JC” were obtained.By treating this compound with concentrated hydro- chloric acid in the cold a solution of the required cis-chloride was obtained from which on the addition of ammonium bromide the cis- bromide YBr was deposited as a bluish-violet precipitate. The cis-dithionate Y,S,O is a violet precipitate obtained from a solution of the bromide by the addition of sodium dithionate. [With G. L~~D~N~~~~.]-~~ac~doditrirnethy~enediaminecoba~t~c salts [X,Co (tn)2]X.-Only the 1 6-dinitro- and 1 6-dichloro-salts have so far been prepared. The 1 6-dichloro-salts are distinguished from the corresponding diethylenediamine salts by their ready hydration (formation of aquo-salts) in aqueous solution. The neutral green solution of a dichloroditrimethylenediamine salt rapidly becomes violet in colour ; the addition of concentrated hydrochloric acid restores the green colour.Carbonate-salts have been prepared from the 1 6-dichloro-salts but could not be made to furnish the stereoisomeric 1 2-dichloro- salts. trans-Dinitroditrimet~yZenedia~ineco~aZ~ic salts YX where Y = [(NO,) Co tn,].1. 96 ABSTRACTS OF CHEMICAL PAPERS. -The niirite Y NO is obtai ued by heating potassium cobaltinitrite with trime t>hylenediamine in ;tqueous solution. I t forms large thick yellowish- brown pleochroic rhornbic crystals. YBr,H,O and the iodide YI,2H20 are .obtained from the nitrite by interaction with potassium bromide and iodide respectively the former as brownish-yellow monoclinic crystals and the latter as yellow t o yellowish-green pleochroic rhonibic prisms.The chlovide PCl,H,O and nitrate YNO are best obtained from the iodide by interaction with silver chloride and nitrate respeotively ; the former gives light to dark brown pleochroic monoclinic c r j stals and the latter rhombic plates. 1 6-Dic?~lorodit~irnethylenediaminecoba2tie chloride [CI Co tnJC1 is obtained by heating the diriitronitrite with hydrochloric acid ; a green solution i s obtained which on cooling deposits green prismatic columnar crystals. The solution is turned red by sodium hydroxide and ammonia and gives characteristic precipitates with the bromide iodide thiocy anate permanganate ferrocyanide ferricyanide or nitrate of potassium and with sodium thiosulpbate. Hydrogen sulphide precipitates cobalt sulphide- Potassium platinichloride gives green crystals of the plati&hIoride [Cl Co tn,],PtC16.Carbonatoditrimetf~yEenediaminecobaEtic chlorzde [CO Co tn,]CI,H?O was obtained by heating a solution of the 1 6-dichloro-chloride with sodium carbonate until i t became bluish-red in colour. The addition of alcohol precipitated a white salt and the red solution remaining deposited the required chloride in red needle-shaped crystals. By interaction with hydrogen chloride no matter under what conditions t h e green 1 6-dichloro-chloride was always obtained. The bromide T. S . P. Optically-active C a m p o u n d s of Cobalt and Chromium. ALFHED WEHNEH. (Arch. Sci. Phys. Nut. 1911 [iv] 32 457-467).- A general account is given of results which have for the most part been already published (Abstr.1911 i 613 S38 960; this vol. i lo). I n addition the author mentions that optically-active com- pounds r of the tetraet?rylerLediurnin,e-p-ccmino~eroxodicobalt and tetra- ethylewdiarnine-p-umino-ol-dicobuZt series have been obtained. The rotations of the compounds of the first series are very large the nitrate of the first series having a specific rotation of 840° which corresponds with a molecular rotation of about 6000'. From a consideration of the results hitherto obtained i t follows t h a t the sign of the rotation is not connected with the configuration of the diethylenediaminecobaltic radicle. This is well shown by the fact t h a t I-tetraethylenediamine-p-aminoperoxodicobalt salts furnish d-tetra- ethylenediamine-p-amino-ol-dicobalt salts on reduction Also I- chl oroisothiocy ana todiet hylenediaminecobaltic salts and d-chloronitrodiethylenediaminecobaltic salts both give rise to d-nitro- isothiocyanatodiethylonediamineoobaltic salts by interaction with sodium nitrite and potassium thiocyauate respectively.ORGANIC CHEMISTRY.i. 97 An examination of the compounds hitherto prepared shows that it is not always the isomeride of the same sign of rotation which gives the least soluble salt with d-bromocamphorsulphonic acid. W Q D 1. IJ. I. Preparation of Acid Chlorides from Two or More Molecules of Carbamide Chloride by Elimination of' Hydrogen Chloride. VEREINIGTE CHININFABRIKEN ZIMMEE & Co. (D.R.-P. .238961).-\Vhen carbamide chloride is heated in the absence of moisture either with or without a solvent two or more molecules condense with evolution of hydrogen chloride. Allophanic chloride NH,*ClO*NH*COCl a fuming colourless readily decomposable powder which reacts energetically with water according to the equation NH,-CO*NH*COCl+ H,O = CO(NH,) + CO + HC1 was thus obtained a t 30° whilst a t about 100' three molecules combined yielding bitwetcccrboxyl chloride C,H,N,O,*COCl a colour- less non-fuming powder decomposed by water with elimination of hydrogen chloride and carbon dioxide C,H,O,N,*COCl + H,O = HCl+ CO + NH,*CO*NH*CO*NH,. ETIENNE BOISMENU (Compt.rend. 1912 154 1482-1484. Compare Abstr. 1911 i 957)- The action of a n aqueous solution of hypochlorous acid on amides at 0' gives rise t o monochloro- or dichloro-amides according to the proportion of amide and of water employed.The dichloro-derivatives are yellow liquids the stability of which diminishes as the molecular weight increases. On treatment with amides they yield monochloro- derivatives. Acetyldichloroumide OH,*CO*NCI has an odour of chlorine and' is insoluble in water. It decomposes above O' depositing crystals of acetyl- chloroamide. Propio?-iyZdichZoroccmic~e and formyldichloroamide have also been prepared. The latter is very explosive and must- be kept in well cooled vessels (compare Mauguin hbstr. 1909 i 892). I?. M. G. M. Hypochlorous [ Acid and] Amides. w. 0. w. Cobalt Thiocyanates and the Cause of the Colour Changes in Cobalt Salts. ARTHUR HANTZSCH and YUJI SHIBATA (Zeitsch. anorg. Chem. 1912 '73 309-321).-Cobaltous thiocyanate is largely bimolecular in urethane solution at 49" but almost completely uni- molecular in alcoholic solution at 78".The existence of complex ions in the alcoholic solution is shown by the method used by Donnan and Bassett (Trans. 1902,81,944). The absorption spectra show the blue cobalt band and a broad band in the ultra-violet with its maximum at l/h 3400 and minimum a t l / X 3850. The absorption is slightly increased at 55" and 80'. Beer's law is departed from at considerable dilutions. The colour of the blue solution is attributed to the presence of the complex salt Co(SCN),Co in confirmation of which it is noted that the compound Co(SCN,)Me is blue. The salt Co(SCN),K is blue but its spectrum in absolute alcohol is practically identical with that of cobalt thiocyanate indicating dissociation into i t s components.Amy1 alcohol gives a n almost identical solution whilst moist ether VOL. CII. i. hi. 98 ABSTRACTS OF CHEMICAL PAPERS contains the salt in an almost undissociated condition. The action of alcohols in prornoting dissociation is attributed to the formation of the known alcoholates of cobalt thioceynnate. The deconiposi tion is still more pronounced in aqueous soltition but is lessened by the addition of potassium thiocyanate. The blue colour of cobalt thiocyanate is changed to pink by the addition of mercuric chloride or zinc chloride. The colour of the salt CO(SCN)~,H~C~ is not altered by further addition of mercuric chloride. This salt has not been isolated but when the alcoholic solution is evaporated with a turther quantity of mercuric chloride pink crystals of a compound 2Co(SCN),,3HgCl2 are obtained. The change of colour in cobalt chloride solution is also due to the formation of a compound [COCI,,(H~C~,)~]CO and not as assumed by Donnan and Bassett to (HgC1,)Co.The molecular weight of cobalt thiocyanate in aqueous solution shows that it only dissociates into two ions except in very dilute solutions whilst the chloride and bromide yield three ions even in concentrated solutions. It is therefore considered to exist in solution as the compound CO@'~) SCN. The whole of the colour changes may be explained as changes of the co-ordinative unsaturated complex COX into the saturated complex COX,. [ (H20),1 C. H. D. Systems Formed by Antimony Chloride and Bromide with Monosubstituted Benzene Hydrocarbons. BORIS N.MENSCIIUT- KIN (J. Russ. Phys. Chern. Xoc. 1911 43 1275-1302. Compare Abstr. 1911 i 273).-The author has subjected to thermal analysis the systems formed by antimony chloride and bromide with toluene ethylbenzene propylbenzene (see Abstr. 191 1 i 532) and isoamyl- benzene. The results are given in the form both of curves and of tables. Rosenheim and Stellmann (Abstr. 1902 i 68) state that antimony trichloride forms with toluene a cornpound having a composition analogous to that of the benzene compound namely SSbCll13,C,H,Me ; but this compound is really 2SbC13,CGH5Me the solid phase corresponding with 3SbC1 C,H,Me being antimony trichloride itself. The melting points of the thirteen compounds formed by tlte eight systems examined are as follows SbXc&jH,Et .SbX,-C,H,Pr . . BSbCI C6H,R. SbCl,,C,H,R. BSbRr C,H,R. SbRr3,C,H,R. . . . . .. . 42.5" 15-16" 38-39" 9" (ciccomp. ) (decomp.) (decornp.) 33 > > 1 ) > -15 9 ) 39.0" - . ...... 37.0 ....... 9-10 1 *5 - (decomp. ) (decornp.) SbX3-C&'C,Hl1 . . . 7 '5' - 20'5 - It will be seen that increase of the magnitude of the benzene sub- stituent is accompanied by decrease in the stability of the compounds formed with antimony trichloride and tribromide. The transition (p) and eutectic (e) points and the corresponding0 RG A N I C C H EM IS TR 1'. i. 99 o,iitions (rnols. of hydrocarbon per 1~01. of antiiuouy chloride) aru given in the following table 2SLC)& U,H,R- SbCl,,C,H,t~. 2SbC1,CtiH&-SbU1,. SbC1:3,C,H5R-SLC1,.-- Temp. Coinposition. Temp Composition. Temp. Composltlon. SbC1,-C H Me .. 11" 1.8 ( p ) 40.0 0.46 (e) - SbCI,-C:HiEt ..... 35 0'62 (c) 36.8 0.47 (e) 33" 0 5 2 ( c ) SbC1,-C,H5Pr ...... - - 8.5 0.88 ( p ) 1 0.98 ( e ) - SbC1,-CGH5*C5HIl. -33 3.1 ( p ) -21.0 1.3 (;u) - 5 1.2 (P) The transition points for SbBr3,C,H,R-SbBr are as follows Tein p. Composition. - - Sbtlr,-C,,H,Me ........ SbBr,-C,H5*C5H1 ...... - 17 5.07 This continual fall in the transition temperature again indicates diminution of stability of these compounds as the magnitude of the hydrocarbon increases. T. H. P. Systems Formed by Antimony Trichloride and Tri- bromide with Disubstituted Benzene Hydrocarbons. BORIS N. MENSCHUTKIN (J. Rum. Phys. Chsm. Xoc. 1911 43 2305-1328). -The systems here described contain 0- rn- or p-xylene or p-cymene.The results of the thermal analyses are given as curves and tables. The replacement of a second hydrogen atom of benzene by an alkyl radicle (compare preceding abstract) produces no change in the character of the system the temperature diagrams being similar to those given by the systems containing monoeubstituted benzenes. Also here too antimony chloride gives compounds of the two types 2SbCl,,C,H4R2 and SbC13,CGH4R2 whilst the bromide as a rule yields only one compound SbBr3,C,H4R2. The compounds are of approxi- mately the same stability as those formed with toluene or ethylbenzene. The results obtained with the three xylenes show that isomerism exerts a marked influence on the physical properties of these compounds.The melting points of the hydrocarbons and of the various com- pounds they form are given below the numbers for methylbenzene being inserted for purposes of comparison .$ bBr,-C H5E t ......... 29" 1.17 SbBr,-C,H,Pr ......... - 5 3'1 SbCI,-p-C,H,hIe ...... S ~ C I - ~ ~ L - C ~ H ~ M ~ J . . . . . S bC I,-C6H 5E t SbBr,-;u-C6€I,Me,. ..... SbRr,-wz-C,H,Mc ... SbBr,-o-CtiH,Me2 ...... SbEr,-C,H,Et ......... SbCI,-o-CGH,Me ...... ......... SbCl,-p-C,H,&IePrS ... SbBr,-p-C,EI,RlePiS . . Hydro- carbon. 2SbX,CGH,R DX. 14" 7 0" 56" - 57 38 95 - 93 33.5 62 5 - 93 37 130 - 75 40 115 14 67.5 53.5 - - - 57 - 29 - 93 - - - - SbX3,C,H4R,. Diff. 56" 4 2" 7.5 64.5 19.5" 48 "5 39 132 5-6 80 (decoinp. ) (decomp. ) - - 13.5 70.5 24 53 33 126 10 85 '1'. H. P. h 2 (cleconip.) (clacoml). )n. 100 ABSTRACTS OF CHEMICAL PAPERS. Relations of Trisubstituted Benzene Hydrocarbons to Antimony Trichloride and Tribrornide. BORIS N. MENSCHUTKIN (J. Buss. Phys. Chem. SOC. 1911 43 1329-1341).-11he systems formed by antimony trichloride and tribromide with 1 3 5- and 1 2 4-trimethylbenzenes (mesitylene and $-cumene) have been examined. Mesitylene forms compounds of the two types 2SbS3,C6H3Me3 and SbX,,C,H,Me with both antimony chloride and bromide and the same is the case with $-cumene. The only other benzene hydrocarbon with which this has been found to occur is toluene. The melting points of these compounds are as follows 2SbX C,H,Me,. SbX,,C6H,Me,. SbC1,-1 3 5-C,H3Me ...... 75.5" 43" (decoinp.) SbCl,-l 2 4-C6H,Me ...... 56'0 - 4 to -5" SbIh-1 3 5-C6H,Me ......69-5 38-39 SbBr3-1 2 4-C6H,Me 36.0 (decomp.) 13 2 9 ...... The eutectic points and the corresponding compositions are as follows System ... (1) C,H,Me,-SbX,,C,H,Me,. (2) 25 bX,,C,H,Me,-SbX,. r A -.c A \ M. p. of Com- hydro- Coni- M. p. of Temp. positiou. carbon. Tcinp. position. SbX,. SbC1,-1 3 5-C,H3Me - 55.6" 126.2 - 54.4" 58.5" 0.15 73" SbBr,-1 3 5-O6H,Me3 - 55'2 147.0 - 54'4 69.0 0.42 94 SbCI,-l 2 4-C,H3Me - 60.0 8'25 -57'4 51.0 0.27 73 SbBr,-1 2 4-C6HiMe - 58.8 28'4 - 57.4 - - - (Tha composition is given in niols. of liydrocarboii per mol. of SbX,.) The transition points SbX,,C,H31\le,-2SbX3,C6H,~~e~ are as follows Temp. Composition. SbC1,-1 3 6-C6H,Rle .............. 38" 1 *8 SbC1,-1 2 4-C,H3Me ...............- 5 1 *83 ShEr,,-l 3 5-C6H,Zle,.,. ............ 29 3 '45 SbBr,-1 2 4-C6H,Me ............... 7 1.72 Increase of the number of hydrogen atoms of benzene replaced by alkyl radicles does not diminish but rather increases the capability of these hydrocarbons to form compounds with antimony trichloride and tribromide. T. H. P. Electrolytic Reduction of Nitrobenzene. RALPH CUTHBERT SNOWDON (J. Physical Chem. 1911 15 797-S4P).-The author endeavoured to develop an electrolytic method of reducing nitro- benzene which should not require the use of a porous cup or a platinum anode. Nitrobenzene was vigorously stirred with ferrous chloride solution a t looo in a long cell provided with iron electrodes. The amount of anode iron dissolved was largely in excess of the electrolytic equivalent and dissolution of iron also occurred at the cathode in increasing proportion as the current density was lowered.With high current densities (10 amp./dm2) cathode corrosion was very small and theORGANIC CHEMISTRY. i. 101 yield attained 95% of aniline on the total iron dissolved. Although sheet iron in ferrous chloride solution will not reduce nitrobenzene on boiling it was found that under the emulsifying influence of rapid stirring the iron electrodes dissolved equally without electrolytic aid and gave a 78% yield of aniline calculated on the iron dissolved so that the commercial reduction of nitrobenzene by massive iron might be rendered possible by suitable agitation to bring the substances into intimate contact. The presence of a dissolved ferrous salt is essential in the electrolytic as in the chemical reduction. Ferrous chloride is apparently without action on nitrobenzene so that its catalytic activity must be attributed to a depolarising influence on the iron. I n this respect ferrous chloride and acetate are more efficient than the sulphate and benzoate.Nitrobenzene is reduced a t 100" by alkaline sodium sulphide freshly precipitated ferrous hydroxide and sodium arsenite but not by alkaline potassium ferrocyanide. Sodium arsenite gives 60-90yA of azoxybenzene 5-14% of aniline and a trace of azobenzene. This is contrary to electrolytic experience where azobenzene is produced above and azoxybenzene below 90'. Alkaline sodium sul phide and ferrous hydroxide give aniline and small amounts of azobenzene. The yield appears to vary with the order in which the three components nitrobenzene sodium hydroxide and reducing agent are mixed.Aromatic Nitro-derivatives. ROBERTO CIUSA ( A t t i R. Accccd. Lince& 1911 [v] 20 ii 523-524. Compare Abstr. 1911 i 931).- The observation of Werner (hbstr. 1910 i 20) that trinitro- mesitylene gives yellow solutions in some organic solvents although i t is not dissociated in formic acid solution indicates that there is no connexion between the dissociability of the aromatic nitro-deriv- atives and 'their power t o form additive products. The author now finds that tetranitromethane also is not dissociated in formic acid solution although it can form additive products. Xsomorphous Mixtures the Systems Chloronitrobenzenea- Bromonitrobenzenes. ROBERT KREMANN (Zeitsch.Kryst. Min. 19 1 1 50 86; from J ~ h r b . k.k. geol. Keichs. 1908 58 659-672).-The time-cooling curves and the freezing curves of t h e three systems (ortho meta para) show that the crystallisation interval for mixtures of the ortbo-series is very small; that of the meta-series is also small but it is larger in ihe para-series. The fusion curves of the two last systems belong to Roozeboom'e type V. 1-Bromo-2 4 6-tri-iodo-3 5-dinitrobenzene and Some of its Derivatives. U. LORING JACKSON and HAROLD E. BIGELOW (Amer. Chem. J. 1911 46 549-574).-1t has been shown by Jackson and Robinson (Abstr. 1890 377) that 1 :3 :5-tribromo-4 6-dinitrobenzene is converted by ethyl sodiomalonate into ethyl 3-bromo-4 6-dinitro- phenylmalonate.It has now been found t h a t when 1-bromo-2 4 6-tri- iOd0-3 5-dinitrobenzene is treated with ethyl sodiomalonate a t the ordinary temperature 1 -bromo-2 6-di-iodo-3 5-dinitrobenzeno and ethyl ethanetetracarboxylate are produced whilst if the mixture is R. J. C. R. V. S. L. J. S.i. 1 0 2 ABSTRACTS OF CHEMICAL PAPERS. heated ethyl 2-bromo-3-iodo-4 6-dinitrophenylmalonate is obtained. This shows t h a t the explanation given previously (Jackson and Moore Abstr. 1890 497; Jackson Abstr. 1890 983) is not correct but t h a t it must be assumed t h a t ethyl sodiomalonate reacts in the enolic form and t h a t the iodine atom and the *C,BrT,(N0,)2 group are added a t the double bond with production of the compound C0,Et *CHI*C( OEt) (ONa) *C,I,Br( NO,),.On acidification tbe hydrogen of the *OH g ~ o u p might combine with the substituted phenyl group with formation of the compounds C,HBr12(N0,) and CHI(CO,Et) ; the latter would then react with the excess of ethyl sodiomalonate to produce ethyl ethanetetra- car box yl a te. 1 -Bromo-2 4 6-tri-iodobenzene C6H2Er13 130. p. 146O obtained by treating a mixture of 2 4 6-tri-iodoanilineY glacial acetic acid and hydrobromic acid with sodium nitrite crystallises in pale yellow needlec and when heated with fuming nitric acid is converted into 1-b7.orno-2 4 6-tri-iodo-3 5-dir~itrobenxene~ C,BrI,(NO,) m. p. 292' which forms white needles. When tri-iodoaniline containing dnrk- coloured impurities was employed the crude 1-bromo-2 4 6-tri-iodo- benzene yielded on nitration some 1 3-dibromo-2 :4 6-tri-iodo-5-nitro- benzene C,Br21,*N02 m.p. about 256' (decomp.) which crystallises in hexagonal prisms. 1-Bromo-2 6-di-iodo-3 5-dinitrobenxene C,HBr12(N02) m. p. 187' crystallises in straw-coloured needles. Ethyl 2-bronzo-3-iodo-4 6-di- nitrophenylrnalonate CGHBrI( NO,),*CH( CO,Et) m. p. 107" forms btout lemon-yellow crystals. A small quantity of another cot)ipound m. p about 250' (decomp.) was also isolated from the product of the reaction between ethyl sodiomalonate and 1-bromo-2 4 6-tri-iodo- 3 5-dinitrobenzene. By the action of sodium ethoxide on 1-bromo-2 4 6-tri-iodo-3 5-di- nitrobenzene 3-bromo-3 4 6-tri-iodo-5-uitr~ph~netoZe CGBr'T3( NO,).OEt m. p. 14S0 is obtained which crystallises in light pink needles and is reduced by zinc and acetic acid to m-aminophenol.3-Bromo-2 4 :6-tri- iodo-5-nitroccnisoZe C,BrJ3(N0,)*OMe m. p. 163' forms pale yellow needles. When 2-bromo-l 3 :5-tri-iodo-4 6-dinitrobenzene is heated with zinc and acetic acid 5-bromo-nz-phenylenediamine is produced hut on reduction with ferrous hydroxide i t is converted into 1-byorno- 2 4 6-tri-iodo-m-phenyZenediarnine C,Br.I,(NH2)2 m. p. 187' which forms stout greyish-white needles and yields a hydrochloride decomposing at 100'. Reduction experiments have been carried out with several other iodo-compounds. Zinc and acetic acid remove iodine from 1 3 5-tri- iodo-4 6-dinitrobenzene. 2 4 6-Tri-iodoaniline is not affected by tin and hydrochloric acid and only very slightly by zinc and acetic acid.1-Bromo-2 4 6-tri-iodobenzene is reduced by zinc and acetic acid with formation of p-iodobromobenzene. These experiments show t h a t iodine is more easily replaced by hydrogen than is bromine. Sodium ethoxide does not react with 2 4 6-tri-iodobenzene and only very slightly with 1-bromo-2 4 6-tri-iodobenzene. E. G.ORGANlC CHEMISTRY. i. 103 Preparation of Alkylamines by Catalysis. PAUL SAUATIER and ALPEIONSE MAILHE (Compt. rend. 1911 153 1204-1208. Compare Abstr. 1909 i 292; 1911 ii 627).-An extension of the general reaction already described to the preparation of new amines. isoPropyl alcohol is transformed into isopropylamine when its vapour mixed with ammonia is passed over thorium dioxide at 250' ; the yield is 20%. A t higher temperatures propylene is formed together with diisopropylamine.The reaction proceeds with difficulty in the case of diphenplcarbinol. A t 280' the corresponding amine is obtained but the chief product is tetraphenylethylene ; this substance is easily obtained a t 300' in absence of ammonia. cycloHexanol and also its 2- 3- and 4-methyl derivatives yield the primary and secondary amines at 290-320'. 4'-Methylcyclohexyl- arnino-4-rneth,ylcyclohexane (C,H,,Me),NH b. p. 275" (decomp.) forms a phenylcnybamide m. p. 181'. The following secondary amines were prepared by passing a mixture of cyclohexylamine and an alcohol over thorium dioxide a t 320'. Ethyl- aminocyclohexane CGH,,*NHEt. Propylaminocyclohexane b. p. 185' ; the phenylcai*bamide has m. p. 113'. iso Butylccminocyclohexan~ b.p. 193" ; the phenylcarbamide has TU. p. 90". i8oAmylaminocyclohexano b. p. 205' ; the phenylcarbamide has m. p. 129'. Benxylaminocyclo- hexane b. p. 195'/80 mm. the phenylcnrbamide has m. p. 121'. cycloHexyZamino-2-methylcyclohe~:ane b. p. 260' with slight decom- position ; the hydrochloride has m. p. 182' and the phenylcarbamide m. p. 140'; the 3-methyl derivative b. p. 270' (decomp.) forms a hydrochloride m. p. 197" and a phenylcnrbamide m. p. 191' whilst the 4-methyl derivative b. p. 2?0' gives a phenylcarbamide m. p. 108'. The yield of the latter was 20%; the lowest yield mas obtained in the Behaviour of Nitrosomonoarylcarbamides towards Primary Amines and 'Phenols. J. HAAGER (Monatsh 1911,32,1089-1102). -Nitrosomonoarylcarbamides condense in alcoholic solution with primary aromatic bases t o diazoamino-compounds which contain the aromatic nuclei of both components and to arylcarbamides which contain the nuclei of the bases.Accordingly the rest of the carbamic acid and not the nitroso-group is eliminated from the nitrosocarbamides. The change is the same when the mixture of the components is heated. Nitrosoarylcarbamides react also with alkaline and with alcoholic solutions or phenols and their derivatives with the formation of hydroxyazo-compounds and alkaline salts of cyanic acid which have been formed by the elimination of -CO*NH from the nitroso- car bamides. Nitrosophenylcarbamide reacts with aniline t o form diazoamino- benzene and phenylcarbamide ; with p-toluidine benzenediazoamino- toluene m.p. 85' and p-tolylcarbamide are obtained. Nitroso-p- tolyl- carbamide and aniline yield the same compounds. Nitrosocarbamide with phenol yields benzeneazophenol ; with resorcinol it gives benzoneazoresorcinol m. p. 161'. p-Nitrosotolyl- carbamide and resorcinal give rise to y-tolueneazoresorcinol m. p. 183-184'. E. F. A. case of methy~um~nocyclohexccne. w. 0. w.i. 104 ABSTRACTS OF CHEMICAJ PAF'EItS. The Action of Phosphorus Thiochloride on Alkaline Solutions of Phenols. WILHELM AUTENRIETH (BRT. 19 11 44 3754-3755).-The author draws attention to the fact that several of the substances prepared previously by himselF (Abstr. 1898 i 41 9) have since been described afresh with different nomenclature (Ephraim Abstr. 1911 i 284; this vol. i 26). Dinitrophenols. FRITZ ULLMANN and SHRIRANG 31.SANE (Ber. 1911 44 3730-3737. Compare Abstr. 1908 i 525; 1909 i 21 23).-0n warming 4-chloro-2 6-dinitrophenol with toluenesulphonyl chloi-irle and diethylaniline 1 4-dichloro-2 6-dinitrobenxene is obtained ; it forms colourless leaflets m. p. 105' (corr.). If however the diethyl- aniline is replaced by sodium carbonate solution the product is 4-chloro-2 6-dinitropilenyl . p-toluenesulphonate ; this crystallises in colourless needles m. p. 127'(corr.) ; the action of ammonia on a boil- ing xylene solution of this ester yields 4-chloro-2 6-dinitroaniline (compare Korner Abstr. 1876 i 230) ; similarly the action of aniline on an alcoholic solution of the ester produces orange-yellow needles of 4-chloro-2 6-dinitrodiphenylamisze m.p. 1 30° the same substance being obtained also from aniline and 1 4-dichloro-2 6-dinitrobenzene. The last-named substance also reacts with dimethyl- NO amine yielding 4-chloro- 2 g-dinitrodimethyl- aniline as orange-yellow crystals m. p. 111' (pro- I bably identical with that already described by "()-'-(/ Pinnow Abstr. 1899 i 203). By the action of the above-mentioned dichlorodinitrobenzene or chlorodinitrophcnyl p-toluenesulphonate on o-aminophenol there is obtained 3-chloro-5-nitrophenoxaxine (annexed formula) in violet needles m. p. about 192'. 1 2-Dichl0s~0-3 5-dinitrobenxeme is obtained from 6-chloro-2 4- dinitropbenol in R similar manner to the 1 4-dichloro-isomeride above; i t forms hexagonal pale yellow tablets m. p. 56'; in boiling alcoholic solution wit,h ammonia it yields yellow needles of 2-chloro- 4 6-dinitroaniline (m.p. 157') and with aniline brick-red crystals of 2-chloro-4 6-dinitrodip?hen$amine. Heated in alcoholic solution with o-nminophenol it yields 3 5-dinitrophenoxazine (compare Turpin Trans. 1891 59 722). 2-Chloro-3 5-dinitrotoluene m. p. 63' (cow.) is obtained by the action of to1 uenesulphoriyl chloride and diethylaniline on 3 5-dinitro- o-cresol; the lower m. p. previously obtained for this substance (Nietzki and Rehe Abstr. 1893 i 15) was due to impurity. I n the above process 3 5-dinitro-o-to191 p-toluenesulphonate (coloarless needles m. p. 167O) is obtained as a by-product. I f the above chlorodinitro- toluene is allowed to react with o-aminophenol 2 4-dinitro-6-methyl- 2'-hydroxydiphenylamine is obtained which crystallises in reddish- brown tablets m.p. 177" (corr.) and by treatment with dilute soda passes into 3-nit!1-0-5-metAylphenoxaxine (brown needles m. p. 205' with decomp.). The methyl esters of 3 5-dinitro-2-hydroxybenzoic acid and of 3 5-dinitro-4-hydroxybenzoic acid on treatment with toluenesulphonyl chloride and diethylaniline give the methyl eaters of 2-chloro-3 5- D. F. T. /\-NH-/\ORGANIC CHEMISTRY. i. 105 dinitrobenzoic acid (compare Purgotti Abstr. 1902 i 777) and 4-chloro-3 5-dinitrobenzoic acid (compare Ullmann Abstr. 1909 i 475) respectively. D. F. T. The Action of Metals on Fused Picric Acid. J. SAPOSHNIKOFF (Zeitsch. ges. Schiess. Sprengstoflwesen 191 1 6 183-185)- Kast's work is discussed (Abstr. 1911 i 852).The author heated one gram of various metals (in shavings or powder) with two grams of picric acid a t 125"; the amount of dissolved metal was estimated and found with the exception of tin to be in proportion to the equivalent weights of the metal. The respective weights dissolved by the picric acid were tin 0.00 ; aluminium 0.0488 ; iron 0.153 ; copper 0.1754 ; nickel 0.1862; zinc 0.2046 and lead 0.2798 gram. P. M. G. M. Electrolytic Reduction of Nitrated Phenyl Thiocyanates. FRITZ FICHTER and THEODOR BECK (Rer. 1911 44 3636-3648).- Muller has shown that the reduction of o-nitrophenyl p-nitrophenyl and 2 4-dinitrophenyl thiocyanates by alcoholic ammonium sulphide causes elimination of the thiocyano-group and the formation of nitrated diphenyl disulphides whilst tAeir reduction by stannous chloride yields thiazole derivatives (Zeit.Farb. Imd. 1906 5 357). The authors now show that different products are obtained by the electro- lytic reduction of these thiocyanates at lead or copper cathodes; the thiocyano-group is only attacked when lead cathodes are used. The reduction of pheny 1 thiocyanate in 2N-alcoholic sulphuric acid at a rotating lead cathode and with a current density of 0.02 ampere per sq. cm. (the anodic compartment contains a lead plate in 2N-sulphuric acid) yields hydrogen cyanide and 57.5% of phenyl mercaptan. Under similar conditions the reduction of o-nitrophenyl thiocyanate yields 1 -aminobenzthiazole which is probably produced by the secondary interaction of the o-aminophenyl mercaptan and hydrogen cyanide initially formed.With a copper cathode and a current density of 0.0 19 ampere per sq. cm. o-nitrophenylthiocyanate is reduced to the sulphate of 2-amino-5-hydroxyphenyl thiocpanate C7H,0N,S,H2S0,,H20 probably through the intermediate formation of a hydroxylamine derivative. 2- Amino-5-hydroxyphenyt thiocyanate NH,*C,H,(OH )*SCN m. p. 121" yields an N-acetyl derivative m. p. 206O (decomp.) (the methyl ether of which has m. p. 81°) a diacetyl derivative m. p. 183O and after diazotisation couples with P-naphthol to form an uzo- compound m. pa 130". p-Nitrophenyl thiocyanate is reduced to p-aminophenyl thiocyanate at a lead or copper cathode but in the latter case the intermediate pro- duct p-thiocyamoaxoxybenzsme ON,( C,H;SCN) m. p. 170-1 7 lo reddish-yellow leaflets can be isolated.The electrolytic reduction of 2 4-dinitrophenyl thiocyanate on account of its slight solubility and the consequent large volume of solution must be effected with large stationary cathodes of lead or copper foil ; also the solution (in alcoholic sulphuric acid) must be hot and a large current density 0.033-0.038 ampere per sq. cm. must bei. 106 ABS'1 RACTS OF CHEMlCAL PAPERS. employed. With r?. lead cathode the product is 1 4-diamino-5-hydroxy- the forma- tion of which is readily explicable in view of the course of the reduc- tion of the 0- and p-nitrophenyl thiocyanates. I n favour of this constitution is the fact tbat the sulphate yields a tliacetylamino- derivative m. p. 268' which is soluble in sodium hydroxide and forms 1 -amino-4-acet y lanzino-5-methoxybenztJLia xo le m.p. 2 5 7 - 2 5 go with methyl sulphate and sodium hydroxide. When reduced at a copper cathode and with a current density of 0*05-0.06 ampere per sq. cm. 2 4-dinitrophenyl thiocyanate yields at f i r p t the sulphate of 4-nitro- 2-umino - 5 - hydroxyphenyl thiocyanate 3C7H,03N3S,H,S04 (diucetyl derivative Cll*H90,NHS yellow microcrystalline powder) and finally the sulphate of 2 ; 4-dzamzno-5-hydroxypl~enyl thiocyanate (NN-diacetyl derivative m. p. 21 7" ; tyiacetyl derivative m. p. 156'). c. s henxthiazole sulphate NH,*C,H,(OH)<N>C*NH2,H2S0 S C,H,ON,S H2S04,H,0 New Halogen Compounds of the Normal Butane Series. JULIUS VON BRAUN and H. DEUTSCH (Ber. 1911 44 3699-3706. Compare Braun Abstr. 1911 i 6101.-Phenoxybutylene C,H,*OPh obtained on decomposition of phenoxybutyltrimethylammonium hydroxide OPh- [CH2];NMe,*0H yields with bromine phenyl-yi3- dihromobutyll ether OYh*C4H,Br2 which is converted by hydrogen bromide into a/3&tribi*omohutune CH,Br*CH,*CHBr-CH,Br.Mag- nesiurn removes two atoms of bromine forming magnesium butylene broviaide MgBr*[CH2J,*CH:CH2 and this is readily converted into Ay-pentenoic acid CH 2 C H CH,*CH,* C02H confirming the structural formula assigned t o the preceding compounds. Phenoxybutylene unites with hydrogen bromide to form phenyl y bromobutyl ether OPh*[CH,!,*CHMeBr. Phenoxybutylene is an oil b. p. 208-210°/760 mm. 94-(35'/ 16 mm. Phertyl y8-dibromobutyl ether is a colourless odourless oil b. p. 191-194°/13 mm. aB6-Tribrornobutane is a colourless liquid of pleasant odour b.p. 115-117'/10 mm. The magnesium compound interacts with a variety of substances so introducing the homoallyl complex CH,:CH*CH2=CH2 ; thus with benzaldehyde phenylbutenylcarbinoll 0 H*CHPh*[CH2],*CH:CH2 is obtained as a viscid colourless liquid of ethereal odour b. p. 125'/11 mm. Phenyl-y-bromobutyl ethey is a colourless odourless oil b. p. 130-1 3179 mm. After prolonged boiling with potassium cyanide t h e nitrile is obtained as a colourless odourless oil b. p. 156-157'1 10 mm. a d this when boiled for ten hours with alcoholic potassium hydroxide gives y-plt,enoxy-a-methylbutyric acid OPh CH,*CH,-C€€Me-CO H which separates in lustrous colourless crystals LTA. p. 79O. salt i s a colourless caseous precipitate. The silver E.F. A.ORGANIC CHEMISTRY. i. 107 Simple Method of Formation of Hydroxyhydrindones. KARL AUWERS (Ber. 1 9 11 44 3692-3699. Compare Abstr. 1910 i 629)-On heating p-tolyl a-bromopropionate with alummiurn chloride 7-hydroxy-4-methyl-l-hydrindone OH*C,H,Me<CO~>CH is obtained instead of o-bromopropionyl-p-cresol as expected. The structure of the hydrindone is established by the facts that it yields a semicarhazone and phenylhydrazone both soluble in alkali and contaiuing therefore a phenolic hydroxyl. The nucleus can be benzoylated and methylated and this methyl derivative still forms a semicarbazone. I n a similar manner the homologous isomeric methyl derivatives have been obtained from the p-tolyl a-bromobutyrate and a-bromoiso- butyrate. It is characteristic of these oxyhydrindones that their aqueous or alcoholic solutions are coloured deep blue by ferric chloride.It is probable in the above reaction that p-cresol vinyl ketone OH*C6H,Me*CO*CH:CH is formed as an intermediate product. The yield of hydroxyhydrindones is only about 50% of the possible ; coixmaranone derivatives are also formed. p- Z'oZyZ a-brornopropionate forms colourless lustrous needles m. p. 33" b. p. 145-150°/18 rnm. ' I - W ~ d r o z ~ - C m e t h y l - l -I,.ydyindone separates in flat colourless 1 ustrous needles m. p. 110-1 1 1". The semicarbaxone crystallises in colourless needles m. p. above 380' ; the pliengZhydraxom forms lustrouc almost colourless fatty needles m. p. 183". The benzylidene compound crys- tallises in faintly yellow-coloured needles m.p. 129". The benzoate is characterised by short calourless lustrous fatty needles m. p. J 24-125O and the methyl ether by stellate aggregates of slender colourless lustrous needles m. p. 112-1l3'. This methyl ether forms a semicarbaxone colourless needles m. p. 220-224° and a benzyzidene derivative colourless lustrous needles m. p. 185-1 86". p-ToZyZ a-bromoisobutyrate forms slender colourless needles m. p. 39-40" b. p. 152"/18 mm. 7-IZydroxy-2 4-dimethgl-1 -Iydrifidone OH*C,H,Me<~~~>CHMe crystallises in colourless needles m. p. 53" ; the benxoyZ derivative yields lustrous colourless needles m. p. 113-114" ; the semicaybaxone gives colourless glass-like crystals which gradually become citron- yellow on exposure; they become brown a t 220° m.p. 230-232'. CH This hydrindone does not form a benzylidene compound. separates in stunted colourless lustrous crystals m. p. 53-54". The senzicarbaxone forms stunted crystals m. p. 217" ; the benzylidene compound gives glass-like,. yellow flat needles m. p. 114". p-ToZyZ a-brontobutprate 1s an oil b. p. 160-163°/20 mm. E. F. A. Retene. 11. ALFRED HEIDUSCHKA and H. GRIMM (Arch. PJmrnz. 1912 250 33-45. Compare Abstr. 1910 i 397).-ltetenequinone reacts with organomagnesium haloids to form dihydroxydialkyl-i. 108 ABSTRACTS OF CHEMlCAL PAPERS. dihydroretenes and these mere isolated in a crystalline condition in the case of the phenyl benzyl p-tolyl naphthyl and methyl derivatives but could not be obtained pure in the case of o-tolyl m-xylyl bromocamphor ethyl or i-amyl derivatives.Experiments on the reduction and dehydration of dihydroxydiphenyldihydroretene are also recorded. Di~,yr€roxyd7pl~enyZdihZ/dro?.etenne CpnH,,O m. p. 172" obtained by condensing magnesium phenyl bromide with retenequinone in ether forms colourless crystals and is coloured red by sulphuric acid yellow by fuming nitric acid. Heated with acetyl chloride i t yields the corresponding anhydride C,,H,,< I >O m. p. 143-144" crys- tallising in clusters of needles and giving when heated with potassium hydroxide in alcohol in closed vessels an acid which probably corresponds with the product described by Acree (Abstr. 1905 i 216) as obtained from diphenylphenauthrone; its ethereal solution is coloured blue by ammoniacal copper oxide and then yields a copper derivative (C,,H,70,)2Cu m.p. 142' which at 125-140" slowly loses ammonia and turns green. When heated with zinc dust dihydroxydiphenyldihydroretene yields diphenyhetene m. p. N O ' crystallising in colourless needles from alcohol or acetone. Reduction with hydriodic acid and phosphorus gives rise to diphen?/lhezahydror~tene (which forms colourless crystals sinters at 8 2 O and melts completely a t 118')) and eventually t o Liebermnnn and Spiegel's retenedodecahydride. On bromination in carbon disulphide dihydroxydiphenyldihydro- retene gives a pale yellow finely granular powder which on distillation with zinc yielded diphenylretene. Chlorination produced a similar product containing 39.5% chlorine. Dihyclroxydi-p-tolyldihydroretene m. p. 203O obtained in a manner analogous to that described for the phenyl derivative forms glancing colourless leaflets.The anhydride m. p. 152-154O) occurs in colourless transparent small tablets. The products of bromination and chlorination resemble those of the lower homologue. Dihydroxy- dibenxyZdihydroretene m. p. 200-201° forms stellate clusters of small glancing needles. Dihydroxydinaphthyldi~ydroretene m. p. 2 17-218O was isolated with some difficulty by treating the crude product with warm toluene ; it yields an anhydride m. p. 188" which forms small glancing crystals from acetone or alcohol. Dihydroxydimet~yldihy~~o- retene IU. p. 166-167O was eventually obtained in poor yield as small colourless crystals giving a violet-brown coloration with sulphuric acid.On chlorination in carbon tetrachloride with iodine as carrier retene furnishes a viscid product which on precipitation from alcohol with water forms an amorphous colourless substance C18H14C19 [?I m. p. 98-100'. Influence of Sulphur and Sulphur-containing Groups on the Order of Substitution of Hydrogen Atoms in Benzene by Bromine. EUOUARD BOURGEOIS and A. A BRAHAM (Bec. trav. chim. 191 1 30 407-425. Compare Abstr. 1904 i 28).-Substances CPh CPh T. A. H.ORGANIC CHEMISTRY. i. 109 containing either of the groups -SH >KO -SO,H are completely transformed by bromine. The authors have studied the action of bromine on aromatic sulphides and disulphides sulphones and sulphonic acids. With bromine the sulphides give rise to dibromides of the type SRR’zBr which show no teridency to split up into the sulphide and free bromine but readily become transformed into substitution products.Phenylmethylsulphoniulin dibromide SMePhBr is obtained as a red crystalline substance m. p. 87-88’ when bromine acts on phenyl methyl sulphide in carbon tetrachloride solution below 0’. Above this temperature it gives off hydrogen bromide and is transformed into p-broi,io;uhe?~yl methyl sulphide m. p. 37-37-5O. This when oxidised by potassium permanganate in acetic acid solution yields the corre- sponding sulphone m. p. 102.5-103° which mlth phosphorus pentachloride gives p-chlorobromobenzene. The sulphide can also be obtained by the action of methyl iodide on the sodium salt of p-bromot hiophenol. Diphenylsulphonium dibromide SPh2Brs is obtained by a similar reaction to the above as a red crystalline precipitate which still more readily passes into the corresponding p-bromophenyl sulphide. Phenyl disulphide when dissolved in bromine yields p-dibromophenyl disulphide (compare Hubner and Alsberg Annulen 1870 156 328).Phenyl methyl sulphone is not attacked by bromine unless a catalyst such as ferric chloride is employed in which case there is produced p-bromophenylmethylsulphone identical with that obtained by the oxidation oE the corresponding sulphide with potassium permanganate (loc. cit.). I n all the above cases the bromine atom enters the para-position to the sulphur-containing group whilst in the case of the sulphonic acids the group -SO,H directs the bromine to the rrieta-position. W. G. Oxonium Compounds.GEORGE L. STADNIKOFF (J. Russ. Php. Chem. Soc. 1911 43 1244-1257).-According to Nef’s theory the first stage of the interaction of an alkyl halide with alcoholic alkali hydroxide consists of the dissociation of the alkyl halide into halogen hydracid which is neutralised by the alkali and the methylene residue R-CH which either combines with the alcohol forming a simple ether or undergoes isomeric change into an olefine. The fact that tert.-butyl iodide which is incapable of methylene dissociation gives no ether when treated with alcoholic alkali hydroxide is regarded as confirmation of Nef’s theory. The author finds that this evidence is fallacious since tertiary alkyl halides such as tert.-amyl bromide do give ethers under the above conditions although the yield is very small ; also te~t.-butyl iodide yields an appreciable amount of ether if treated with the alcoholic alkali in a sealed tube.Another observation which is not in agreement with Nef’s theory is that triphenylmethyl chloride reacts with alcohols giving ethers in theoretical yields. The most obvious method of explaining these reactions is t o assume that the alkyl halogen compound RX dissociates into ttlkyli. 110 ABSTRACTS OF CHEMICAL PAPERS. and halogen which then cotribirie with the alcotiol forming an oxoniuin compound R'H:O:KX. Tho latter may then decompose in two W L ~ giving (1) R'.O*R+I-IX or (2) K'H:O:HX+ an oiefine. Those reactions would herice he closely analogous t o those between alkyl halides and amines (see this vol. i 116). Owing t o the doubt which exists concerning the intermediate formation of oxonium compounds in such reactions as the above and i n the Grignard reaction the author has studied the following reactions.(1) The action of propyl iodide on triphenylmethF1 ethyl ether in presence of magnesium. E e r e the first stage of the reaction con- sists in the formation of the oxonium compound CPh,*OEt:PrI which then decomposes giving triphenylmethyl iodide and ethyl propyl ether. (2) With the same ether as in (1)) isobutyl iodide in presence of magnesium combines to form a n oxonium derivative which i H subsequently resolved into triphenylmethyl iodide and ethyl isobutyl ether. (3) Diphenylmethyl propyl ether and isobutyl iodide react in presence of magnesium giving the oxonium compound CHPh,*OPrI*C,H which decomposes in three ways giving (a) CHPh21 + C,H;OPr ; (bj C,H,T + CHPh,*OPr ; and ( c ) C,H,I +CHPh,-O-C,€I,(?).Diphenylmetibyl proppl ethey CHPh,*OPr prepared by the inter- action of diphenylbromorriethane and propyl alcohol in presence of potassium hydroxide is a colourless mobile liquid b p. 161°/11 mm. T. H. P. Some Chlorine Derivatives of Cholesterol. S'I'EPHAN MINOVNI and BELLA HAUSKNECHT (Biochem. Zeitsch. 19 12 38 46-52).- When cholesterol in alcoholic solution is treated with chlorine gas two substances are formed ; one C',,H7,O,Cl2 or C4,H7,OHCI2 is soluble in alcohol and contains water of crystallisation m. p. 125O and when anhydrous m. p. 130' ; the other C,GH,o,0,C12 m. p. 195' (precipitated from ethereal solution by alcohol) is insoluble in alcohol.The formation of the former substance can be explained on the assump- tion that two molecules of cholesterol combine t o form an ether from which by tha chlorinating and oxidising action of the chlorine two vinyl and two isobutyl groups are eliminated and replaced by hydroxyl and chlorine. By the action of hydrogen chloride and hydrogen peroxide a third chlorine derivative C,6H,70Cl was obtained ; it forms slender needles containing water of crystallisation m. p. 123'. S. B. S. Preparation of Arylpolymethylenechloro - compounds. EMANUEL MERCK ( D.R.-P. 23895 9). -When benzo-e-chloroam ylamide C6H,:CO*NH*[CH2],Cl is heated with aluminium chloride in benzene solution and the mixture subsequently treated with steam it yields benzo- ephenylam ylamide C,H CO -3 H [ CH,],.P h a yell0 w oil b. p. 273-275O115 mm. which on hydrolysis furnishes qdmylwtrql-ORGANIC CHEMISTRY i. 111 umine NH2*[CH2],Ph b. p. 131’/15 mm. picrdta m. p. 158-153O and platinichloride m. p. 220’. 4‘hZoroamylbefixene obtained by heating the foregoing benzophenyl- amylamide with phosphorus pentachloride has an unpleasant odour and b. p. 134’/18 mm. Benxo - 8 - pkenylbutyZarrLide glistening needles m. p. 83*5” is analogously prepared from benzochlorobutylamide with phosphorus pentachloride ; it furnishes 6-chlorobutyt?benxene C,H,*[CH2],Cl b. p. 122-1.23’/17 mm. F. M. G . M. Preparation of Derivatives of o-Thiolbenzoic Acid. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 237773).-When dichloroethylene (1 mol.) reacts with an alcoholic solution of a thiolbenzoic acid (2 mols.) i t yields acetylbisthiolbenzoic acids (bismethinethiolbenzoic acids) of the general formula CO,R’*R*S*CH:C H:S*R*CO,R’ where R is a benzene or naphthalene residue and R a metal aryl or alkyl group.The preparation of acetylenebisthiolbenzoic acid is described. F. M. G. M. Products Formed by the Action of Heat on y-Sulphamido- benzoic Acid. W. B. STODDARD (Amer. Chew&. J. 1912 47 1-20) -Remsen and Muckenfuss (Abstr. 1896 i 481) found that when p-sulphamidobenxoic acid is heated at 220’ for eight hours there are formed p-sulphobenzoic acid ammonium hydrogen p-sulphobenzoate an ‘‘ infusible diamide of p-sulphobenzoic acid,’’ and “ iso-p-sulphamido- benzoic acid.” When the ‘‘ infusible diamide ” is heated with phosphorus penta- chloride at 194-197’ p-chlorobenzonitrile is produced.An attempt mas mado to remove one of the nitrogen atoms whilst leaving the other by heating the compound with hydrochloric acid but without success. It was also found t h a t the desired result could not be attained by ciiazotisation or by heating with sodium carbonate solution. When a current of steam was passed through a mixture of the diamide and magnesium hydroxide ammonia was liberated and a magnesium salt was obtained of an acid isomeric with p-sulphamidobenzoic acid but entirely different from ‘‘ iso-p-sulphamidobenzoic acid.” The corre- sponding potassium salt reacts readily with phosphorus pentachloride but the infusible diamide is not thereby regenerated. These facts indicate that the nitrogen atoms of the infusible diamide are both attached t o carbon and that the acid isomeric with p-sulphamido- benzoic acid is probably p-carbamido benzenesulphonic acid.When Remsen and Muckenf uss’ ‘‘ iso-p-sulphamidobenzoic acid ” is heated in a sealed tube with concentrated hydrochloric acid a t looo the infusible diamide is produced. If the acid is heated in a sealed tube with water a t 220° a small quantity of a substance is produced which crystallises in thin plates. Analyses of the barium and sodium salts of “ isop-sulphamidobenzoic acid ’’ have shown that this acid is not isomeric with p-sulphamidobenzoic acid but has the composition OF an anhydride of the latter C,H,<Co->NH. Determinations have so2i. 112 ABSTRACTS OF CHEMICAL PAPERS.been made of the electrical conductivity of solutions of both these acids. It is suggested that the action of heat on p-sulphamidobenzoic acid may be represented by the equation 4C02H-C,H,*S0,~NH2 = C,H4<S0,>(NH2)2 CO- + C0,H*C,H4*S0,H + E. G. Bornylene from P-Iodohydrobornylenecarboxylic [ P-Iodo- camphanecarboxylic] Acid Dibromobornylenecarboxylic [ap- Dibromocamphanecarboxylic) Acid and Dihydrobornylene- carboxylic [ortho-Camphanecarboxylic] Acid. JULIUS BREDT and W. HILBING (J. p r . Chem. 1911 [ii] 84 778-786. Compare Abstr. 19 10 i 498).-P-lodocam;olza~~,zec~s.6ozylic acid CH*C02H CSJ314<(5HI ' prepared by the action of hydrogen iodide on a glacial acetic acid solution of bornylenecarboxylic acid crystallises in needles m. p. 129-130'. It dissolves in hot aqueous sodium carbonate yielding a crystalline sodium salt together with the hydroxy-acid Cl1H,,O3 pre- viously described (Zoc.cit.). When heated with strong aqueous sodium hydroxide the sodium salt yields bornylene which has [.I - 23.68' in toluene and [a] - 23.94Oin benzene. A glacial acetic acid solu- tion of bornylene when heated at '70' with sulphuric acid yields a bornyl acetate b. p. 103-104'/14 mm. which on hydrolysis furnishes a borneol of m. D. 175-178'. I YBr*CO,H ap-Dibromocamphanecccrbox?/Eic mid C,EIl,<aHBr obtained by the addition of bromine to bornylenecarboxylic acid in carbon tetrachloride solution and purified by means of the sodium salt crystallises in needles m. p. 159-1609 ortho-Camphanecar boxylic acid (Zoc. cit.) prepared by reducing /3-iodo- camphanecarboxylic acid yields a chloride b.p. 114-115'/14 mm. and an amide m. p. 166-167" which is con- CH2*CH-CH*NH2 verted by the Hofmaun reaction into an I amine of the annexed formula. Improvements in 1 UMe2l the preparation of hornylenecarboxylic acid are CH~.&X~*CH also described. Ethyl bornyles~ecurboxylale obtained as a by- product in crystallising the anhydride from alcohol has b. p. 121-122°/16 mm. F. B. Electrolytic Reduction of Oamphononic Acid to cis-trams - Camphonolic Acid Camphonololactone. JULIUS BREDT [and in part with WILHELM LUND and AUGUST AMANN] (J. pr. Chem. 191 1 lii] 84 7S6-799).-When subjected to electrolytic reduction camphon- onic acid yields a mixture of two stereoisomeric camphonolic acids 2>CMe*C0,H OH*F)H-CMe CH2-CH,ORGANIC CHEMISTRY.i. 113 which may be separated by distillation whereby the cis-camphonolic acid is converted into the corresponding lactone whilst UH2*7H-0 the cis-trans-isomeride distils unchanged. I ?Me I cis-Canzpi6or~oZoZactorze (annexed formula) has m. p. CH,*CMe.CO 160-161' b. p. 239.2' [a] - 16.2' in alcohol. cis-Camphonolic acid is obtained by the addition of the calculated amount of cold dilute hydrochloric acid to its barium salt which is prepared by the action of barium hydroxide on the preceding lactone. It has [a] - 33.4" in alcohol aud a varying m. p. according to the rapidity of heating; when rapidly heated it has m. p. 197-198'. The isomeric cis-trans-ccc.lnphonolic acid has m. D. 249-250'. $!HBr* CMe CH,-C H 2 y-Bromocarn~Zion~nic acid 2>CMe*C02H obtained by the action of saturated aqueous hydrobromic acid on the cis-laclone has m.p. 146-147' and when treated with aqueous sodium carbonate 1s reconverted into the lactorre. Both cis-trans-camphononic acid and cis-camphonololactone are oxidised by concentrated nitric acid to camphoronic acid. Improvements in tile method of preparing camphononic acid (Lapworth and Lenton Trans. 1901 79 1287) are also described. F. B. Resolution of Mandelic Acid into its Active Gomponents by means of Phenylethylamine. LENNART Simwr (J. pr. Chem. 1911 [ii] 84 743-744).-The resolution of r-mandelic acid has been accomplished by crystallking the I-P-phenylethylamine salt from water the salt of the d-acid being the less soluble. The pure d-acid is obtained from the rnandelic acid recovered from the mother liquor by crystallisation with d-phenylethylamine. F.B. Atrolactic [a-Hydroxy-a-phenylpropionic] Acid. LENNART SMITH(J.~. Chem. 1911,[ii],8477Y1-743).-The first part of thispaper contains an account of a large number of experiments on the formation of acetophenonecyanohydrin and the hydrolysis of the latter compound to atrolactic acid. This is followed by a description of the resolution of tlhe acid into its optically active components and of its behaviour towards hydrochloric acid. I n the preparation of atrolactic acid by Spiegel's method (Abstr. 1881 277 ; compare Staudinger and Ruzicka Abstr. 1911 i 462) better yields are obtained by replacing the hydrochloric acid by glacial acetic acid. Atrolactic [a- hydroxy-a-phenylpropionic] acid crystallises with $H,O and the potassium sodium and mugnnesium salts with 2H,O; t h e strontium salt Sr(C,H90,),,4H20 and caclcium salt CaH2(CgH,0,) m.p. 216' (decomp.) are also described; the affinity constant K= 0.0341. The resolution of the acid into its optically active component is accomplished by crystallisation of its salt with I-/3-phenylethylamine the salt of the d-acid being the less soluhle (compare McRenzie and Clough VOL. CII. 1 2:i. 114 ABSTRACTS OF CHEMICAL PAPERS. Trans. 1910 9'7 1016). The pure 1-acid is obtained by crystallising the acid recovered from the mother liquors with d-phenylethylamine. The l-phen?/lethyZarrai?ze salts of both the d- and the I-acids were analysed. The barium BaX,,&H,O calcium CaX,,3$H,O and potassiuim KX,2H20 salts of the active acids are also described (X - C,H,O,).Hydratropic acid is readily obtained from atrolactic acid by heating it with concentrated hydrochloric acid for three-qurtrters of an hour on the water-bath and reducing the product with sodium amalgsm. When heated with concentrat,ed hydrochloric acid for four hours a t 130-1 35' atrolactic acid yields P-chloro-a-phenylpropionic acid together with a- and P-isoatropic acids. By heating tropic acid a t 170-180° it is converted into atropic acid which is accompaDied by small quantities of a- and P-isoatropic acids. From these experiments the conclusion is drawn that the action of hydrochloric acid on atrolactic acid yields successively atropic /3-chloro- a-phenylpropionic and isoatropic acids.F. B. a-Phenyl-a-ethylglycollic Acid. LENNART SMITH (J. pr. Clzem. 19 1 1 [lii] 84 744-745). - a-Phenyl-a-ethylglycollic [a-hydroxy- a-phenyl butyric] acid is best prepared by the addition of glacial acetic acid to a mixture of potassium cyanide and propiophenone and hydrolysis of the nitrile thus obtained by means of hydrogen chloride in ethereal sclution the resulting amide being finally hyclrolysed by aqueous sodium hydroxide. Jt crjstallises in needles m. p. 132' (corr.) (compare Grignard Abstr. 1903 i 32) and is resolved into its optically active components by crystallisation of the d-P-phenylethyl- a m i n e salt. Z-a-HpdPox y-a-phen ylbut yric acid has in aq rieous solution [a];* - 14'. F. B. Ethyl Anisoylacetates. AND& WAHL and C. SILBEEZWEJG (Bull.SOC. chim. 1912 [iv] 11 25-34. Compare Abstr. 1908 i 647 ; 1910 i 1163).-Ethyl rn- andp-methoxybenzoylacetates have been prepared by condensing ethyl acetate with ethyl m- and p-methoxy- benzoates in presence of sodium. The corresponding ortho-compound has already been prepared by Tahara (Abstr. 1892 844). Ethyl p-anisoylucetate OMe*C6H4*CO*CH,*C02Et is a pale yellow liquid b. p. 180-190°/10-12 mm. decomposing partly into p-anisoyldehydracetic acid. It yields a green copper salt (CI2HI,O4),Cu m. p. 2 loo and a nitroso-deri vative m. p. 11 3-1 14'. Ethyl m-methoxybenxoylacelate also decomposes very readily on tfis- tillation. I t yields a green copper salt m. p. 168-169O and a nitroso- derivative m. p. 94'. W. G. Preparation of Halogenated 2-Anthraquinonglaminobenzoic Acids.FRrrz ULLMANN (D.R.-P. 238106. Compare Abstr. 1906 i 426 953 ; 19 10 i 270).-4-Bromo-2-anthrapuinonylarninobenzoic acid Ci,H7O2*NH*C,H,Br.C0,H a violet powder which does not fuse a t 300' is obtained by heating l-chloroanthraquinone (24.2 parts) with 4-bromoan thranilic acid (22 parts) potassium acetate (20 parts) copper acetate (1 part) and copper powder (1 part) at 160' in amyl-alcoholic solution. F. M. G. M.ORGANIC CHEMISTRY. i. 113 Fagaramide a New Nitrogenous Substance from the Root- bark of Fagara xanthoxyloides. HERMANN THOMS and F. THUMEN (Ber. 1911,44,3717-3730).-The root-bark of Fagarcc zanthoxyloides contains a nitrogenous substance C,,H,,O,N crystallising from alcohol in well-formed crystals m. p. 119-120". Thirty grams were obtained from 40 kilos.of the drug. The compound termed fagaramide is identified as the isobutylainide of piperorzylcccrylic acid CH2:O2:CG)IT,*CH CH-CO*NH-CH,*CHMe,. On prolonged boiling with 50% alcoholic potassium hydroxide it is decomposed into isobutylamine and piperonylacryl ic acid. Pagaramide is prepared synthetically by condensing piperonyl- acrylic chloride and isobutylamine in ethereal solution. In a similar manner the isomerides are prepared namely the normal secondary and tertiary butylamides of piperonylacrylic acid. All four isomerides form chitracteristic crystalline dibromo-derivatives. Fagaramide reacts neutral and does not form salts; it belongs to the same group as piperine. All four isomerides have the same physiological action namely narcotic on cold-blooded animals but practically none 01 warm-blooded animals.Fugccramide is obtained by extraction with benzene. The dibronaicle C,,H,703NBr forms slender colourless needles m. p. 154-155'. i)n oxidation of fagaramide piperonal and piperonylic acid m. p. 230' (not 227.5-228') are obtained. Piperonylacrylic acid has m. p. 242" (not 2.38' or 232-234' as stated in the literature). isoButy1- amine hydrochloride bas in. p. 177-178' (not 160'). Piperonylacrylic chloride CB202:CGH,-CH:C1H*~OCl is conveniently prepared by the action of thionyl chloride on the acid. Piperonylacry I-n-butylarnide CH,0,:C,H3*CH:CII*CO*NH~[CH2]~l*CH forms very minute crystals m. p. 85-86'. in small colourless needles m. p. 134-135" (decornp.). CH20, C,H,* CH CH CO*NH*CHMeEt yields colourless needles m.p. 161-162'; the dibromide has m. p. 164-165" (decornp.). Piperonylacryl-tert. -6utylumide CH,O,:C,H,*CH CH*CO*NH* CMe forms strongly refractive pale yellow prisms which are colourless when powdered m. p. 138-139' ; the dibromide crystallises in slender colourless needles rn. p. 182-183" (decornp.). SIEGMUND GABRIEL and JAMES COLMAN (Bev. 191 I 44 3628-3636).-The analogous behaviour of ketones and sulphones in many reactions led the authors to hope that 7- and 6-aminosulphones might yield heterocyclic bases just as y- and 6-amino-ketones yield pyrrolines and tetrahydropyridines respectively. This expectation has not been fulfilled but the work has led to the production of the following substances. When warmed with phosphoriis pentachloride phthalyltaurine The dibromide separates Pzperonylacr?ll-sec.-butylalnide E.P. A. Aminosulphones and Allied Gompounde. i 2i. 116 ABSTRACTS OF CHEMICAL PAPERS. This substance is very stable to hoL water does not react with benzene and aluminium chloride but is converted into the methyl ester C,H4<CO>N*02H,*S0,Me co C6H4<Co>N* co C H,-CH,*SO Ph m. p. 103-104" by methyl-alcoholic sodium methoxide. Phenyl /3-phthcclimidoethyl sulphone m. p. 185-185.5" obtained from benzenesulphinic acid alcoholic sodium ethoxide and P-bromoethylphthalimide a t loo" yields by hydrolysis by acetic acid and hydrochloric acids a t 140° phenyl- P-nminoethylsulphone hydrochloride NH,*CH,*CH,*SO,Ph,HCl m. p. 155-155.5" glistening needles. Yhercyl-y-~ht?Lalirnidopropylsulphone m.p. 126' and phenyl-y-ccminopropylsulphone hydrochloride m. p. 222O are obtained by similar methods from y-iodopropylphthalimide. Phenyl mercaptan and P-bromoethylphthalimide react with boiling alcoholic potassium hydroxide tp form phcsnyl P-phthcclimidoethyl sulphide C6H4<CO>N-C H,*CH,*SPh m. p. 59-60" long needles by the hydrolysis of which plcenyl P-aminoethyl sulphidc hydrochloride NH,*CH,*CH,*SPh,HCl m. p. 160-161° is obtained. /3-Phthnlirnidoethyl mercaptan is converted by warm nitric acid D 1 '2 into ~ - p h t l c u l i ~ ~ ~ i c l o e t ~ ~ y ~ d ~ s u l p ~ ~ o ~ ~ c l e co (C,H,<g>N*CH,.CH ) + w. p. 155-156" which reacts in benzene with aluminium chloride on the water-bath to form after treating the product with hydro- chloric acid /3-pht~alimi~oet~~yl~~lp~Linic mid C,H4<Ez>N*CH,* CH,.S02H m. p. 149-1495' (decornp.) glistening white leaflets This acid which is also obtained by reducing the disulphoxide or phthalyltauryl chloride by zinc dust and 96% alcohol is decomposed by boiling 20% hjdrochloric acid yielding phthalic acid taurine and /I-phthalimido- Action of a-Hydroxyisobutyronitrile on the Nitrile Ester of Iminodi-phenylacetic Acid. GEORGE L. STADNIKOFF (J. Rues. Phys. Chem. Xoc. 1911 43 1235-1244).-1t has been previously suggested (Abstr. 1909 i 771 772; 1910 i 825) by the author that in the action of a-hydroxypropionitrile on the nitrile esters of propionyliminocycloheptanecarboxylic and iminodi-phenylacetic acids an intermediate unstable compound of the ammonium hydroxide type is formed this then undergoing decomposition into other hydroxy- nitriles and nitrile esters of imino-acids.Such intermediate forma- tion of ammonium hydroxide compounds is assumed also (1) in the formation of amines and amino- imino- and nitrilo-acids by the action of hydroxy-nitriles on either ammonia or its derivatives ; (2) in the interaction of alkyl halides or halogen derivatives of acids with ammonia or its organic derivatives and in a number of other reactions. ethyldisulphoxide. c. s.ORQAXIC CHEMISTRY. i. 117 Most of the reactions represented in this way are explained equally well by Nef’s ‘‘ methylene-dissociation ’’ ; thus the interaction of the nitrile ester of iminodi-phenylacetic acid and a-hydroxypropio- nitrile may be regarded as occurring in the following stages (I) the hydroxynitrile dissociates into rnethylene derivative arid water CH,*CH(OH)*CN = CH,*C(CN) + H,O ; (2) water and the nitrile ester give the ammonium hydroxide compound CN*CHPh*NH,(OR)*CHPh*CO,Et ; (3) the ethylidenecyanogen combines with the ammonium hydroxide compound giving the nitrile ester of a nitrilo-acid CK*CHPh*NH(OH)( CHMe*CN)-CHPh*CO,Et which then decomposes into derivatives of an imino-acid of lower molecular weight and mandelonitrile. I n order to arrive at4 a decision between these two explanations the author has investigated the action of a-hydroxyisobutyronitrile which is incapable of methylene dissociation on the nitrile ester of iminodi-phenylacetic acid.The result confirms the author’s view of these reactions the product of the reaction being anhydronitrilo- diisobutyricphenylacetic acid which is formed as follows CN*6HPh*NH*CHPh*CO2Et + OH.CMe,.CN = CN*CHPh*NH(OH)(CMe2*CN)*CHPh*C02Et = OH*CHPh.CN + UN*CMe,=NH*CHPh*CO,Et ; the latter + 0H*CMe,.CN = CN*CMe,*NH(OH)(CMe,*CN)*CHPh*CO,Et = H20 + CN*CMe2-N(CMe,*CN)*CHPh*C02Et.This nitrile ester then under- goes hydrolysis to the substituted triacetic acid which is subsequently transformed into the corresponding anhydride. AnAydronitriZodiisobutyricphen~lacetic acid C1,H,,O,N (see above) crystallises from aqueous alcohol in silky needles m. p. 180-181° (slowly heated in sealed capillary). As would be expected from the fact that iminodicarboxylic acids are rendered neutral to phenol- phthalein by one equivalent of alkali hydroxide two equivalents of the latter are sufficient to neutralise this anhydride.Photochemical Behaviour of Nitroterephthalaldehyde. HERMANN %IDA (J. pr. Chem. 1911 [ii] 84 827-83O).-The author finds that nitroterephthnlaldehyde is very sensitive to light. A cold xylene solution of the aldehyde on exposure to direct sunlight rapidly becomes turbid and deposits a yellow solid consisting of 2-nitroso- 4-aldehgdobenxoic acid CHO*C,H,(NO)*CO,H. The acid sl0wly chars at 250-300° but when placed in a bath a t 300’ instantly melts with decomposition It dissolves in alkalis and alkaline carbonates yield- ing yellowish-green solutions. Its solution in concentrated sulphuric acid develops with a trace of phenol an emerald-green coloration. Details of a lecture experiment illustrating the photochemical transformation of the aldehyde are given.Angeli-Rimini Reaction of the Aldehydes. ANGELO ANGELI ( A t t i R. Accad. Lincei 1911 [v] 20 ii 445-449. Compare Balbiano Abstr. 1911 i 987).-The author has prepared Wallach’s ketone OMe* C,H,*CH,*COMe and Balbiano’s product from anethole T. H. P. F. B.i. 118 ABSTRACTS OF CHEMICAL PAPERS. glycol and Gnds that they are identical and do not give the Angeli- Rimini reaction when i t is carried out as originally described. ' h e reaction however is given by these substances when an excess of alkali is employed. This explains Balbiano's resirlts. It is advisable to add the calculated quantity of alkali in small portions (compare Angeli and Castellana Abstr. 1909 i 392) and in the qualitative test it is better to use the sodium salt of Pilot,y's acid.Deoxybenzoin benzoin b e n d and dibenzyl ketone behave similarly giving the reaction only when an excess of alkali is employed. R. V. S. o-Hydroxyacetophenone 5-Chloro-o-hydroxyacetophenone and Certain Chlorochalkones and Chloroflavones. FRANZ Compare Abstr. 1901 i 213).-The authors describe the preparation of o-hydroxyacetophenone from 5-acetylamino-?-hydroxyacetophenone and of 5-w-dichZoro-2-1~7~drox~acetophenone (rn. p. 64") from o-chloro- 5-nrni~~o-2-hydroxyacetophenone. The corrsspondiug w-chloro-5-bromo- 2-h~droxyacstophenone has m. p. 68". 5-Chloro-2-bydroxyacetophenone condenses with benzaldehyde in the presence of sodium hydroxide t o form 5-chloro-Z-hycll.oxychalkone m. p. 10So which readily combines with bromine to form il dibl.omide of m. p.185'. H. W. GUIDO BARGELLTNI and LEDA RrNr (Gazzetta 191 1 41 ii 435-445).-Hydrochalkoues may be prepared conveniently by reducing chalkones with hydrogen in the presence of platinum-black. I n this way from an ethereal solution of 2-hydroxychalkone 2-hydroxydihydrochalkone was obtained ; the product is best purified by conversion into the semicurbaxone CI6Hl7O2N3 which forms white needles m. p. 174-175' (softening a t 170"). The reduction of 4-methoxychalkone with zinc dust and acetic acid yielded n substance (probably a diketonic condensation product) C32H.7004 which crystallises in colourless needles m. p. 224-225O. When 4-methoxychalkone in ethereal solution is reduced with bydrogen iu preseuce of platinum- black 4-methoxydihydrochaZkor~e C,6H1602 is obtained ; i t crystallises in colourless needles m.p. 59-60" (softeniog at 55O) arid it gives a yellow coloration with concentrated sulphuric acid. The semicarbaxone C17Hl,0,N3 forms colourless needles m. 1). 118-120". 3 4-Dimethyleneoxychalkone when reduced with zinc and acetic acid yields a substance C32H2S0 which crystallises in colourless needles and is solid a t 260'. When the reduction is effected with hydrogen in the presence of platinum-black 3 4-dinzethyEeneoxydi- hydrochalkone C16H1403 is produced ; it crystallises in colourless needles m. p. 39-40' (softening at 35O) and gives a red coloration with concentrated sulphuric acid. The semicarbaxone C17H1703N3 Preparation of Ben zoylaminoh ydroxy antbr aquinon es.FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (19. K-P. 238488).- When I 5-dibenzoyldiami~ortptbraquinones are oxidised with either KUNCKELL [with ALBERT FURSTENBERG] (Ber. 1911 44 3654-3666. Chalkone and Hydrochalkones. forms colourless needles m. €7. 153-154'. K. v. s,ORGANIC CHEMISTRY i. 119 manganese dioxide a persulphate or a perchlorate a by droxy-group is introduced into either position 4 or 8. 1 5-Dibenzoyldiamiooanthr:tquir1one (10 partsj dissolved in 100 parts of siilphuric acid (10% SO,) was slowly treated at 5-10" with manganese dioxide (3.5 parts) maintained below 15" with continual stirring during two hours and the 4-hydroxy-1 5-dibennxoyldiamiizo- nnthrayuinone subsequently isolated by known methods. 4-Chlo~o-8-hydroxy-1 5-dibenxoy Idiaminoanthraquinone was prepared in R similar manner with pot'assium persulphate from 4.chloro-1 :5- dibenzoyldiarninoanthraquinone whilst 2-chloro-1 5-dibenzoyldinmino- anthraquinone furnished 2-~7~lor0-4(8)-hydroxy-l 5-dibenzoyldiamino- anthmguinone.F. M. G. M. Preparation of Dianthraquinonyl- or Polyanthraquin onyl carbamides. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P 238550 238551 238552 and 238553. Compare Abstr. 1911 i 469 655 995).-The preparation of dianthraquinonylcarbamides has previously been described and the reaction has now been extended to the case of heteronuclear PP'-diaminoanthraqixinones. These compounds orange-yellow powders are obtained by the action of /3p'-anthraquinonyEenedicarboxyE chlorides (obtained from 2 6- or 2 7-diaminoanthraquinones with excess ef carbonyl chloride) on amino- or diamino-antlirayuinoncs. The second and third patent's state that PP'-dianthraquinonyl- carbamide can be readily prepared by heating P-aminoanthraquinone a t 170" with carbamide or ethyl urethane either with or without solvent until evolution of ammonia (and in the latter case alcohol) ceases.The foiirth patent deals with the employment of substituted iiryl- or diaryl-carbamides and describes p-tolyl-2-anthraqii.irionyl- carbamide yellow crystals obtained by the prolonged boiling of $2-toluidine with 2 2'-dianthraquinonylcarbamide. F. M. G. M. [Preparation of Anthracene Derivatives.] BADISCHE ANILIN- dz SODA-FABRIK (D.R.-P. 238980).-It is now found t h a t the compounds previously described (Abstr.1907 i 226) can be prepared from 1 1'-dianthraquinonyl-2 2'-dialdehyde by reduction with either an alkaline solution of sodium hyposulphite or with zinc in concentrated sulphuric acid solution. F. M. G. M. Decomposition of Alkylidenehydrazines Conversion of Ionone and +-Ionone into the Corresponding Hydrocarbons C,3H22. NICOLAI M. KIJNER (J. Russ. Phys. Chem. SOC. 1911 43 1398-1 402).-The decomposition of iononehydrazone in presence of potassium hydroxide is an exothermic reaction and gives rise t o a-ionane CHEt:CH=CH<CMeLC-$>CH CMe *CH which is a colourless liquid with a faint odour of turpentine b. p. 220-221°/747 mm. Dto 0.8530 n 1.4784. It readily oxidises in the air combines with 4 atoms of bromine and in acetic anhydride solution gives a raspberry-red coloratiolz with R drop of sulphuric acid.It shows the normal molecular refraction whereas the similar hydrocarbon correspondiog -i. 120 ABSTRACTS OF CHEMICAL PAPERS. with p-ionone should exhibit considerable exaltation owing t o the presence of conjugated double bonds. +-Io~mne C kiEt:CH*CH2*CMe:CH*CH2*CH:CMe ('t) obtained in a similar manner from +-ionone is a colourless faintly-smelling liquid b. p. 224-225'/751 mm. Di0 0.8151 73 1.4725; it rapidly turns yellow in contact with the air unites with 6 atoms of bromine and is converted into a-ionane when its acetic acid solution is boiled with a small quantity of sulphuric acid. The formula given above is of doubtful accuracy as the hydrocarbon does not exhibit optical exaltation. T. H. P. Crystalline Form and Optical Characters of Pinocampheol Methyl Xanthate.N. I. SURGUNOFF (Zeitsch. Rryst. Min. 1911 50 62-63; from Bull. SOC. Nat. Moscow 1907 543-551).-The crystals of pinocampheol methyl xanthate (Tschugaeff Abstr. 1908 i 93) are orthorhombic with a b c = 1.3747 1 0.9787. Constituents of Essential Oils. The Constitution of the Active Caryophyllenes ; Transformation of the Active Caryophyllenes into Monocyclic Derivatives. FRIEDRICH W. SEMMLER and ERWIN W. MAYER (Rer. 1911 44 3657-3679).-The authors have subjected caryophyllene to the action of ozone and studied the decomposition products of the ozonide so formed. They consider that crude caryophyllene is composed chiefly of three cnryo- phyllenes namely Deussen's inactive a-caryophyllene and two active caryophyllenes which they name terp-caryophy Ilene and lim-caryo- phyllene and to which they assign the respective provisional formulae L.J. S. CMe CH C'Me CH \ /\ \/ \ CH Me \ \ /,! \ \ CH Me Commercial caryophyllene when dissolved in ethyl chloride and subjected to the action of ozone yields a soluble ozonide C,,H,,O together with a small quantity of an insoluble ozonide which probably contains seven or eight atoms of oxygen. When the soluble ozonide is heated in glacial acetic acid solution it yields carbon dioxide and formaldehyde together with n mixtmre of acidic and neutral products. From the acidic products a keto-acid C,,H,,O a diketo-acid C,+H,,O and an acid C,H1,O were isolated. l'he keto-acid CllH1,03 is a pale yellow mobile oil of b. p. 183-187'/11*5 mm.D20 1.040 a +44' rt; 1.4677. Its siluev salt was analysed. The methyl ester has b. p. 139-142O/15.5 mu. D20 0.9913 n$ 1,4527 a? +42'. The samicarbazone has m. p. 183'. When oxidised with nitric acid the keto-acid yields dimethylsuccinic acid and dibasic caryophylkenic acid C9H1,0,. The latter forms a non- crystalline syrup of b. p. 215-218'/9 mm. 222-225'/13 mm. It isORGANIC CHEMISTRY. i. 121 remarkably stable towards nitric acid. The silver and copper salts were prepared. The methyl ester. has b. g . 127-131"/11 mm. D20 1.0456 n$ 1.4462 a + 44'. When boiled with acetic anhydride caryophyllenic acid yields an anhydride of b. p. 152-158'/10 mm. D20 1.1399 n$ 1.4755 a -25". Similar products were obtained when the keto-acid was oxidised by Iwomine in alkaline dolution.Oxidation with permanganate also gave caryophyllenic acid to which the formula CH ~~CMe(Co2H2>CMe \CIqCO,p) is assigned. The diketo-acid C,,K,,O is a viscous yellow oil of b. p. 239-2.32'/ 11.5 mm. D20 1.0830 nZ1.4804 az,O +41'. Its silver salt begins to darken at 130' and has m. 1). about 3145". Its methyZ ester has b. p. 184-188°/12 mm. DZo 1.047 a$ +38" n D 1.4680 With semi- clzrbazide hydrochloride i t gives no product of definite m. p. When oxidisod with nitric acid it. yields succinic acid and caryophyllenic acid. On kreatment with bromine in alkaline solution it yields caryophyllenic acid together witlh a mixture of acids of high boiling point. The acid CsH1402 has b. p. 120-128"/9 mm. DZo 0.9527 nD 1.4457 [a] + 17' and is monobasic.Its methyl ester has b. p. 64-6So/ 9 mm. D20 0.922 [a];' + 20' nD 1.4326. From the neutral portion (see above) a ketone CioH180 a probable keto-aldehyde C11Hls02 a diketone C1,HZoO2 and a deketo-aldehyde C,,H,,O were isolated. The ketone C,,H,,O is a mobile pale green liquid of b. p. 73-76"/ 11 *5 mm. It has DZo 0.8823 9b 1 *4387 - 7". Its semicarbaxone has m. p. 176'. When reduced by sodium :tmalgam i t yields an aZcohoZ Ci,H200 b. p. 87-89"/11*5 mm. D20 0.8707 7 ~ 1.4507 [a] - 6'. This on treatment with phosphorus pentachloride passes into the corresponding chloride (b. p. 70-73'/10 mm. D20 0*882) which when heated with quinoline yields the hydrocarbon CloH16. The latter has b. p. 50-54"/11*5 mm. D20 0.812 72 1.4410 a;' - 6'. When oxidised by bromine in alkaline solution the ketone yields carbon tetrabromide together with a nao~,obasic acid C,H,,P b.p. 131-133'/13.5 mm. D23 0.9773 12 1.4500 a - 7" the szlver salt of which had m. p. 219' after darkening at about 160". The methyl ester has b. p. 86-89'/15 mm. D23 0.9208 n 1.4360 a -5.5'. The amide has tn. p. 114". On oxidation with nitric acid the ketone yields an acid C,H,,02 b. p. 119-122"/12 inm. DZo 0.972 nz 1.4457 uz +7*5'. This yielded a methyl ester of b. p. 69-73"/15 mm. D20 0.9369 n$' 1.4307 a$ 3-22' and an umide rn. p. 115-116'. The formation of these compounds is represented by the scheme on p. 122. The diketone C,,H after treatment with permanganate to destroy any aldehyde present is a colourless mobile oil b. p. 137-142'/9 mm. DZo 0.9600 n 1.4677 uz +34".The b. p. mas unaltered by a second treatment with permanganate whilst the follow- ing values were found for the remaining constants D20 0.9598 nD 1.4622 uD + 39". On oxidation with nitric acid the diketone yields dimethylsuccinic acid and caryo- phyllenic acid. Oxidation with bromine in alkaline solutiorl leads to the same products. The dikuto-aZdzhyde Cl4H2,O3 is a viscous yellowish-green oil of I t s amide melts at 9 6 O . Its semicarbaxone had m p. 219O.i. 122 ARS'I'RACTS OF CHEMICAL PAPERS. b. p. lSl-l84O/13 mm. DZo 1.0280 nz 1.4774 a? -25". It does not yield a uniform semicarbazone. When oxidised with perman- ganate it yields the acid CI4Hz2O4 (see above). Nitricacid converts i t into succinic acid and caryophyllenic acid. CMe CH \ /\ \/ \ CH Me L terp.-Caryophyllene. HNOs CHMe ,f CHMe CHMe HC-CMe NaOH+Br HC-GMe HC-CMe \ \ \ cH,* CO Me CH;CO,H CO,H Ketone C,,H,,O. Acid C9H1,0,. Acid CsH,,O,. Deusseri's c:qwphyllene was converted into caryophyllene dihydro- chloride which on treatment with methyl-alcoholic potassium hydroxide yielded the previously-described '' recovered " dextrorotatory caryo- phyllene (Abstr. 1911 i 73). An attempt to transform this through the nitrosite into Deussen's la?vorotatory caryophenyllene was unsuccessful. Reduction of the blue nitrosite (Deussen Abstr. 1907 i 945) led to the formation of a substance C,,I-12?N which is probably an amine. It has in. p. 148-150"/13 mm. DZo 0.929'7 a2,0 + 1 3 O nz 1.5030. H. w. New Philippine Essential Oils. BENJAMIN T. BROOKS (PhiZippine J. Sci.1911 6 333-351. Compare Abstr. 1911 i 1000).-The essent,ial oil from the fl.owers of Michelia Zonpfolia contains linalool eugenol methyl ether and methylbutyric and acetic acids and a very small percentage of thymol. The leave.. of Toddalia asiatica (L.) (T. Acdeata Pem. Kurz) yield 0.08% of an essential oil which gave the following constants n3,0 1.4620 Di,O 0.9059. The oil is largely linalool but also contains a white crystalline camphor-like compound m. p. 96*5-97O which is very unstable. The lenves of Clausena anisum olens yield 1.20% of an essential oil with the following constants n? 1.5235 Dg8 0.963 ester number 3.6. It contains chavicol methyl ether to the extent of 93%. About 0.2% of an essential oil with 0.850 is obtainable from the leaves of LimnophiZn sp.Orange-peel oils were also examined the naranjita variety giving a much greater yield than the cajel. The two oils resemble oneORGANIC CHEMIS'I'ILY. i. 123 another very closely the former having constatits it 1.4700 [u] 90*85" ester number 8.0; the latter ng 1.4675 Di 0.8390 ester nnmter 8.5. The leaves of Citrus decumana yield 1.7% of an essential oil with constants n3,n 1.4644 D~~0*8700 [a] 22-90' ester number 10. It contains tlipenteue and linalool and a trace of an aldehyde. Tho oil from the leaves of Citrus hyatrix has the following constants 7tE 1.4850 IXi 0.9150 [a] - 10*50° ester number 50.2. W. G. The Essential Oil of Seseli bocconi. LUIGI FRANCESCONI and X. SERNAGIOTTO ( A t t i R. Accad. Lincei 191 1 [v] 20 ii 481-4S6).- The essential oil of this plant has been obtained by distilling it in steam By fractional distillation OF the oil a number of fractions mere isolated of which the more volatile consist of terpenes I-pinene and P-phellandrene having been identified.The oil also contains compounds with carbonyl groups (probably aldehydes) and ethers and alcohols are also present. R. V. S. Chemistry of Caoutchouc. 111. Theory of Vulcanisation. 11. DAVID SPENCE [with J H. SCOTT] (Zeitsch. Chem. Ind. Kot?t?oidp 1911 9 300-306. Compare Spence and Scott Abstr. 1911 i 657).-Further experiments have been made on the extrdction of sulphur from vulcanised caoutchouc by treatment for measured time intervals wit ti equal successive quantities of boiling acetone. These show that equilibrium between the adsorbed sulphur and that in the acetone solu- tion is rapidly attained aud this fact is regarded as favourable to the interpretation which has already been given to the exponential form of the extraction curves.From two series of observations made with the same mixture of para-caoutchouc and sulphur which had been subjected to the vulcnnisiug process for different periods of time it i t is found that the proportion of chemically combined sulphur increases with the period of vulcanisation and that the initial portions of the extraction curves corresponding with the removal of the free sulphur are also different in the two cases. When a non-vulcanised mixture of caoutchouc and sulphur is similarly extmctcd with boiling acetone the form of the extraction curve obtained is qliite different,.The removal of the sulphur from the unvulcani>od mixture is how- ever also a slow process by reason of the inclusion of the free huiphur in tbe jelly-like mass which the non-vulcanised caoutchouc forms in contact with the boiling acetone. An extraction experiment with ebonite. gave an extraction curve differing from those obtained with samples of vulcanised caoutchouc but in this case also there appears to be it considerable amount of sulphur which is present in the chemically combined form. H. M. D. Brazilian Copal. STANISLAUS MACHENBAUM (Arch. Pharrn. 19 12 250 6-12).-The copal was red to yellow in colour and was in small pieces showing a thin weathered layer. It sintered at 1 3 7 O melted completely at 160° and had the following percentage solubilities iui.124 ABSTRACTS OF CHEMICAL PAPERS. the solvents named alcohol 76 acetone 80 alcohol and ether 92 light petroleum 20. The copal gave the following constants acid numbers ( a ) direct 123.2 ( b ) indirect 128.5 ; sapouification numbers (a) cold 136.2 (6) hot 144.2. An ethereal extract of the resin was shaken with ammonium carbonate solution which (1) extracted two acids of which one brazil- copalic acid C24H4003 m. p. 170-175° yielded a lead salt insoluble in alcohol and (2) precipitated ,z mixture of two acids of which one m. p. 195-200° gave a lead salt insoluble in alcohol. Sodium carbonate solution then extracted from the ethereal solution two acids of which brazibopalolic acid Cz2€13s02 m. p. 95-10O0 gave an insoluble lead salt.The residual ethereal solution yielded nothing to potassium hydroxide solution but on steam distillation furnished a volatile oil boiling chiefly at E245-255° and a residue of a-6raxil- copaloresen as a brownish-yellow viscid mass. The portion of the copal insoluble in ether was dissolved in a mixture of alcohol and ether and extracted with potassium hydroxide solution which removed n mixture of resin acids. These were dissolved in alcohol precipitated as lead salts by lead acetate regenerated and separated into two portions by treatment with cold alcohol the soluble portion is a-brazilcopalinic acid C H 3o02 m. p. 180-1 S5O. The solution after extraction with potassium hydroxide contained P-brazilcopaloresen arid a little volatile oil. All the substances described are amorphous.The acids give phytosterol-like reactions and their acid numbers are recorded. T. A. H. Columbia Copal. STANISLAUS MACHENBAUM (Arch. Pharrn. 191 2 250 13-19).-'l'he copal was in large pieces and had a slight turpentine-like odour. It sintered at 120° melted completely at 155O and had the following percentage solubilities ether 56 alcohol 78 alcohol and ether 90 light petroleum 18. Its constants were as follows acid numbers ( a ) direct 105 ( b ) indirect 106.1 saponifica- tion numbers ( a ) cold 106.8 (b) hot 110.6. An ethereal extract of the resin was extracted with (1) ammonium carbonate solution and (2) sodium carbonate solution. I n each case a mixture of two resin acids was extracted and was separated into its components by solution in alcohol and precipitation by lead acetate.The acid giving an insoluble lead salt alone was examined in each case the other being viscid and intractable. As in the case of Brazilian copal (preceding abstract) ammonium carbonate precipitated two resin acids from the ethereal extract; of these the one giving an insoluble lead salt had m. p. 170-175O. That extracted by ammonium carbonate is cotumbia- copnlic acid C22H4003 m. p. 145-150O. The acid subsequently removed by sodium carbonate is columbiacopalolic c~cid (;122H4002 m. p. 90". The residual ethereal extract contained volatiIe oil boiling chiefly at 2 I 0-220° and brqwn viscid a-colwmbiacopalores~?~ The portion of the crude copal insoluble in ether was dissolved in a mixture of alcohol and ether and extracted with potassium hydroxide solution which removed a-cotunzbiacopalinic acid ClqH240 m.p. 180-1 85O soluble in cold alcohol and ~-colurnbiacopalznw acid C,Hz,03 xn. p.ORGANIC CHEMISTRY. i. 125 1 go’ soluble in hot alcohol. solution. and phytosterol-like reactions of the resin acids are recorded. ~-Co~urr~bic6copa~oresen reuaiued in the The acid numbers All the products mentioned are amorphous. T. A. H. So-called Chicle Gum. J. E. QUINTUS Bosz and N. H. COHEN (Arch. Phawn. 1912 250 52-62). -Tschirch and Schereschewski’s work on this material (Abstr. 1905 i 685) has been repeated and it is shown that their a-chiclalban is a-amyrin acetate their P-chiclalban is a mixture of esters of lupeol and /3-amyrin their y-chiclal ban con- tains as its principal constituent a substance C,GH,i,O C57H1,40 or C,,T3,,,0 m.p. 68’ which on admixture with Hesse’s p-cerotinone nielts a t 66-68’ and is possibly identical with that subst.ance (Abstr. 1893 i 57). Chiclafluavil is a mixture of all the substances mentioned above. On steam distillation chicle ‘‘ gum ” yielded a minute quantity of an alkaline distillate with an odour of amines and on hydrolysis by alkalis furnished acetic hexoic and cinnamic acids. The portion of the “gum” insoluble in acetone is brittle and has none of the properties of caoutchouc 90 that the properties of chicle ‘‘ gum,” which render it suitable for “chewing gum” manufacture do not depend on the presence of caoutchouc-like substances. T. A. H. Occurrence of Chitin. EDMUND 0. VON LIPPMANN (Ber. 1911 44 3716-3717).-A colourless thin tough skin foxming a light grey amorphous powder when dry which collected on the surface of some waste liquors in a sugar factory which had been set aside for several months is shown to be composed of chitin produced by bacterial action.E. F. A. Lutein from Yolk of Egg. RICHARD WILLSTATTER and HEIN- XICH H. ESCHER (Zeitsch. physiol. Chern. 1912 76 214-225).-The chemically indifferent yellow pigments of plants and animals are divided into the hydrocarbons of the carrotene group C40H56 soluble in light petroleum and the oxygen compounds of the xanthophyll group C40H5G02 soluble in alcohol (Willstiitter and Rlieg Abstr. 1907 i 865). Lycopene the colouring matter of tomatoes has been shown (Willstiitter and Escher Abstr. 1910 i 330) to belong to the carrotene group and it is now proved that lutein from the yolk of eggs is a xanthophyll isomeric with and closely related to that derived from chlorophyll.The methods of separating lutein from the phosphatides fats and cholesterol of the yolk are described the pure pigment crystal- ises slowly from carbon disulphide in well formed prisms or quickly in fire-red conglomerates of pointed microscopic needles m. p. 195-1 96’ (corr.). It crystallises from methyl alcohol in prisms with V-shaped indentations which arc amber-yellow with metallic lustre. Lutein forms an additive compound with iodine in ethereal solution ; the iodide is a dark violet powder consisting of microscopic pointed needles. It absorbs oxygen to the extent of 23% of its weight.i. 126 ABSTRACTS OF CHEMICAL PAPERS.I n alcoholic solution it. shows ahsorption bands in the blue and indigo- blue corresponding with thwe of xauthophyll froni leaves but differing from carrotene. E. F. A . [Preparation of Thionaphthen Derivatives.] KALLE & Co. (D.R.-I?. 239089. Compare Abstr. 1911 i 666 667 1009).-An account of the preparation of substances having the general formu1:t RS*C,H,(S*CH,.CO,H)*CO,H some of which have been previously described (Abstr. 1911 i 666). The following new compounds are mentioned 2-Carboxy-5 -methylthio~?'enylthiolacetic acid yello wish-white needles m. p. 220' (decomp.). 3-Keto-6-methyZth~ioZ-( I j-thionu~hthen-2-c~rbox?/lic acid :i colourl ess powder and 3-keto-6-nzeth?/ZthioZ-( 1 )-ti't,ionccphthen glistening needles m. p. 133-134'.F. M. G . 311. [Preparation of Thionaphthen Derivatives.] KALLE SS Co. (D.R.-P. 239092 j.-o-Nitro-m-xylidine was diazotised and converted by the action of potassium cyanide and copper sulphate into 2-nitro-m- zylonitrile needles m. p. 126'; this when heated a t 100° during twelve hours with 80% sulphuric acid yielded 6-nitro-2 4 -di.r,wtl'yl6enxoic acid yellow needles m. p. 180° and on reduction furnished the correspond- ing 6-amino-S 4-dimethylbenzoic acid :t yellow crystalline powder m. p. 126' (decomp.). The foregoing amino-acid when diazotised xanthogenated and treated with chloroacetic acid yielded 4-carboxy-m- xyZyZ-5-thioZacetic mid CO,H.C,H,n'le,*S.CH,.CO,H a microcrystallin e powder ru. p. 158-159' which on fusion with sodium hydroxide furnished keto-4 6 - d i r n e t ? ~ y l t ~ ~ i o n a p ~ ~ t ~ ~ e n c ~ c r ~ ( ~ ~ ~ ~ c acid red flakes arid was subsequently converted in to kelo-4 6 -clii,ietl~?llt?~ioi~(6p~~t~'en needles m.p. 93" which rapidly darkens on exposure to light. F. &I. G. ill. [Preparation of Anthraquinonethioxanthones.] FRITZ ULL- MANN (D.R.-P. 238983. Compare Abstr. 1911 i 1010).-Anthra- puinone-thioxanthorte orange-red leaflets m. p. 335' is prepared by healing anthraquinone-l-o-thiolbenzoic acid with phosphorus penta- chloride in nitrobenzene solution ; t b e anthraquiijone-thioxanthone m. p. 272O described previously (Abstr. 1910 i 270) has now been obtained by fusing anthraquinone-2-o-thiolbenzoic acid with p-toluene- sulphonyl chloride at 205O whilst anthraquinonyl-1 5-cli-o-thiol- benzoic acid and phosphorus pentachloride furnish an ccr~tl~raquinone- dithiozanthoue glistening orange needles which do not melt at 350".F. M. G. M. LPreparation of Thioindigo " Derivatives.] KALLE & Co. (D.R.-P. 239673).- When 3-oxy-( l)-thionaphthen-?-carboxylic acid arid its derivatives containing a free or substituted amino-group in the benzene nucleus are oxidised in either alkaline solutioii or neutral suspension they yield '; thioindigo " derivatives. " 6 6'-Diantinothioindigo " was obt;tined as a brown flocculent pre- cipitate by the oxidation of an aqueous alkaline solution of 6-amino-ORGANIC CHEMISTRY i. 127 3-oxy-(l)-thioiiaphtheu-2-carboxylic acid with air a t 70-80" ; cjthor MAX SIEGFIUED (Zeitsch. pluysio2. Cheni. 1912 '76 234-237).-The platinichloride of active lysine when dried over sulphuric acid has the composition C,H,,U,N,,PtH,CI,,EtOH and crystallises in needles more slender and darker than those of the platinichloride of inactive lysine which forms stouter paler yellow prisms having the composition C6H1,0,N,,PtH,Cl,.Racemic and active lysine may be sharply differentiated in this manner. oxidising agents can also be employed. F. ill. 0. nil. Lysine Platinichloride. E. F. A. Hzmopyrrole. RICHARD m T ~ ~ ~ ~ ~ B and ~ A S U H I K O ASAIIINA (Ber. 1911 44 3707-3710).-Haemopyrrole from haemjn or from chlorophyll has been shown to contain phyllopyrrole C,H,,N iso- haemopyrrole C,H&N and another base C,H,,N. The constitutions 2 3 4- and 2 4 3-dimethylethylpyrrole respectively were ascribed to the two latter compounds (Willstatter and Asahina this vol.i 41) but further investigation is necessary as neither of them proves to be identical with the 2 4-diruethyl-3-ethylpyrrole synthesised by Knorr and Hess (Abstr. 191 1 i 1019; compare also Fischer and Bartholomiius this vol. i 50). The synthesis of Knorr and Hess is confirmed; 2 4-dimethyl- 3-ethylpyrrole has b. p. 84"/10 mm. 197'/710 mm. Dfo 0.913. The styphnats forms four-sided prisms rn. p. 136' ; the cldoropicrute gives pri~ms m. p. 140O. On oxidation with nitrous acid methylethyl- maleiniinideoxime is obtained cryst$allising in prisms m. p. 215-21 6' (Knorr and Hess give 201'). The pyrrole base was reduced with hydrogen iodide and phosphorus a t 240° and finally with platinum and hydrogen.The pyrrolidine obtained has b. p. 145" and forms a plutirddoiide crystallising in pointed prisms m. p. 220° and an u-nu~hthylcarbamide crystnllising i n irregularly-defined rhombic plates m. p. 109-1 10'. It is essentially different from isohsmopyrrolidine. ~ I G I MARINO and v. SQUINTANI (Atti R. Accad. Lincei 1911 [v] 20 ii 666-670. Compare Marino Abstr. 1908 ii 833)- When absolutely dry recently sublimed selenious anhydride is mixed with an equimolecular quantity of a solution of pure piperidine in arihydrous benzene cooled with ice a colourless crystalline mass is deposited. The reaction is complete in eight or ten hours. The product after being washed with anhydrous benzene gives on analysis figures corresponding with the formula C5H,,N*Se0 but allowance has to be made for absorbed water owing to the extremely hygroscopic nature of the substance.The compound has m. p. 70-71' but traces of water may lower it t o 64-65'. It probably reacts with alcohol but the reaction product has not been isolated. E. F. A. Asymmetrio Selenites. The piperidine group is not involved in the reaction. R. V. S. Cyclic Ammonium Bases. JOHANNES GAUAMER (J. pr. Ci~en~. 1911 [ii] 84 817-820).-A reply to Decker and Kautman ( Abstr.,i. 128 ABSTRAOTS OF CHEMICAL PAPERS. 1911 i SO?') who erroneously attributed to the author the view that the cnrbinol bases have in all cases the structure of amino-aldehydes or ketones. F. B. Action of Methylamine and Aniline on Benzoyldehydracetic Acid. [Mutual Replacenient of Ammonia and Amines in Pyridone Derivatives.1 PAVEL I. PETRENKO-KRITSCHENKO and JOH. SCHOTTLE (Ber. 1911 44 3648-3654. Compare Abstr. 1911 i 102O).-The interaction of benzoyldehydracetic acid with methylamine and aniline has been studied whereby the methyl- and phenyl-lactams of benzoyldehydracetic acid have been obtained. These have m. p. 188" and 203" respectively. Unlike the lnctam described previously (Zoc. cit.) neither of these compounds yields a pyridonecwboxylic acid when warmed with alkali. The methyl-lactam on treatment with hydrochloric acid yielded 2 6-diphenyl-4-pyridone the plcctinichloricle of which m. p. 218-221° (clecomp.) was analysed. When similarly treated the phenyl-lactam yielded 2 6-diphenyl-1 4-pyridone. The methyl- and phenyl-lactams were also prepared by the action of alcoholic solutions of methylamine and aniline on the lactam. Con- versely the methyl-lactam when treated with alcoholic ammonia yields the lactam which was identified by conversion into 2 B-diphenyl- 4-pyridone-3-carboxylic acid and 2 6-diphenyl-4-pyridone ; on trent- ment with an alcoholic solution of aniline i t yields the phenyl-lactam.Similarly the anilino-group of the phenyl-lactam is replaceable under the action of ammonia or methylamine. H. W. The Condensation of Acetonedicarboxylic Ester with Aldehydes Ammonia and Amines. PAVEL I. PETRENKO- KRITSCHENKO (J. pr. Chem. 1912 [ii] 85 1-37).-A rksumQ of the results of already published investigations by the author and various co-workers (Abstr. 1906 i 452; 1907 i 708; 1908 i 564; 1909 i 605 959; 1910 i 188).D. F. T. Preparation of Derivatives and Homologues of Indole. GESELLSCHAFT FGR TEERVERWERTUNG (D.R.-P. 2381 38).-When aryl- hydrazones (or their keto- or aldehyde derivatives) are heated with zinc chloride they furnish indole derivatives. 2-Methylindole was obtained in 75% yield by heating acetonephenylhydrazone (1 part) in 3 parts of solvent naphtha with zinc chloride (1 part) at 150" during one hour extracting with water and subsequently fractionating in a vacunm. 3-Methylindole previously prepared by E. Fischer in 38% yield was produced in 80% yield from propionaldebydephenylhydrazone a t 200° whilst ethyl phenylhydrazonepyruvate furnished a 60% yield of 2-indolecarboxylic acid at 130". F. M. G. M. New S y n t h e s i s of Benzylidine-2- methylquinoline. VON ISMAILSKY (J.pr. Chem. 1912 [ii] 85 90-92).-1n the presence of sodium hydroxide solution o-aminobenzaldehyde slowly condenses with excess of styryl methyl ketone yielding benzylidene-2-methyl quinoline. The product agrees entirely with previous descriptionsORGANIC CHEMISTRY. i. 129 (Wallach and Wusten Abstr. 1883 1096 ; Jacobsen and Reimer Abstr. 1884 335 ; Doebner and Peters Abstr. 1890 1'76 ; Eibner Abstr. 1901 i 64). D. F. T. Condensation of para-Quinones w i t h Indolee and Pyrroles Containing Hydrogen in the 3-Position. RICHARD MOHLAU and ALFRED REDLICH Ber. 191 1 44 n60Fi-3618).-a-'Methylindole arid p-benzoquinone (2 mols.) react in boiling alchhol t o form 2-methyl- .inclyZ-3-bonxopuinone CH<Co.CH>C-C<C A 1 >NH dark violet CH-CO C Me bronze needles m.p. about 185' a n d quino1"in quantitative yield. That the reaction occurs directly a t the 3-hydrogen atom not a t the iruinic hydrogen atom is proved not only by the fact that the colourless buco-compound obtained by the action of hydrazine hydrate forms a diacetnta m. p. 132' (a triacotnte should be formed had the reaction occurred in position l) but also because 1 2-dirnethyl- indole and p-benzoquinone yield in a similar manner an almost quanti- tative amount of 1 2-dirnat~~y1ind~l-3-benzoqzcinone7 G16H1302N m. p. about 1 GO" violet-black needles. I n a similar manner 2-methylindole and toluquinone yield a corresponding substance Ci,H,802.N m. p. about 195' (decomp.) reddish-violet needles ; the colourless dzacetate of its leuco-compound has m.p. 146". 2-Phenylindole and p-benzo- quinone give about 40% of 2-phenylindyl-3-benzoquinone7 C H130,N m. p. about 205' blue needles ; 2 5-dimethylindole reacts wlth p-benzoquinoue and with toluquinone to form about 90% of 2 :5- dimethylindyl-3-benzoquinone Cl,H,,02N m. p. about 301" (decomp.) violet-black bronze needles and 3 5-dimethyZindyl-3-tol~quinon~~ C17H,,02N reddish-violet needles. As IS to be expected from the preceding pyrroles unsubstituted in positions 3 and 4 react with p-quinones (4 mols. two of which are utilised in oxidising the initially-formed leuco-compound) to form diqninonylpyrroles ; thus 2 5-dimethylpyrrole yields 3 4-diquinonyl- 2 3-dimeth,ylpyrrole9 black microcrystalline powder whilst 5-phenyl-2-methylpyrrole yields 3 4-diquii~onyl-5- phenyl-2-methylpyrrole C23H1504N brownish-black powder.Whilst with the preceding indoles and pyrroles only one nucleus enters the benzoquinone mole- CH,-CHMe 9. /- \ cule it is found that the more ' strongly basic 2-methyldihydro- indole reacts like the following bases with p-quinones in hhat CHMe*cH two nuclei enter the quinone molecule ; thus 2-methyldi- hydroindole yields a su6stance (annexed formula) m. p. 18'To9 brown needles ; met h ylaniline y ieldu bismethylccnilinoqucinone (NPhMe),C6H2O reddish-brown leaflets ; tetrahydroquinoline yields biststrahydroquino- Zinoquinone (C9NH1,),C,H202 m. p. 189O brown needles and 4-methyltetrahydroquinoline yields bis-6-methyltet~ahydroquinolino- CMe:~*C,H,O NH<CMe:C.C 6 4 2 \-/ 0 quinone !C,H,MeN) Z:,H,O m p.197". c. 5. VOL. CII. i. ki. 130 ABSTRACTS OF CHEMICAL PAPERS. Products of the Condensation of 9-Methylcarbazole and Phthalic Anhydride. FRANZ EHRENHEICH (Monatsh. 191 1 32 1103-1 11 4. Compare Scholl and Neovius Abstr. 191 1 i 567).- By the interaction of molecular proportions of 9-methylcarbazole and phthnlic anhydride the main product is 9-methylcarbazole-3-phthaloylic acid C H 4 ~ / U H * C 0 C,H,* CO,H together with small quantities of 9-methylcarbazole-3 6-diphthaloylic acid CO,H C,H4*CO* C,H,ywC,H,* CO*C,H,*CO,H. When twice as much phthalic anhydride is used the quantity of the latter is increased considerably. 9-Methylcarbazole is conveniently prepared by the action of methyl iodide or of methyl sulphate at the ordinary temperature on potassium carbazole.9- Methp Zcavbaxole- 3-pJhtha ZoyZic acid prepared by the interaction of the components in benzene solution with aluminium chloride crystal- lises in large well-formed rhombs m. p. 232'; i t shows a character- istic cherry-red coloration with Concentrated sulphuric acid changing t o green or. the addition of strong nitric acid. The methyl group is only very slowly and partly eliminated on boiling with hydrogen iodide and the attraction of alkyl to nitrogen is apparently increased by the phthaloyl group; indeed no trace of halogen alkyl is obtained on heating the diphthaloyl derivative with hydrogen iodide. The same methyl ester is obtained from the silver salt and methyl iodide or from the acid chloride and methyl alcohol; i t crystallises in monoclinic prisms m.p. 146". 9 - Methyl car baxole- 3 6 -diphthaZop Zic acid cry s tallises in slender needles m. p. 330O; the cherry-red coloration with sulphuric acid turns yellow on the addition of strong nitric acid. The dimethyl ester crystallises in large colourless prisms m. p. 196". 2 3 6 ; 'I-DiphthaZoyZ-9-metJ~ylcarbazoZe C H 4 < ~ ~ > C H 2 ~ / c H 2 < C O > C 6 1 r 4 ' co prepared by heating 9-methylcarbazole-3 6-diphthaloylic acid with sulphuric acid at 90' (compare Scholl and Neovius Zoc. cit.) crystal- lisea in reddish-yellow plates which have not melted at 400". With concentrated sulphuric acid a bluish-violet solution is obtained which becomes orange when strong nitric acid is added. E. F. A. Ester Acids of Thiocarboxylic Acids with Aliphatic Alcobol Acids.V. BROR HOLMBERG (J. pr. Chem. 1911 [ii] 84 634-636. Compare Abstr. 1910 i 361 834).-A detailed account of the action of amines towards the following acids xanthoacetic acid OEt*CS*S*CH,*CO,H ; ethyl dithiocarboglycollic acid SEt*CS*O*CH,*CO,H ; dithiocarbodiglycollic acid CO,H*CH,*S.CS-O*CH,*CO,H ; carbo- dithioglycollic acid CO(S*CH,*C0,H)2 and trithiocarbodiglycollic acid CS( S*CH,*CO,H),. The previously -observed formation of diphenylcarbamide by the action of aniline on xanthoacetic acid is considered by the author toORGANIC CHEMISTRY. i. 131 be due to the intermediate formation and decomposition of an additive compound with aniline according to the following scherrie CO H* C tI,*S*CS*OEt-+ C0,H.C H,*S.C(S*NH,Yh)(NHPh) QEt -+ CO,H*CH,*SH + EtOH + H,S + CO(NHPh),.Evidence in support of the author's view is furnished (1) hy the non-formation of diphenylcarbarnide in acid solution and in the absence of excess of aniline and (2) by the isolation of similar additive compounds of the thiocarbarnylglycollic acids with amines (see b+low). P-Phenylethylamine reacts with xsnthoacetic acid yielding an oily thiouret hane C fl MePh N H CS 0 Et . Ethyl dithiocarboglycollic acid forms with aniline in aqueous solution the ardine salt SEt=CS*O*CO,*NH,Ph m. p. 77.5-78" ; when heated with aniline in alcoholic solution diphenplcarbnmidd is produced. Dithiocarbodiglycollic acid reacts with ethylamine to form ethyl- thiocltrbamylthioglycollic acid and the anhydride of ethylthiocarbnmyl- glycollic acid mentioned below.With aniline in ethereal solution i t yields tile aniline salts C,H605Q0,2 NH,Ph lustrous pale yellow leaflets m. p. 97-97.5" and C,H,O,S,,NH,Ph m. p. 110-1 10.5". When heated with aniline in aqueous solution dithiocarbodi- glycollic acid gives rise to a mixture of substances the nature of which depends on the ratio of aniline t o acid and the temperature and duration of the reaction ; the following compoun Is were isolated from the product s-diphsnylthiocitrbamide phenylrhodanine trithiociwbo- d iglycollic acid g!ycollic acid t hiog I y co I lie acid p hen y 1 t hiocar ba m y 1- glycollic acid and its anhydride and phenylthiocarbamylglycollanilide. Trit hiocarbodiglycollic acid re'w t a with primary amines yielding thioglycollic acid and rhodanines (compare A bstr.1910 i 361); with P-phenylethylamine it forms 3-P-p?~enylethylrl~oda.nine s-cs>N CH MeP h bO*CH pale yellow tabular crystals m. p. 11 1-1 12'. Ethyltrithiocarb~glycollic acid and aniline in aqueous solution yield phenylrhodanine and ethyl trithiocarbonate. X-S,ibstituted derivatives of thiocarbamylglycollic acid are readily obtained by the intecaction of amines and ethyldithiocarboglycollic acid. EtiLylthiocarbamylg1;ycoZlic acid NHEt*CS*O*CH,*CO,H prepared from ethylamine in aqwous solution crystallises in stellar aggregates of smill white needles m. p. 97.5-98' ; the s o d i u ~ i ~ salt is amorphous; the barium salt (NEIEt%S-O*CH,*CO,),B~,3H2O forms colourless plates. It is oxidised by bromine to ethylcarba,nylyZ~collic ucid colourless prisms m.p. 85-86" and when warmed in aqueous sol 11 tio u forms a n anhydride (2 - thion-3 - ethyl - 4-oxozoliclone) bH,*CO '-">NE t which crystallises in colourless Iplstes m. p. 43-10*5". L)iethykhiocarb~myZ~lycolZic acid NEt,*CS*O*CH,*CO,H prepaid from diethylamine crystallises in flat colourless prisms m. p. 90.5 -9 lo VOL. CII. i. I?i. 132 ABSTRACTS OF CHEMXCAL PAPERS. and yields crystalline sodvum and barium salts; the eth$ ester is an oil. Phen y Zthiocarbumplyl yco Elic acid NHPh- CS 0 CYH,*CO €1 m. p. 11 1-1 12O obtained together with phenylrhodanine and diphenyl- carbamide by heating aniline with ethyldithiocarboglycollic acid in aqueous solution crystallises with one molecule of acetic acid in long colourless prisms which lose their acetic acid on exposiire to air ; the d i e c o l a salt and barium salt (NHPh*CS*O*CH2*CO,)Ba,3H,O were analysed.It readily loses water forming the anhydride (2-thion- 3-phenyl-4-oxaxolidone) I ">NPh which crystallises in stout irregular plates or short prisms m. p. 172-173' and dissolves in aqueous sodium carbonate to form the sodium salt of the original acid. When heated in neutral or alkaline solution it yields glycollic acid and diphenylcarbamide ; in aqueous ammonia phenylthio- carbamide is produced. Oxidation with potassium permanganate yields phenylcarbamylglycollic acid. Phemy Ethiocarbamy 29 Zycolluni Zide NHPh*CS-O*C H COO NHPh pre- pared by heating the acid with aniline i n aqueous solution forms lustrous white needles m. p. 133-134'. 2 - Thion - 3 - phenyl - 4 - oxazolidone is oxidised by bromine to 2 4-diketo-3-phenyloxazolidine.When dissolved in alcoholic sodium >C(SNa) *OEt ethoxide it forms a gelatinous sodium salt which is decomposed by acetic acid yielding 2-ethoxy-2-thiol-3- phen yl-4-oxaxolidor~ ~o*NPh>C(8H)*OEt. This crystallises in colour- less needles m. p. 73-73.5' and dissolves in alkalis forming salts of phenylthiocarbamylglycollic acid. The above-mentioned sodium com- pound reacts with ethyl iodide yielding a reddish-yellow oil probably >C(SEt)*OEt which on treatment with aqueous sodium QO*NPh CH,-0 hydroxide is converted into ethyl mercaptan and phenylcarbamyl- glycollic acid ; with ethyl chloroacetate it forms the compound YooNPh>C( OEt)-S*CH,-CO,Et which by dilute hydrochloric acid is hydrolgsed and converted into 2 4-diketo-3-phenylthiazolidine and by acetic acid is hydrolysed to phenylcarbamylglycollic acid and a substance crystallking in small flat prisms or white needles m.p. 171-172'. The latter substance is'probably diphenylisohydantoin eo*NPh>C:NPh. The interaction of chloroacetanilide and the sodium salt of 2-thiol-2-ethoxy-3-phenyl-4-oxazolidone yields a thiazolidone cornpound f;H2-S S-CH >C:NPh or & Npi>C:NPh which forms pale yellow CO*NPh crystals m. p. 174-175". The prolonged action of alcoholic sodium ethoxide on 2-thion- 3-phenyl-4-oxazolidone at the ordinary temperature gives rise to 0- CH,*CO $!O*NPh CH,-0 CH,-0 CH,--0 CH,-0ORGANIC CHEMISTRY. i. 133 sodium phenylthiocarbamylglycollate ; at 1 O O O xanthanilide is produced.Yiperidine combines with 2 - thiori - 3 - ethyl - 4 - oxazolidone in alcoholic solution to form 2-thiol-2-piperidyl-3-ethyZ-4-oxaxolidone ~o"Et>C(SH)*N:C~alo colourless prisms rn. p. 146-1 47' and CH,-0 with the corresponding phenyl derivative yielding Z-thioZ-2-piper- >C( SH) C5NHlo which forms iclyl-3-phen yl-4-oxaxolidme white needles m. p. 130-132O. 2-Thion-3-ethyl-4-oxazolidone condenses with benzaldehyde in the presence of sodium ethoxide yielding a-keto-py-diphenylbutyro- lactone (Erlenmeyer and Knight Abstr. 1894 i 592); the same compound accompanied by s-diphenylthiocarbamide is obtained by the condensation of 2-thion-3-phenyl-4-oxazolidone with benxaldehyde by sodium ethoxide. $!O*NPh CH,-0 2 - Fhion - 5 - belzzylidene - 3 - ethyl- 4 - oxazolidone rEt*Co>C CHPh cs-0 prepared by condensing 2-thion-3-ethyl-4-oxazolidone with benz- aldehyde in the presence of piperidine crystallises in colourless plates or short prisms m.p. 94-5-95'; when the condensation is effected by means of acetic anhydride a stereoisorneride crystaliising in long pale yellow prisms m. p. 137*5-138' is obtained. prepared by condensing 2-thion-3-phenyl-4-oxazolidone and benz- aldehyde by means of acetic anhydride forms slender golden-yellow needles m. p. 181.5-182O. 3-Phenylrhodanine reacts with piperidine in alcoholic solution yielding phenlyZpi(pe~idyZthioc~~.~a~~de NHPh-CS*C,NH,, thin white prisms m. p. 100-100~5' and with alcoholic sodium ethoxide t o form a sodium salt which on acidification with acetic acid yields yO*NPh CH,-S 4- ket 0-2-thiol-2-ethox y-3-phenyZthiaxolidine >C(SH)*OEt ; this L crystallises in colourless flat prismatic needles m.p. 61 -5-62'. in support of the thiazolidine formula assigned to the rhodanines. The formation of the latter compound furnishes additional evidence E. B. Nitro-derivatives and Nitro-hydrazones ROBERTO G~IUSA (Atti R. Accad. Lincei 1911 [v] 20 ii 578-583. Compare Hantzsch Abstr. 1910 i 475).-The author refers to the different coloured modifications of hydrazones of nitro-aromatic aldehydes whioh he has described and suggests that they are chromo-isomerides like the nitro- anilines of Hantzsch. According to him a nitrohydrazone of the formula NO,Ar*CH:N-NRPh can exist in the two forms P,NmAr*'H:N*~PhR (red) and O,N*Ar-CH:N -NPhR (yellow).Since %he hydrazones contain a -C:N- linking they can exist in 1 2i. 134 ABSTRACTS OF CHEMICAL PAPERS. s p - and anti-forms and it ie suggested that the red isomerides are the syn-forms because that configuration mould favour the origin of the internal additive product containing a secondary valence. R. V. S. ConBtitution of Buchner's so-called Pyrazolinecarboxylic Acids. CARL B~LOW (Ber. 1911 44 3710-3716).-By the inter- action OF phenylhydrazine and acraldehyde Fischer and Knoeve- nagel obtained phenylpyrazoline NPh<CH"*CH,. Subsequently N- FH L I N=QH pyrazoline NH< was obtained by Curtius and Wirsing by CHn*CH,' the interaction of hyiraziie and acraldehyde. This is very unstable towards oxidising agents but it can be distilled unchanged and is stable towards hydrochloric acid On the other hand the pyrazolinecarboxylic acids described by Buchner (Abstr.1893 i 430; 1894 i 348) obtained from aliphatic diazo-compounds and unsaturated mono- or di-carboxylic acids of the ethylene series are characterised by giving up all their nitrogen on heating or distillation and forming cyclopropanecarboxylic acids. When boiled with dilute mineral acids hydrazine is eliminated. Lastly they are readily converted into pyrazole derivatives. These facts are not in agreement with the relatively stable nature of heterocyclic five-membered rings and it is considered that Buchner's cids are more correctly formulated as mixed azines of glyoxylic and oxalacetic acid esters ; thus the product from ethyl diazoacetate and ethyl fumarttte has the formula CO,Me*CH N*N C( C0,Me) CH,* C0,Me.Azines such as benzylideneazine CHPh:N*N:CHPh give up the whole of their nitrogen on heating and the other properties of Buchner's acids are shown to be in accord with formulating them as mixed azines instead of as pyrazolinecarboxylic acids. E. F. A. Pyrimidines. LIV. Condensation of Carbamide and Guanidine with Esters of Allylmalonic and Some Alkyl- s u b s t i t u t e d Allylmalonic Acids. TREAT B. JOHNSON and ARTHUR J. HILL (Amer. Chem. J. 1911 40 537-549).-In an earlier paper (Abstr. 1911 i 502) it has been shown that ethyl allylmalonate reacts with thiocarbamide to form ethyl 2-amino-4-lceto-7-methyItetrshydro- hexathiazole-5-carboxylate instead of the expected allylthiobarbituric acid whilst ethyl benzylallylmalonate and diallylmalonate condense with thiocarbamide with production of acylthiocarbamides or their y-lactones.I n view of this abnormal behaviour experiments have been carried out to ascertain whether barbituric acid derivatives are formed by the condensation of ethyl allylmalonates with carbamide and guanidine. v 5- Allylmalonylcar bamide (allylbarbituric acid ) CO<~~:~~>CH~CH,-CH:CH m. p. 1 6 7 O obtained by the action of carbamide on ethyl malonate inOhGRNIC CHEM 1S'l'K.Y. i. 135 presence of sodium ethoxide crystallises in nearly colourless plates and is hydrolyscd by potassium hydroxide with formation of allpl- malonic acid. 5-AllylmaEonylyuan~dine NH C < s g ::>OH* CH,*CH:CH 2H20 m. p. 265-266" crystallises in pink prisms or hexagonal tablets.5 5 - DiallylmaZon?/lcnrbamide (dia?lyZbag*bituric acid) CO<~~:~~>C(CH2-CH:CH2)2 m. p. 173" obtained by the action of carbamide on ethyl diallyl- maloaate forms colourless rhombohedra1 crystals and on hydrolysis with potassium hydroxide yields diallylmalonic acid. 5 5-Diallyl- malonylyuanidine NH :C<zE gg>C( CH,*CH CH,) crystallises in colourless rhombohedral prisms does not melt below 300° and is hydrolysed by potassium hydroxide with formation of diallylmalonic acid. 5- Benx yl-5-allylmalon ylcarbamide (5- benxyl- 5 -all ylbarbituric ad) co<NH*CO NH*Co>C(CH2Ph)*CH2*CH:CH2 m. p. 19S0 prepared by the condensation of carbamide with ethyl benzylallylmalonate crystallises in prisms ; it can also be obtained by the action of ally1 iodide on silver benzylbarbiturate.The compound is not hydrolysed smoothly by potassium hydroxide. When gumidine is heated with ethyl benzyl- a1 ly 1 malon a t e in presence of sodium e thoxide benx ylally liminoma lonuric acid NH2*C(NH)*NH*CO*C(CH2Ph)(CH2*CH:CH2)*C02H or more probably NH:C<~&o~~~>C(CH2Ph)*CH2*CH:CH2 is produced which crystallises in needles does not melt below 300° and is immc- diately transformed by dilute bydrochloric acid into 5- benzyl-5-allyl- malonylguanidine hydrochloride. 5 -BenxyE5 - allylnialonylguanidine ,H*d<NH*CO NH.c-,>C(CH,Ph)*CH2*CH:CH can also be obtained by . the action of benzyl iodide on 5-allylmalonylguanidine ; it forms a fine cdourless powder and does not melt below 300". Attempts to obtain pure benzylallylmalonic acid by the hydrolysis of this compound with potassium hydroxide were not successful.Benzylallylmnlonic acid CH CH*CH,*C(CH,Ph)(CO,H) was obtained as a viscid uncrystallisable liquid by the hydrolysis of its ethyl ester with potassium hydroxide ; the silver salt was prepared. E. G. Preparation of 1 -p-Dimethylaminophenyl-2 3 4-trimethyl- 5-pyrazolone. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 238256).-1 -p- A minophenyl-2 3 4- trimethy l-5-pyruxolone m. p. 225-22'io prepared by the reduction of 1-p-nitrophenyl- 2 3 4-trirnethyl-5-pyrazolone cryst,aIIises from water in colourless crystals containing 9H,O. When heated at 90-1 00" with methyl iodide it yields 1 -p-di~rlet~,?/Za?n~inop~e?~yl-~ 3 4-triinethyZ-~-pyraxololae which crystallises with 2H,O and has m.p. 140" (anhydrous). 1-p-Aminophenyl- The following compounds are also described :i. 136 ABSTRACTS OF CHEMICAL PAPERS. 3 4-dimet?~yl-,5-py1~azolone ti colourless crystalline powder m. p. 232O obtained by reducing the corresponding nitro-compound. 5-Elhoxy- 1-p-tcminophenyl-3 4-dimethylpyraxole m. p. 95-97O. 1-p-Acetylaccmilzo- phenyl-3 4-dimathyZ-5-pyi-axoZone a colourless crystalline powder m. p. 2 72-273". 5-Ethoxy- 1 -p-met ylaminophenyl-3 4-dirnethylpyruzole m. p. 130'. 5-Acetoxy- 1-p-acet~laminop~e?ayl-3 4-dimethylpyraxoEe m. p. 167-1 6 8". 1 - p-Meth ylaminophmyl- 3 4-cEirnothyl-5-pyraz010~ needles or leaflets (lH,O) m. p. 108-110'. 1 -p-Dimetl~?/Zaminophenyl- 3 4-dimethyl-5-pyruzolone LLI p.199-200". I-p-Acet?ilmethylamin~- phenyl-3 4-dimethyl-5-pyruxolone crystallises with 2H,9 m. p. 80" or 1 6 2" (anhydrous). 5- Ethoxy-l -p-methylaminophenyZ- 3 4-dzrneth ylpyraxoZe is an oil; its nitroso-derivative has m. p. 75". 1 -p-Acatylmethylaminophenyl-2 3 4-trimethyl-5-pyraxolone has m. p. 139-1 40". l-~-Methylai??ino~~enyl-2 ; 3 4-~rimsthyZ-5-;uyraxolone has m. p 168'. F. M. G. M. FARBWERKE VORM. MEISTER LUCJUS & BR~NING (D.R.-P. 238373).-1t is found that 4-&0- valerylamino-1 -phenyl-3-methyl-5 - pyrazolone and its derivatives can be methylated (methyl sulphate) without eliminating the isovaleryl group in position 4 ; the following compounds are described 4-iso- Vklerylumino-l -phenyt-2 3 -climst?iyl-5-pyrazoEone forms colourless crys- tals KU p.203". 4-iso74aleryZumino- 1 -phenyl-3-methyl-5-pyraxoZone forms colourless crystals m. p. 230". 4-iso ~ a z ~ ~ y l a l l ~ i ~ o - 5 - e t h o x y - l -pher&yl- 3 mthylpyrcmole has m. p. 115". 5-CT~Zoro-4-isovaZerylamino-1-p~n~l- 3-metlqlpyraxolee has m. p. 1 ZOO 4-isoVaZerylamino-5-isovaleryZoxy- l-;uhenyl-3-methylp~ruxoZe has m. p. 122-123". 4-a-Bromoisovaler~l- amino-1-phenyl-2 3-dintethyl- 5-pyraxolone forms colourless crystals m. p. 206". 4-a-BromoisoaccZeryZamino-5-a-bromoisouule~yZoxy-1-phenyl-3-~tAyl- pyrccxole colourless crystals m. p. 114-1 16" is obtained by treating an aqueous solution of 4-amino-l-phenyl-3-methyl-5-pyrazolone hydro- chloride with a-bromoisovaleryl bromide in the presence of sodium acetate. F. 31. G. M. [Preparation of Substituted Pyrazolones.1 Hydantoins.VIII. Action of Bromine on Tyrosinehydan- toin. TXEAT B. JOHNSON and CHARLES HOFFMAN (Amer. Chem. J. 1912 47 20-27).-It has been found by Wheeler Hoffman and Johnson (Abstr. 1911 i 923) that tyrosinehydantoin is converted by chlorine into the 3 5-dichloro-derivative and that the latter is hydro- lysed by barium hydroxide with formation of 3 5-dichlorotyrosine. It is now shown that iodine reacts in a similar manner with tyrosine- hydantoin with production of a nearly theoretical yield of 3 :5-di- iodotyrosinshydantoin. Witb bromine however tyrosinehydantoin behaves abnormally giving 3 5-dibromobenzylidenehydantoin as the chief product of the reaction and only a small quantity of 3 5- dibromotyrosinehydantoin. m. p. CO-y H NH-CO' 3 5-Di-iodotyrosinehydantoin OH*C,H,I,-CH,*CH< 235" (decornp.) crystallises in hexagonal plates.3 5-Dibronio- 4 -h yclroxybenzo ylhydantoic acid (3 5-dibmmotyrosine- hydantoic acid) NH,*CO~NH~C1~(C0,H)~CW,.C,H2Br.,.0H m. p.ORGANIC CHEMISTKY. i. 137 19l0 obtained by the action of potassium cyanate on 3 5-dibromo- tyrosine forms rhombohedra1 plates or square prisms and is hydrolysed bv concentrated hvdrochloric acid with formation of 3 5-di6romotvrosine- J .I CO-YH I m. p. 223-225O (decomp.) NHmCO' h yd an toin 0 H C,H Br,* C H2* C H< which crystnllises in prisms. 3 5-~~bronto-4-Ay~~oxybenzylideneh,~dccntoin CO-TH OH*U,H2Br,*CH:C<NH. co m. p. above 295" (decomp.) obtained by condensation of 3 5-dibromct- 4-hydroxy benzaldehyde with by dantoia forms small brownish-yellow needles yields a yellow ccmrnoniurn salt and is reduced by hydriodic acid with production of 3 5-dibromotyrosinehydantoin. 3 5-Dibromo- 4-hydroxybenzylidenehydantoin is also produced by the action of bromine on tgrosinehydantain and on 3 5-dibromotyrosinehydantain. The Reduction of Aromatic Aldazines.THEODOR CURTIUS (J. pr. Chem. 1912 [ii] 85 37-77. Compare Abstr. 1900 i 610). -The paper first gives a summarised account of the results of the investigations published hitherto by different workers on the products obtained by the reduction of benzaldazine (benzylidenehydrazine) and its substituted derivatives under various conditions. [With FRANZ SCHNEIDERS.] -Benzylhydrazine easily undergoes atmospheric oxidation giving a deposit of benzaldehydebenzyl- hydrazone (private communication from August Darapsky).Towards the esters of p- and y-ketonic acids benzylhydrazine behaves like phenylhydrazine. Warmed with benzoylacetic ester i t yields 3-phenyl-l-benxyl-5-pyraxolone a white crystalline powder m. p. 204-205'. Ferric chloride solution is without action on the substance (contrast the 1-benzy l-3 -methyl compound below). When treated in glacial acetic acid solution with sodium nitrite 4-oxirnino- 3-phenyl-1 -benzyl-5-pyrazolone is obtained ; it forms deep red needles m. p. 161-162'. On warming benzylhydrazine with ethyl hvulate l-benzyl-3-mebhyl- 6-p yridaxinone CH2< CH20co>N*CH,Ph CMe=N is obtained ; this crystal- lises from light petroleum in colourless prismatic crystals m. p. 56-57".When cautiously added to ethyl acetoacetate benzylhydrazine yields 1-benzyl-3-m,etl~yE-5-;r?yrcczolone a white crystalline solid m. p. L75-176O b. p. 192-194"/14 mm. ; the intermediate benzylhydr- azone of acetoacetic ester could not be isolated. The product is acid t o litmus and the copper cobalt nickel and silver salts are described ; the hydrochloride forms prismatic crystals m. p. 120'. l-Benzyl-3-methyl-5-pprazolone is exceedingly reactive. Ferric chloride solution in the cold gives a brown coloration and on boiling causes oxidation to the corresponding pyrazole-blue. Heated with phosphorus pentachloride it yields 4-dichloro- 1-benzyl- S-rnethyZ-5-pyrazolone which crystallises in leaves w. p. 59-61O ; the analogous 4-dibromo-compound forms small hard crystals with a tinge E.G.i. 138 ABS1'RACTS OF CHEMICAL PAPERS. of yellow (m. p. 81-83'); these two dibaIogen compounds am unlike the original substance indifferent t o both acid and alkali. 4-p-Tolueneaxo-1 -benxyl-3-methyl-5-pyrazolone obtained by the action of tolifenediazoniurn sulphate forms slender yellow needles m. p. 123-1 24'. 1 -Benx yl-4-6eraz ylidene - 3-methyl-5-pyrazolone ob taiiied by the action of benzaldehyde on benzylrnethylpyrazolone forms rcd crystals m. p. 11 1-1 12'. On heating benzylmethylpy I azulone with phenylhydra zine ammonia is cvolved and 4-bis-1-benzyl- 3-nieth yl-5-pyrazoZone SJ :CMe CMe:N obt'ained which forms white needle crystals melting above 330'; by oxidation with various oxidising agents it passes smoothly into CH,Ph*N-CO >CH*CH<C-J-r(T.CH,Ph' 7:CMe CMd? 1 -hen2 yl-3-meth ylp yraxole- bZue CH,Ph*N-CO >C:C<c()-N.CII,pb ; this crystallises in almost black needles m.p. 142-144' and is decomposed by strong acids and boiling alkali solutions. Careful oxidation of benzylmethylpyrazolone by pot,assium permanganate gives a white acid substance of indefinite m. p. which could not be further purified; the silver salt was obtained as a white precipitate m. p. 185-189' ; excess of permanganate causes oxidation to benzaldebyde and benzoic acid. On treating l-benzyl-3-metbyl-5-pyrazolone in dilute hydrochloric acid solution with sodium nitrite 4-oximino- 1 -benzpl- 3-methy 1-5 - pycczolone is obtained crystallising in yellow needles or prisms m. p 152-152.5'. By reduction with zinc dust in acetic acid solution the oximino-compound gives a solution of 4-amino-1-benxyl- 3-meth yl-5-pyrazoEone which was not isolable and attempts to isolate it as the benzylidene derivative merely caused oxidation to the corresponding rubazonic acid of 1 -benxyl-3-methyk5-pyrazolon~ :CMe CMe:N CH,Ph*N-CO >CH*N:C<Co-&.(7H2ph ; this more conveniently prepared by oxidation of the amino-compound with ferric chloride forms cinnabar-red crystals m.p. 160-161' ; its solutions in alkalis are violet-red. The ammonium salt of 4-oximino-l-benzyl-3-metbyl-5-pyrazolone forms a yellow powder (m. p. 175-176') ; with silver nitrate it yields fhe silver salt as a reddish-brown insoluble amorphous powder which decomposes completely a t 179'. On the other hand silver nitrate decomposes an acetic acid solution of the free oximino-compound nitrous fumes are evolved and finally microscopic needles of the silver salt of 4-nitro-1-benzyl-3-methyl- 5-pgrazolone are obtained which decompose at 245-246".4 - Nitro - 1 - benxy I - 3-naeth yL5-pyrazo Zone can be obtained from the silver salt or by oxidation of the oximino-compounds with nitric acid ; it forms colourless needles m. p. 144-145' (decomp.). The silver salt of t,hs nitro-compound gives with aniline a suhatcmee >(!:N(NHPh),*OAg which separates on couling i n y CR4e CH,Yh* N-UOORGANlC CHEMIS'l'KY. i. 139 yellow capillary crystals ; treatment with solvents removes aniline from the substance regenerating the original silver salt. 1-Benxyl-2 3-dimethyl-5-p~ruxolone (1 -benzylantipyrine) is obtained by methylating l-benzyl-3-metbyl-5-pyrazolone.It forms anhydrous hygroscopic crystals m. p. 84-S6' ; from moist solvente i t crystallises with &H,O and then has m. p. 102-103'. The picrata forms long yellow needles (from hot water.) m. p. 143-145'. 4-0ximino- i -benzyl-2 3-dimethylpyrccxolone is an unstable deep green viscous oil. If benzylantipyrine is oxidised with concentrated nitric acid 4 -nitro- 1- benzyl- 2 3-dimethylpyvazolone is obtained as colourloss prismatic crystals m. p. 161-162O. The physiological action of benzylantipyrine was investigated ; it appears to possess certain advantages over ordinary antipyrine. [With GUSTAV SPRENGER.] - p - Methylbenzylhydrazine (compare Abstr. 1900 i 612) is best prepared by reduction of p-metbyl- benzaldazine by sodium amalgam ; on dilution with water and cooling crystals of the p-methylbenzylhydrazone of p-tolualdehyde separate and can be decomposed by hydrochloric acid.The dihydro- chloride m. p. 150' (decomp.) the sulphate m. p . 178-179' and the oxalate m. p. 180° were obtained. Benzaldehydep-methy2benxylhydrazone forms large transparent tablet.G m. p. 88' ; the diacetyl derivative C6H4Me*CH2*N,HAc forms crystals m. p. 75' (indetinite). The stable nitroso-compound C,H4Me*CH2*N\NO)*NH2 crystallises from water in needles m. p. 78O and when warmed with dilute sulphuric acid yields p-methylbenzylazo- imide C,H,Me*CK,*N b. p. 94'/12 mm. (compare Curtius and Parap- sky Abstr. 1902 i 844). With ethyl acetoacetate p-methylbenzyl- hydrazine gives 1 - p - methylbenzyl-3-methyl-5-pyrazolone (compare Abstr.1900 i 61 2) ; its hydrochloride has m. p. 130'. By treat- ment with nitrous acid the above pyrazolone is converted into yellow 4-oximino-1 -p methyl benzyl-3-methyl-5-p yrazolone m. p. 1 54'. By methyl- ation the pyrazolone is converted into 1 -p-meth?~lbenxyl-2 3-dimethyl- 5pyraxolorie which forms prismatic crystals m. p. 78'. The sub- stance behaves analogously to antipyrine and benzylantipyrine towards nitrous acid and ferric chloride. I t s physiological effect has not yet been investigated. D. F. T. RALPH H. MCKEE (J. pr. C'hem. 1911 [ii] 84 821-826).-By the interaction of etbyl cyanoimidocarbonate and ethyl anthranilate Finger and Zeh (Abstr. 1910 i 382) obtained a compound which t)hey considered to be ethyl cyanoanilide - o-carbox y late. The author 11 as investigated the action of cyanogen bromide on ethyl anthranilate and finds t h a t the resulting compound which undoubtedly has the structure of ethyl cyanoanilide- o-carboxylate is different from Finger and Zeh's compound.The latter substance is considered to be ethvlbenzovleneisocarbamide Ethyl Cyanoanilide-o-carboxylate. .I >C*OEt or ~o*NH>C*@Et and this co--N C,H;N I3 C,H;N [2-ethc xyquinazolone] 1 view is supported by the- formation of the corresponding methyl com- pound by the interaction of methyl cyanoimidocarbonate and ethyl anthranilate. According to Finger and Zeh the products obtainedi. 140 ABSTRACTS OF CHEMICAL PAPERS. from both the methyl and ethyl cyanoimidocarbonates should be identical.Finger and Gunzler had already shown that it is a quinazo- line derivative (Abstr. 1911 i 237). Methyl cyartoimidocarbonate NH:C(CN)*OEt prepared by the action of hydrogen chloride on methyl alcohol and potassium cyanide is a colourless oil b. p. 115"/760 mm. having an odour of mice excre- ment. It reacts with ethyl anthranilate a t 80" in the presence of cuprous chloride yielding 2-methoxyquinaxoZorae I >C*OMe m. p. 231-232" (corr.) which is hydrolysed by hydrochloric acid to 2 4-diketodihydroquinazoline m. p. 3 5 7 O (corr.) ; Griess (Bey. 1869 2 416) gives 344O. Methyl cyanoanilide-o-carboxgiate CN*NH-C6H;C02Me obtained by the action of cyanogen bromide on methyl anthranilate in ethereal solution crystallises in needles m. p. 105' (corr.).When heated a t looo it polymerises t o tri-o-carbomethoxyphenylmelamine c27H240~N6 which has M. p. about 1 6 0 O . Ethyl cyanoanilide-o-carboxylate prepared from cyanogen bromide and ethyl anthranilate has m. p. 93-94O and polymerises to tri-o- carbethoxyphenylrnelanzine C3,,H3006N6 m. p. 1 90° with previous sintering. Methyl anthranilate forms a picrude N H2*CGH,*C02Me,C,H,07N3 crystallising in deep yellow microscopic needles m. p. 106O (corr.) ; the picrate of ethyl anthranilate has m. p. 1 16c (corr.). Preparation of Derivatives of Indophenols. LEOPOLD CASSELLA & Co. (D.R.-P. 23885'7). -1ndophenols prepared from carbazolecarb- oxylic acids and nitrosophenols co2R NH have previously been described ; .A/ \A - these substances on reduction I t 1 I NH-/ \OH furnish leuco-derivatives having \/- \/- \-/ the annexed general constitution which when slowly dropped into a hot solution of sodium polysulphide yield dark blue sulphur cotton dyes which are extremely fast to light washing or chlorine.Preparation of Anthraquinone Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 235981. Compare following abstract),- When acyl o-diaminoanthraquinones are treated with dehydrating reagents the following action takes place OO--N CGH4*NH F. B. F. M. G. M. = A<EC>CR + H,O where A is an anthraquinone residue (substituted or otherwise) R hydrogen alkyI or aryl and R' alkyl aryl or an ethoxy-group. 1 2-PhenyZanthraquirtoneiminnzoEe prepared from benzoyl-1 2- diaminoanthraquinone and 4-amino- 1 2 - phenylanthraquinonehin- azole obtained from benzoyl-1 2 4-triaminoanthraquinone by the action of sulphuric acid at 150° form yellow crystals and glistening metal1 ic need 1 es respectivoly.1 2-HydroxyanthraquinoneiminaxoZe (I) prepared by the action of carbonyl chloride on 1 2-diaminoanthraquinone crystallises from quinoline in needles.ORGANIC CEEMISTRY. i. 141 4 - Hpdrolcy- 2 - ethoxy- 1 -p-tol~lanthl.aquinolzeimincczole (II) yellow needles was obtained by the fusion (at 100') of p-toluidine with dinitro-P-amiooanthrnquinoneurethane ; it yields a sdphonic acid when heated with fuming sulphuric acid. 1 2-MsthyZanth~aquinn~~m~~uzoZe yellow needles obtained from 1 2-diaminoarithraquinone and acetic anhydride and the compound from the same base and formic acid are alco mentioned in the or i g i nal.NE-C*OH N(C,Ht )-C* OEt /VCO\/\-N I /\/ CO \/\--+ I I t I / I (OH \/\c(/\/ Preparation of Anthraquinone Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R-P. 238982).-Condensation products of benzaldehyde and P-arninoanthraquinones have been described by Kaufler (Abstr. 1904 i 207) ; this condensation is now found to take place readily with o-diaminoanthraquinones and either aliphatic or aromatic aldehydes. The compounds prepared from 1 2 - diaminoanthraquinone and 1 2 4-triamimanthraquinone respectively with benzaldehyde are identical with those obtained from the benzoyl derivatives of these compounds when heated with sulphuric acid (compare preceding abstract) whilst 1 2diaminoanthraquinone with para-acetaldehyde in concentrated aulphuric acid at &lO0 yields the 1 2-methylanthra- qninoneiminazole also previously described.F. 31. G. M. [Preparation of Anthraquinoneacridone Derivatives.] 238978).-Anthraquinoneacridone can be conveniently nitrated with nitro-sulphuric acid at 0 - 5 O ; the nitrated product is yellow and does not fuse at 300'; when reduced with sodium sulphide at loOo i t furnishes aminoanthraquinoneacridone (not melted at 300'). Benzoylaminoanth4.u~u~noneacridorte separates in crystalline form when a nitrobenzene solution of aminoanthraquinoneacridone is boiled with benzoyl chloride ; the acetyl compound has also been prepared. The second patent states that the foregoing benzoylaminoanthra- quinoneacridone can be obtained by boiling a nitrobenzene solution of bromoanthraquinoneacridone with benzamide in the presence of copper and sodium carbonate during t wenty-four hours.AKTIEN-GESELLSCHAFT FUR ANrLIN-FABRIKATION (D.R.-P. 2389'77 and F. M. G. M. Nature of the Indanthren Fusion of 2-Aminoanthra- quinone 2-Hydroxylamino- and 2 2'-Azoxyanthraquinone. ROLAND SCHOLL and FRITZ EBERLE (Monactsh. 19 11 32 1035-1 042). -2-Hydroxylaminoanthraquinone obtained in small quantity by reduction of 2-nitroanthraquinone could not be converted into indanthren by fusion with an alkali hydroxide. I n alkaline solution hydroxy l r u n i n o a n t ~ a q ~ i ~ o n e ia very readily oxidised by atmospherici. 142 ABSTRACTS OF CHEMICAL PAPERS. oxygen to 2 2'-azoxyanthraquinone. This compound could not be reduced to the corresponding hydrazoanthraquinone 2-aminoan thra- quinone always resulting.The formation of indanthren from 2-aminoanthrnquinone is explained on the assumption that on fusion with an alkali hydroxide 2-aminodihydro-1 2'-dianthraquinonylamine is formed and that this loses hydrogen forming dihydroindanthren NH,*C,,H,( OH)2*NH*4,H102 C,,H,(0H),<~~>C14B~02' ~ydroxyla~~inoanthraquinone C,,H70,*N H*OH was obtained as an It dissolves in 2 2'-Azox~unthraquinon e ON,( C,H,<gg>C,H,)2 crys t allises in small light brown prisms and prismatic plates m. p. 342.5'. The solution in concentrated sulphuric acid is red. A solution in hot acetone gives a very characteristic cornflower-blue coloration on the addition of a few drops of sodium hydroxide. orange-red solid sintering at 140° m.p. 158-160". dilute sodium hjdroxide with an intense green coloration. E. F. A. [Preparation of Dimethylindanthren.] BADISCHE A NILIN & SODA- FA BRI K (D . R. -P. 2 3 89 7 9) .-3 3'- Dimet h ylind an thren a bluish- grey crystalline powder can be prepared by boiling an acetic acid solution of 2-amino-3-met hylanthraquinone (1 part) with lead peroxide (3 parts) during three hours or by boiling a naphthalene solution of 1 -bromo-2-amino-3-methylanthraquinone with copper oxide and anbydrous sodium acetate during four to five hours. A similar conyound can be obtained from Z-amino-6(7)-methylanthraquinone. F. M. G. M. Action of Semicarbazide on Hydroxamic Acids. HANS RUPE and F. FIEDLER (J. pr. Chem. 1911 [ii] 84 809-816).-It has been shown previously (Rupe and Kessler Abstr. 1910 i 93) that the action of semicarbazide hydrochloride on aliphatic oximino- ketones leads t o the replacement of the oximino-group by the semi- carbazide residue :N*NK*CO*NH,.A similar elimination of the oximino-group is found to take place with hydroxarnic acids resulting in the formation of semicarbazidts. The reaction is however not a general one. The replacement occurs readily with benzhydroxamic and acethydroxamic acids and with difficulty in the case of phenyl- acethydroxamic acid whilst with salicylhydroxamic and cinnam- hydroxamic acids no reaction takes place. Benzoylsemicarbazide obtained by heating benzhydroxamic acid with semicarbazide hydrochloride in aqueous solution has m. p. 215O and may also be prepared by the action of ethyl benzoate or benzoic anhydride on semicnrbazide.The high m. p. (225') given by Widmann and Cleve (Abstr. 1898 i 335) is due to the presence of hydrazo- dicai~boxylttrriide. The acetyl derivative C16Hl103N3 forms lustrous white leaflets m. p. 174O and is instantly hydrolysed by cold aqueous sodium bydroxide. . Cinnamoylsemicarbaxide C,,H,,O,N prepared by heating cinnamicORGANIC CHEMISTRY. i. 143 anhydride with semicar bazide crystallises in needles ; t be clcelpl derivative forms slender white needles LU. p. 177-178O. ~ ' ~ ~ e n ? / Z ~ 6 c e t ? / Z u e n ~ i c a r ~ u ~ ~ ~ ~ CYH1102N3 o btilined from the acid chloride or anhydride in a similar manner or by the interaction of phenyltiydroxamic acid aud semicarbuzide hydrochloride in aqueous solution crystallises in slender needles m. p.167-168'. Azines and Quinonediazides of the A n t h r a q u i n o n e Series. ROLAND SCHOLL FRITZ EBEHLE and M 7 ~ ~ ~ ~ ~ TRITSCR (Monatsh. 19 11 32 1043-1056). -( 1) Azines from Triuminoanthrccquinone.-On con- densiug 1 2 3-trinminoanthraquinone with o-dicarbonyl compounds azines of entirely different nature are to be expected according as the pytwine nucleus becomes attached in the angular 1 %position or the linear 2 3-position. The linear derivatives should possess the same properties as the azines from 2 3-diaminoanthraquinone (Scholl and Kacer Abstr. 1905 i 88) characterihed by their giving brown reduction products with alkaline sodium hyposulphite (Scholl and Edlbacher Abstr. 1911 i 756). Oxalic acid benz 1 1 2-naphthaquinone phenanthraquinone and isatin yield azines with triaminoanthraquiuone which all form insoluble brown products in alkaline sodium hyposulphite.The azines are accordingly regarded as linear (for nomenclature see Scholl Abstr. 1911 i 677). 1 2 3-Triaminoanthraquinone has m. p. 325" (decornp.). Bihydmxy-2 3-pyrazino-1-arninounti~ruguinone (annexed formula) produced on coudensation with oxalic acid sublimes in lustrous dark brown needles. /\/\/\/\OH It is not melted at 400'; in boiling with 1 I I 1 ]OH dilute sodium hydroxide it dissolves giving '\/\/\/\/ a red solution from which a red sodium salt separates on cooling. C,H4<CO>C,H(NH,)<N :&h' F. B. CO NK,N GO Diphen$-2 3-pyrazino-l -amirLoantl~~waquinono co KCPh prepared by condensation of triaminoanthraquinone and benzil crystallises in tiny red or brownish-red needles m.p. 241'; it sublimes without decomposition and gives a red coloration with concentrated sulphuric acid. 2 3( 1' 2'-)-Naphthanino-l(or 4-)-arninoanthraquinone is obtained as a dark brown amorphous compound m. p 266 -267O. 2 3( 9' IO'-)-Pllenanthruxiro- 1 -nmiroalnthrapuinone crystallises in well formed reddish-brown lustrous needles m. p. 361". 2 3-lndazino-1 (or 4-)-anzinoanthraquinone forms a dark brawn indefinitely crystalline powder m. p. above 400'. When heated with sodium hyposulphite and sodium hydroxide it forms a reddish-brown vat which dyes cotton yarn light brown. (2) QuiNoneuxides of the Anthraquinone Series. -The quinonediazides of the anthraquinone series in contrast to those of the benzene series cannot be coupled with naphthol or naphthylamine to azo- dyes.With resorcinol they couple only very slowly on prolonged heating.i. 144 ABSTRACTS OF CHEMICAL PAPERS. 2 6-nibror~~oant7~rnquinrme-l 5-bisdiazonium sulphate (I) produced on diazotisiug dibromodiaminoanthrayuinone separates in yellowish- red crystals m. p. 185-186O. When boiled with dilute sulphuric acid it is converted into ~6nth~apuinone-2 1 6 5-bisquinonediazide (11). CO N2*S04H co N2 Br CO N /\/\/\Br / \ / \ A 0 /\A& I l l I I I I ?/\/\/ OH CO Br Brl I I I \/\/\/ S04H-N2 CO (1.1 (11.) (111.) This crystallises in well-formed metallic-green lustrous crystals which explode at 156'. 4 6 8-~rib.rorno-5-hydroxyantl~raquinonc-2 1-qwinonediazide ( I I I ) prepared by diazotising 2 4 6 8-tetrabromo-1 5-diaminoanthra- quinone and boiling the crude diazo-product was obtained in a brown crystalline form from acetone which blackens and sinters above 360".E. F. A. [Preparation of ~-Azimino-compounds.] CHEMISCHE FABRPK GRIESHEIM-ELEKTRON (D.R.-P. 238353). When the azo-compounds obtained by the combination of /3 - diazoanthraquinones with /\/\'\ N' '\/\/\ p - naphthylamine are oxidised I I I- "-I I they yield +-azimino-compounds \/\/\/ \/\/ such as up-nayl~tl~ylene-~C/-azimino- ( a n n e x e d CO formula). The sulphonic derivatives are soluble in water and form valuable cotton dyes. co /3 - cbnthraquinonyl F. M. G. 31. Action of Hydrazoic Acid on Cyanogen. Formation of Cyanotetrazole. E.OLIVERI-MANDALA and T. PASSALACQUA (Gaxxetta 191 1 41 ii 430-435. Compare Oliveri-Mandal& Abstr. 1910 i 343; 1911 i 337 ; Oliveri-Mandalh and Coppola Abstr. 1910 i 593; Oliveri-Mandala and Alagna Abstr. 1911 i 243; Dimroth and Fester Abatr. 1910 i 645).-When cyanogen is passed in to a 40% aqueous solution of azoirnide cyanotetrazole [tetrazo&-5- ca~boxylonitrile] C'2HN5 is produced. The substance becomes slightly red at 70' and melts at 9 9 O forming a reddish-brown liquid. It yields ammonia quantitatively when boiled with potassium hydroxide solution. The silver salt C,N,Ag and the barium salt were prepared. When the silver salt of cyanotetrazole is treated with ethyl iodide 1 -ethyltetrazole- 5-carboxyllonitrib y(CN)*NEt>N is obtained; it is a colourless liquid b.p. 127"/46 mm. On distillation a t ordinary pressure it explodes at about 200". 1-E'thyltetraxoZe-6-carboxyZamide C,H70N is prepared by heating at 50-60" an alkaline solution of 1-ethyltetrszole-5-carboxy lonitrile with hydrogen peroxide solution ; (C2N5)2Ba,S&H20 N--NORGANIC CHEMISTRY. i. 145 i t crystallises in minute lustrous scales m. p. 125-126". I-EthpZ- tetrazole-5-cccrboxyl~c acid C,H,O,N is obtained by heating 1 -ethyl- tetrazole-5-carboxylonitrile with methyl-alcoholic potassium hydroxide and neutralising the potassium salt with sulphuric acid. The acid crystallises in acicular prisms m. p. 124-125'. In addition to the pohsium salt C,H,O,N,K the silver salt C,H,O,N,Ag was pre- pared. When 1 -ethyltetrazole-5-carboxylic acid is kept at 130-140' it loses carbon dioxide and 1-ethyltetrazole (identified as platini- chloride) is obtained identical with the N-ethyltetrazole formerly described.R. V S. Identity of the Guanine Pentoside from Molasses with Vernine. ERNST SCHULZE and GEORG TRIER (Zeitsch. physiol. Chem. 1912 76 145-147).-Vernine (guanine-d-ribose) for which the com- position C,,H,,O5N,,2H,O was recognised by Schulze and Castoro (Abstr. 1904 11 506) is identical with the guanosine obtained by Levene and Jacobs from nucleic acid and with the guaninepentoside isolated by Andrlik (Abstr. 1911 i 397) from molasses. I n 1.5% sulphuric acid it has [a]2,0 - 8.4". JS. F. A. The Fastness t o L i g h t of Hydroxyazo-compounds. Some Derivatives of a-Methoxy naphthalenes. N. WOROSHZOFF (ZeitscA.Farb.-Ind. 1911 10 169-173).-1t is found that the alkylation of the hydroxy-group in hy droxyazo-compounds increases the fastness to light of the colouring matters obtained therefrom and that methyl- ation can be conveniently carried out by shaking an alkaline solution of the compound with methyl sulphate. Sodium 1 - me thox y naphthalene- 4- su lphona te prepared by shaking a-naphthol-4-sulphonic acid with methyl sulphate in the presence of sodium hydroxide separates in glistening leaflets. 4-Xitro-l-rnethoxynaphthaZene yellow needles m. p. 8l0 is obtained by slowly adding an intimate mixture of the foregoing acid (10 parts) and anhydrous sodium carbonate (0.6 part) in small portions to a cooled solution of 1.5 grams of carbamide in 20 C.C. of nitric acid (D 1.4) ; on reduction with stannous chloride and hydrochloric acid it furnishes 4-msthoxy-a-naphthyZamine hydrochloride in colourless crystals ; the free bme is a dark oil ; its ucetyl derivative has m.p. 180-181". F. M. G. M. Salicylic Acid Azo-dyes. EUGEN~ GRANDMOUGIN (Ber. 191 1,44 3756).-8 claim for priority against Bulow (Abstr. 1911 i 338). D. F. T. Decomposition of Azines by Heat. I. and 11. PAUL PASCAL and LEON NOXMAND (Bull. Xoc. chim. 1911 [iv] 9 1029-1037 1059-1068).-Curtius and Jay (Abstr. 1889 393) showed that bnzaldazine decomposes when heated forming stilbene and Bouveault obtained di-ju-methylstilbene in a similar way from tolualdazine (Abstr. 1897 i 347 530) but failed t o generalise the reaction. In the first OF these gapers the authors show that in general the aromatic aldazines melt with very slight decomposition but when the tempera-i.146 ABSTRACTS OF CHEMICAL PAPERS. ture is raised above the melting point evolation of gizs commences and incrcastx with rise of temperature tho principal reaction being the production of nitrogen and the stilbene corresponding with the aldazine used. At the higher temperatures some ammonia and hydrogen are formed with as a solid product the corresponding phenanthrene due to loss of H atoms a t positions contiguous to the azine side-chain. The rate of decomposition was determined by measuring the gas evolved. By plotting temperatures as abscissse and volumes of ( I ) nitrogen and (2) ammonia disengaged as ordinates tw curves were obtained cutting one another on the temperature axis and thus giving the temperature of decompositioti which is sometimes 50" below that actually observed subjectively. \Vhen the evolution of gas ceases the contents of the tubes were distilled and give as a rule (1) a mixture of aldazine and t h e stilbene ; (2) green oils containing the phenanthrene ; (3) red oils and (4) a resinous or coke-like residue.I n the case of the '' red oils " from bonzaldazine the chief constituent is a substance m. p. 261° b. p. 460' crystallising in long needles and giving a yellow picrate m. p. 1 9 8 O ; it may heidentical with the product C,,K,,N obtained by Curtius from benzoin-hydrazine. The amounts of t h i s substance and its hornologues produced increase with rise in the molecular weight of the alduzine employed.Benzaldazine CHPh:N,:CHPh begins to decompose a t 275O furnish- ing stilbene phenanthrene and the product C,,H23N already referred to. Tolualdazine C,H,Me:N2:C6H,Me begins to decompose a t 3 14O forming di-p-methylstilbene ni. p. 18 1'. C H,Pr@*CH N, CH C6Y4Pr@ m. p. 113*6" forms yellow leaflets and begins to decompose a t 281° yielding cli-p-isopropylstilbene C,H4PrP*CH:CH*C6H4Pr@ m. p. 1 2 9 O which separates from alcohol in colourless scales and yields a dibromide m. p. 186-187O (approx. decomp.) crystallising in small brilliant colourless spangles. p-~ethyZbe?Lxaldaxine CKPh:K,:CH*C,H,Me m. p. 1 12' forms pale yellow crystals from alcohol and when heated gives p-methylstil bene m. p. 119.6'. Aldazines in which the benzene nucleus is replaced by naphthalene decompose only at high temperatures and the unsaturated product is difficult to free from tarry by-products.Furfuraldazine C40H4*CH:N2:CH*C,0H4 is decomposed by heat yielding furfuryl- stilbene m. p. 97.4". The aliphatic azines of low molecular weight distil easily and decompose only at a red heat The higher terms decompose slowly on distillation forming a fluorescent liquid with an odour of petroleum and of pyridine bases ; there is no evolution of nitrogen or ammonia. Di-p-cl~lorobenxnk~axine m. p. 2 1 lo forms yellow spangles from alcohol or boiling benzene ; it begins to decompose at 284' furnishing di-p-chlorostilbene m. p. 153*8' in silver-grey spangles which yields a dibrornide m. p. 195-197". Di-p-iminobenzaldaxine m. p. %5O obtained by the interaction of p-aminobenzaldehyde with hydrazine sulphate is a yellow powder ; it begins to decompose at 307' giving off a little nitrogen and much ammonia so that i t was impossible to isolate di-p-aminostilbene from the accompauying tarry by-products.Cuminaldazine,ORGANIC CHEMISTRY. i. 147 Di-o-methoxp benzaldazine begins to decompose at 270' and yields 80% of di-o-methoxystilbene m. p. 136' which separates from alcohol in colourless crystals and gives a dibromide m. p.. 190'; the corre- sponding meta-compound furnishes di-m-methoxystilbene m. p. 97*5' the dibromide of which m. p. 183*5-184.5' is colourless and crystal- line. Di-p-methoxybenzaldazine begins to decompose at 289' and yields di-p-methoxystilbene m. p. 213'. Bi-o-ethoxybenzaldazine m. p. 131.6" forms yellow crystals and commences t o decompose at 287' giving di-o-ethoxylstilbene m.p. 87*5' colourless crystals the dibromzde of which m. p. 218-219' forms pale yellow crystals. ~i-p-ethox?~benzcddazine m. p. 172*3' crystallises in pale yellow lamellz3 and begins t o decompose at 308' furnishing di-p-ethoxystilbene I ~ I p.' 208". Di-o-benxyZoxybenxaZdazine m. p. 157*7' yellow plates gives di- 0- benzyloxystilbene m. p. l l 7*6" in small brilliant colourless spangles whilst the corresponding. para-compound m. p. 209*3" pale yellow leaflets decomposes less easily forming a bulky '' coke " froni which no stilbene derivative has yet been isolated. T A. H. Decomposition of Azines by Heat. 111. PAUL PASCAL and L d o ~ NORMAND (Bull. SOC. chirn. 1912 [iv] 11 21-25. Compare preceding abstract).-The methoxynaphthaldaxine gives only a small yield of dimethoxynaphthylethylene at 362'.Vercctraldaxine gives but little 3 4 3' 4'-tetramethoxystilbene whilst the azine from piperon- aldehyde N,(:CH*C,H,:O,:CH,) does not yield a corresponding stilbene. The main conclusions arrived a t from results described in this and the preceding abstracts are as follows. Aromatic azines decompose at about 300" evolving nitrogen and ammonia and giving stilbene derivatives the yields being increased if the position ortho to the group *CH:N, is filled by any radicle. In the same homologous series the yield diminishes on ascending the series. If a substituent group such as amino- in the nucleus of the azine possesses a residual affinity the yield of stillnene compound is considerably lowered. Esterification in the case of several hydroxy- groups attached to each aromatic nucleus does not prevent decom- yosi tion. A study of the physical constants of the azines and stilbenes shows t h a t the iritroduction of one or more atoms of oxygen into the molecule produces a rise in the melting point. The reverse is the case if a hydroxyl group is replaced by a methoxy- or ethoxy-group. Finally the more symmetrical the molecule the higher is the melting point. W. G. The Existence of Sulphur Fixed as Sulphite in Wool. H. STRUNK and HANS PRIESS (Zeitsch. physiol. Chem. 1912 76 136-144).-Raikow (Abstr. 1905 i 725; 1907 i 666; compare Grandmougin Chem. Zeit. 1907 31 174) has stated that wool when kept for some time in contact with large quantities of concentrated phosphoric acid liberates small quantities of sulphurous acid. This is confirmed but the amount 0.0064 gram of sulphur dioxide from 300 grams of wool is too small for it to be assumed that part of thei. 148 ABSTRACTS OF CHEMICAL PAPERS. sulphur in the keratin molecule is united with oxygen as sulphite. Dry wool has a very pronounced affinity for hydrogen sulphide ; this is sufficient to explain the variations experienced in the amount of sulphur in wool. The hydrogen sulphide fixed by the wool is easily oxidised to sulphurous and sulphuric acids and it is probable that n small quantity of sulphurous acid may arise in the wool of the living animal in such manner. The Separation of Rennet and Pepsin. W. E. BURGE (Amer. J. Ph,ysioZ. 1912 29 330-334).-The passage of a direct current of 10 milliamperes for twenty-four hours through a solution containing both enzymes causes a complete destruction of peptic activity but leaves the rennet apparently unchanged. Activation of Sucrase [lnvertase] by Different Acids. GABRIEL BERTRAND M. KOSENBLATT and (Mme.) M. ROSENBLATT (Compt. rend. 1912,154,1515-1518).-The effect of the more commori organic and inorganic acids on the diastatic activity of sucrase has been determined under conditions more precisely defined than those of other observers. I n each case the optimum concentration of acid was determined. The results which are displayed in tabular form shorn that generally speaking the order of efficiency in which the acids stand as activating agents is the same as Ostwald’s order for their activity as catalysts in hydrolysis. Hydrochloric and nitric acids however are exceptions to the rule being less effective as activators than a s Action of Phospbatese. HANS EULER and STXTEN KULLBERG (Zeitsch. physiol. Chem. 1912 ’76 241. Compare Abstr. 1911 i 1051 ; this vol. i 61).-Reference is made to von Lebedeff’s work which does not agree with that of the authors; perhaps different kinds of yeast will explain the discrepancy ; no further experimental work is adduced. W. D. H. 4-Amino-3-hgdroxyphenylarsinic Acid and its Products of Reduction. LUDWIG BENDA (Ber. 19 11,44. 3578-3582. Compare this vol. i 61 -64) .-3-Nitro-4-aminophenylarsinic acid can be diazotised in the usual way yielding a solution of a diazonium salt which loses the *AsO(OH) group when boiled with dilute sulphuric acid. However by treatment with sodium acetate t o destroy the mineral acid the solution of the diazonium salt exchanges its nitro- for a hydroxyl group ; the solution of the resulting diazonium salt can be coupled with alkaline P-naphthol to form a red azo-dye which is reduced by sodium hyposulphite or by sodium hydroxide and aluminium yielding 1 -amino-2-napht hol and 4-amino-3 -h ydroxyphen ylarsinic acid NH,*C,H,( OH)*AsO<O H)2 the sodium salt C,H70,NAsNa,5H20 and silver salt of which are described. Under suitable conditions the red azo-dye is reduced by sodium hyposulphite yielding 4 4’ - diarnino - 3 3‘ - dihydroxyarsenobenxene As2[C,H,(NH,)*OH] the hydrochloride and sulphate of which are described c. s E. F. A. W. D. H. catalysts. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9120200065

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 7 5 Chemistry of Vegetable Physiology and Agriculture. Formation of Calcium Carbonate in the Soil by Bacteria. CONRAD T. GIMMINGHAM (J. Agric. Sci. 1911 4 145-149. Compare Munro Trans 1886 49 648 ; Hall and Miller Abstr. 1906 ii 119). -Six organisms were obtained from two soils which have the power of producing calcium carbonate from calcium oxalate. The time required as measured by the number of days which elapsed before crystals of calcium carbonate could be detected varied from fourteen to sixty-fiveii. 76 ABSTRACTS OF CHEMICAL PAPERS. days. An impure mixed culture was found to be more active. No production of carbonate took place under anaerobic conditions. It is probable that soils contain a number of organisms which oxidise calcium oxalate ; the organisms seem to be more active in this respect when the soil is deficient in organic matter.I. Ammonification. CHARLES B. LIPMAN (Centr. Bakt. Par. 191 1 ii 32 58-64).- Chlorides of sodium potassium calcium and magnesium have been shown to exert a marked toxic effect on Bcm7Zus subtilis and it apkeared of interest to ascertain the effect. of alkali salts on the ammonia producing flora of normal soils. To 100 grams of air-dried soil were added 2 grams of dried blood and 18 C.C. of water or of a solution of sodium chloride sulphate or carbonate so that the amount of salt added varied from 0.2 to 2.0% of the soil. After incubation at 26-28' for four days the ammonia formed was distilled over with magnesium oxide. It was found that even such quantities as 0.2% of sodium chloride exerted a marked toxic effect on the soil bacteria and the amount of ammonia was only about one-third of that formed by the untreated soil.Sodium sulphate acts more gradually but leads t o a similiar diminution of bacterial activity. Sodium carbonate stimulates ammonification in doses up t o 1% and only begins to be toxic when present in quantities above 1.4%. This may serve t o explain the presence of large amounts of plant food associated with '' black alkali " (sodium carbonate) Eoils. Increased or decreased bacterial activity cannot be correlated with plant growth on such soils as the behaviour of bacteria towards these salts is the reverse of that of higher plants. H. B. H. The Bio-chemical Conversion of Pyrrolidine-2-carboxylic Acid i n t o n- Valeric and 6-Aminovaleric Acids.CARL NEUBERG (Biochem Zeitsch 191 1 37 490-500).-By treatment of proline with the putrefactive bacteria derived from putrid meat in a suitable medium the two above-mentioned acids were obtained the valeric acid being separated by distillation with steam and the amino-acid left in the residue along with unchanged proline which latter substance was separated by means of its copper salt. A recapitulation of the putrefactive changes of the amino-acids already investigated by the author is also given. The Origin of Optically Active Valeric Acid in the Putre- faction of Proteins. CARL NEUBERG (Biochem. Zeitsch. 191 1 37 50 1-506).-d-isoLeucine yields on treatment with putrefactive bacteria as chief product d-valeric acid (a-methyl butyric acid) and also d-hexoic (d-P-methylvaleric) acid.The isoleucine employed was prepared synthetical 1 y . Does d-Ornithine Undergo Racemisation on Treatment with Putrefactive Bacteria 3 CARL NEUBERC (Biochem. Zeitsck. 1911 37 507-509).-The author could detect no racemisation of the d-base during putrefaction and in this respect obtained a result not in accordance with that obtained by Ackermann. N. H. J. M. Toxic Effects of " Alkali Salts " in Soils on Soil Bacteria. S. B. S. S. B. S. S. B. S .VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 7 7 Nitrogen Nutrition of Aspergillus niger. WIDAR BRENNER (Ber. Deut. botan. Ges. 191 1 29 479-483).-Experiments with Aspergillus niger on the assimilation of various forms of nitrogen showed that the most suitable of the compounds employed mere ammonium lactate tartrate succinate and oxalabe and asparagine.Carbamide and the mineral salts of ammonium come next in the following order sulphate chloride nitrate and phosphate ; then ammonium acetate and formate formamide nitrosodimethylamine hydrochloride and pyridine nitrate I n tho case of pyridine nitrate only the nitric nitrogen seems to be assimilated. Normal butylamine hydrmhloride follows immediately after nitrates. Guanidine nitrate and hydrochloride come next then isobutylamine hydrochloride and lastly isoamylamine hydrochloride hydroxylamine sulphate benzylamine sulphate dicyanodiamide and acetonitrile. Free ammonia sodium nitrite ammonium valerate and potassium cyanide are toxic whilst tetramethylammonium chloride nitro- guanidine nitromet hane isoamylamine acetat,e and pyridine and piper- idine chlorides were not utilised as sources of nitrogen.N H J. M. Cellobiose as a Source of Energy for Nitrogen Fixation by Azotobacter. ALFRED KOCH and SIEGFRIED SEYDEL (Centy. Bakt. Par. 1911 ii 31 567-570).-Cellulose cannot be utilised directly by Axotobacter and must undergo a preliminary decom- position by certain soil organisms before any nitrogen is assimilated. An attempt was made to cultivate Axotobacter on agar with 2% cellobiose but only one culture showed any gain (10.7 mg. N per gram of cellobiose supplied). This was due no doubt to the presence of soil bacteria capable of attacking the compound tested with the formation of sugar. Other cultures gave slight gains (2.55 mg.) when Aspergillzcs was grown on the medium previous to inoculation with Axotobacter.The conclusion is drawn tbat this organism is unable to utilise cellobiose in pure culture but does so in the presence of certain soil bacteria or of Aspergillus niger. The Process of Nitrogen Assimilation by Azotobacter. ALFBED KOCE and SIEGFRIED SEYDEL (Centr. Bakt. Pay. 1911 ii 31 570-577).-The usual method of estimating the nitrogen-fixing power of Axotobacter. whereby the amount of nitrogen gained is calculated on the amount OF carbohydrate supplied does not accurately represent tho intensity of the process. By means of a series of sugar and nitrogen estimations i t is shown that nitrogen fixation only occurs during active growth and comes to an end after five to eight days.The rest of the carbohydrate is used for respiration and other purposes. In one series of estimations the amounts of nitrogen fixed per gram of dextrose used were 53 70-80,20-30,5-8 mg. on the second third seventh and eighth days respectively. The Permeability of the Yeast Cell. SYDNEY G . PAINE (Proc. Roy. Xoc. 1911 B 84 289-307).-Pressed brewers' yeast was H. B. H. H. B. H.ii. 78 ABSTRACTS OF CHEMICAL PAPERS. immersed for varying times in solutions of various substances and the distribution of the substance between the cells and the surrounding liquid ascertained. With dilute alcohol in concentrations varying from 5 to 20% the ratio of tho concentration within the cells to that without rapidly becomes constant and is independent of the absolute concentra- tion.Alcohol is believed to diffuse readily into the cell arid as this ratio is not unity but approximately 0.85 it is probable that all the water within the yeast cell is not available for diffusion of the alcohol. All salts which have been tried are taken up by yeast from moderately concentrated solutions but differ from alcohol in that equilibrium is roached very much more slowly and the absorption is not nearly so corn- plete. Thus in the case of alcohol equilibrium was reached within three hours whereas with 0.1 molar sodium chloride none had entered in the same time and only a small quantity after twenty hours. With 0.1 molar disodium hydrogen phosphate no salt had entered the cells even after twenty hours’ immersion but from 0.3 molar solutions a marked entrance was observed in the same time.Sodium hexose- phosphate behaved in a similar manner to sodium phosphate. As there is no evidence that the latter is fermented by living yeast whilst it is readily fermented by yesst-juice i t seems probable that this salt does not penetrate into the seat of fermentative activity of the yeast-cell. W. J.Y. Fermentations with Yeast in Absence of Sugar. VI. CARL NEUBERG and L. KARCZACI (Biochem. Zeitsch. 1911 3’7 170-176. Compare Abstr. 1911 ii 320 520 1019 1020).-The action of the yeast ‘‘ carboxylase,” under the influence of which aldehyde and carbon dioxide are formed from oxalylacetic and pyruvic acids was investigated in the presence of the following substances Acetone- dicarboxylic acid chelidonic acid dihydroxytartaric acid benzoyl- acetic acid phenylpyruvic acid p-hydroxyphenylpyruvic acid phenyl- glyoxylic acid and acetylenedicarboxylic acid.A negative result was obtained wibh benzoylacetic acid and a doubtful one with acetylenedicarboxylic acid. All other acids showed evolution of carbon dioxide when treated with the enzyme. 8. B. s. Behaviour of Pentoses in Fermenting Mixtures. W. E. CROSS and BERNHARD TOLLENS (J. Landw. 1911 59 419-428. Compare Schone and Tollens ibid. 1901 21 ; Cross Bevan and Smith Trans. 1898 73 462).-The results of experiments with arabinose xylose arid rhamnose show that solutions free from sugars of the hexose series do not ferment and that the pentoses remain unchanged for a long time. Similar results were obtained in presence of dextrose when yeast-water was employed.I n artificial nutritive solutions however containing only small amounts of organic matter the pentoses are utilised for the growth of the yeast. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 79 Chemical Composition of Some Higher Fungi. A. GORIS and M. MAYCB~ (Compt. vend. 1911 153 1082-1084. Compare Abstr. 1909 ii 175).-Two cholesterols probably identical with Tanret’s ergosterol and fongosterol have been isolated from fungi of various species such as Lactrcrius piparatus Psalliota cccrnpestris Tricholoma album etc. A new compound apparently not a cholesterol has been obtained from cartnin fungi notably from CoZlyhia macdata. This substance is extracted from the dried material by means of acetone and occurs as large colourless crystals m.p. 201-202°. It is neutral does not contain nitrogen and is insoluble in water and ether. Carbamide is not invariably present in the higher fungi. The extent to which it occurs depends on the season and the mode of cultivation. w. 0. w. Narcosis and Want of Oxygen. 111. The Action of Narcotics and Oxygen-withdrawal on Germinating Seeds. G. MANSFIELD [witb in part B. FARKAS] (P’iiger’s Archiu 1911 143 175-185. Compare Abstr. 1910 ii 222).-The experiment,s recorded support Meyer’a views on the action of narcotics. They delay germination in exactly the same way as does the withdrawal of oxygen. W. D. H. Probable Function of the Essential Oils and Other Volatile Products of Plants as the Cause of the movement of Sap in Living Tissues. ITALO GIGLIOLI (Atti R.Accad. Lincei 1911 [v] 20 ii 349-36l).-The vapours of carbon dioxide ether chloroform and formaldehyde and of many essential oils decrease the surface tension of aqueous solutions as may be shown by the rapid disintegra- tion of soap-films exposed to them. Porous rock or sand which contains just as much water as it can hold by capillarity gives out water in an atmosphere containing these substances. A similar behaviour is observed in the case of many plants. When the dried comprsssed yeast of commerce is exposed to air containing the vapour of chloroform oil of eucalyptus or camphor or of camphor it becomes soft and juicy in a few hours ; in a few days the mass is wet enough t o filter and the filtrate is not water but a juice containing zymase. Boletus behaves in the same way exuding :t liquid containing much organic matter. The organs of the higher plants are similarly affected by these vapours and by those of a large number of essential oils; the tissues become more succulent and sap is exuded.The action may be revealed in the earlier stages by the activity of the enzymes which the moving saps contain; thus the seeds of the apricot and the leaves of the cherry-laurel are caused t o produce hydrogen cyanide by the vapours of a large number of essential oils and other sub- stances. The evolution of hydrogen cyanide is explained by the author as being due to the action of enzymes brought into contact with their substrates by the movement of the sap which the vapour initiates. Since the activity of plant enzymes often leads to the formation of essential oils the author regards the effect as cumulative and finds in it an explanation of the movement of sap in plants. R.V. S.ii. 80 ABSTRACTS OF CHEMICAL PAPERS. Plants Containing Essential Oils. ANNE W. K. DE JONG (Rec. trav. chim. 1911 30 211-219. Compare Abstr. 1905 i 802).- The quantity of essential oil in the plant is measured by distilling a definite weight of leaves with about five times the weight of water the water distilling over being returned from time to time until the quantity of essence in the distillate no longer increases. I n the case of Singapore Patchouli (Pogostemon tomentosw) i t is found that the essence is formed in the three top leaves and that the quantity only diminishes slightly with age.The branches also contain the essence and the roots contain an essence heavier than water. With Java Patchouli the quantity of essence also diminishes after the third leaf. Contrary to the idea in text-books on the subject the author finds that the quantityof essence in fermented leaves is not greater than in dried leaves. The first leaves however show by distillation a much smaller amount of essence than the other two. Formation of Anthocyanin. (Miss) MURIEL WIIELDALE (J. Genetics 1911 1 133-158. Compare Nierenstein and Wheldale this vol. i 42)-From the consideration of analogous reactions and the results of observations on the distribution of anthocyanin and from experimental evidence on the concentration of sugars and glucosides in various tissues on the existence of enzymes and on sugar feeding the following conclusions are drawn.The soluble pigments in flowering plants collectively termed antho- cyanin are oxidation products of colourless chromogens existing in the tissues as glucosidee. The production of the glucoside from the chrornogen and sugar is of the nature of a reversible enzyme reaction chromogen + sugar s glucoside + water and the oxidation of the chromogen which is effected by one or more enzymes can only take place after its liberation from the glucoside. The amount of free chrolriogen (and hence of pigment) formed at any time is thus inversely proportional to the concentration of sugar and directly proportional to the concentration of glucoside in the same tissue. The local production of anthocyanin is due to local variation in concentration either of the free sugars or the glucosides.Abnormal production of pigment results from similar differences in concentration caused by changes in metabolism due to altered conditions. The above hypothesis brings the formation of anthocyanin into line with that of other pigments produced after the death of the plant (indigo t i n e tc.) . C. A. JACOBSON (J. Amer. Chern. Xoc. 1911 33 2048-2051).-Experiments are described which indicate that alfalfa contains myristone in combination with one or more other substances. The compound or compounds can be extracted with hot 95% alcohol and the myristone can be isolated by means of dilute nitric acid. E. G. Amount of Hydrogen Cyanide during the Ripening of Bitter and Sweet Almonds.G. DE PLATO (Chem. Centr. 1911 ii 882 ; from Stax. sper. agrar. ital. 1911 44 449-458).-1n bitter W. 0. N. H. J. M. Myristone Obtained from Alfalfa.VEGETABLE PHYSIOLOGY AND AGRICULTURE ii. 81 almonds the amount of free hydrogen cyanide diminishes whilst the glucoside hydrogen cyanide increases with the growth of the cotyledons. The hydrogen cyanide in sweet almonds disappears as ripening proceeds. N. H. J. M. Chemical Examination of the Leaves of Anona muricata. THOMAS CALLAN and FRANK TUTIN (Pharm. J. 1911 [iv] 33 743-745).-The alcoholic extract of the leaves on distillation in steam yielded a small amount of a green volatile oil having a strong rather agreeable odour. The water-soluble portion of the extract con- tained potassium chloride tannin dextrose uncrystsllisnble alkaloid and amorphous products the latter being extracted in turn by ether chloroform and amyl alcohol.The portion of the extract insoluble in water consisted of a soft oily green resin which was extracted suc- cessively with (a) light petroleum ( b ) ether ( c ) chloroform (d) ethyl acetate and ( e ) alcohol of which the first two alone gave extracts which yielded definite products (a) This was a dark green oily mass which when liydrolysed by potassium hydroxide in alcohol furnished myricyl alcohol and sitosterol with linoleic oleic and stearic acids and a fourth acid which may be lignoceric acid C,,H,,O,; (b) this formed a dark green soft mass which after the removal of a dark green solid sparingly soluble in ether was hydrolysecl by potassium hydroxide in alcohol and yielded a mixture of acids giving non-volatile methyl esters together with myricyl alcohol sitosterol and anonol y.-p. 294-29s’ (decomp.) crystallising in colourless leaflets and giving colour reactions similar t o those of ipurganol; the diacetyl derivative m. p. 1664 forms colourless flattened needles and the dibensoyt? derivative m. p. 197-19So small colourless needles. No glucoside was present. T. A. H. Crystalline Protein from the Latex of Antiaris toxicaria. YAS~IRO KOTAKE and FRANZ KNOOP (Zeitsch. physiol. Chern. 1911 75 48S-498).-The residues of Antiayis toxicaria latex after extraction with 85% alcohol (compare Kiliani Abstr. 191 1 i 138) when extracted with 0.8% acetic acid yield a substance crystallising in needles or short characteristic prisms.When purified by crystallisation from normal hydrochloric acid i t forms polyhedra and is free from ash. It is precipitated from solution in acetic acid by half-saturation with ainmonium sulphate and shows the protein colour reactions excepting that of Molisch. It has the composition C 48.02 H 5.7 N 15.6 8 7.2 [aID - 19-25’ and contains On hydrolysis the foimation of cystine tyrosine lysine glycine alanine proline and valine was detected. KAN KATO (Zeitsch. physiol. Chern. 191 1 ’75 456-474).-The sap of bamboo shoots con- tains nuclease and a ‘‘ deamidase,” which decomposes urea strongly and asparagino slightly but does not attack glycine. A proteolytic enzyme acting on fibrin was detected and is being investigated and one or more diastases.Amygdalin and salicin are also decomposed. H. B. H. ~,,H36O,(OH) 15.7% of water of crystallisation. E. F. A. The Enzymes in Young Bamboo Shoots. VOL. CII. ii. 6ii. 82 ABSTRACTS OF CEEMICAL PAPERS. The Influence of Chemicals on the Germinating Capacity of Cuecuta arvensis and Cuscuta trifolia. G. D'IPPOLITO (Chem. Zentr. 1911 ii 370; from Xtax. sperirn. agrrccv. ital. 44 301-308).- The action of chemicals in sterilised and ordinary soils on the germina- ting capacity of the seeds was investigated. Ammonium nitrate sodium carbonate calcium cyanamide and formalin kill the seeds potassium nitrate and carbonate almost ebtirely inhibit the germinating capacity sodium and calcium nitrates act less powerfully and mag- nesium sulphate has hardly any action.For killing Cuscutu the author recommends the treatment of the soil with either 2% ammonium nitrate or 1% formaldehyde solution. S. B. S. The Presence of Sucrose in Gentian Root Dried in the Air without Fermentation. MARC BRIDEL (J. Phccrm. Chim. 19 11 [vii] 4,455-458).-Gentian root which has been dried without under- going fermentation contains large quantities of carbohydrates hydro- lysahle by invertase. On the other hand commercial preparations which are fermented in the process employed in their production contain very much less of these carbohydrates. The principal carbohydrate is sucrose which was isolated from the root by extraction with alcohol. No gentianose could be obtaiued. W. J. P. A Proteolytic Enzyme in the Must of Over-ripe Grapes.ENHICO PANTANELLI (Centr. Bakt. PUT. 191 1 ii 31 545-559).-The must from over-ripe white and black grapes contains an enzyme which breaks down the proteins with the formation of soluble products not precipitated by copper hydroxide. This change is probably due to the action of several enzymes since it occurs also when the reaction is neutral or slightly alkaline. The presence of tannin does not inhibit the change. The decomposition products primarily formed become condensed by the act'ion of a substance to which the name synprotease has been given and a state of equilibrium is established Among the antiseptics employed thymol and potassium meta- hydrogen sulphite allow of a greater enzyme action than formaldehyde but the eulphite probably acts chemically as the amount of change increases with the sulphur dioxide content of tbe solution.H. B. H. Action of Certain Diureides and of Hippuric Acid on the Development and Tuberisation of Radishes. MABIN MOLLIARD (Compt. rend. 1911 153 958-960).-Radishes were grown in nutrient solut,ions to which 0.1% of different nitrogen compounds were added. Glycine carbamide xanthine sodium urate and allantoin increased the yield of dry material in the plants whilst sarcosine theobromine caffeine and sodiun hippurate exerted a toxic action diminishing the yield. Caffeine was the only compound which corn- pletely stopped development. Xanthine was less toxic than sarcosine ; sodium urate amd allantoin exerted the most favourable effect on development. The proportion of water in the plants showed anVEGETABLE PHYSIOLOGY AND BURICULTURE.ii. 83 increase with all the compounds examined except caffeine. Sodium urate increases the number of tubers formed and raises their total Presence of Glycogen in Phanerogame and its Relation to Calcium Oxalate. IOANNES POLITIS ( A tti R. Accad. Lincci 191 1 [v] 20 ii 431-439).-Glycogen which has hitherto been found among plants only in the cryptogams occurs also in certain phsnero- gams but always in cells in which deposits of calcium oxalate after- wards appear. The mucilage of the tubers of Orciris M ~ i o which has been cousidered to be cellulose is shown by its microchemical behaviour to be glycogen which has been similarly demonstrated in Blctia content of dry material. w. 0. w. y acin t hina Pit cair nia xaiz t hocub y x and Bi I? I b c rg i a nut ans.R. V. S. The Action of the Respiratory Enzymes of Sauromatum Venolsum. TH. WEEVERS (Proc. K . Akad. Vetensch. Antslerdam 1911 14 370-377).-1f the juice expressed from the spadices of Saurornatwn venosurn is precipitated with alcohol a crude preparation of an enzyme is obtained which decomposes dextrose with the forma- tion of carbonic and organic acids but without the production of alcohol either in air or an atmosphere of hydrogen. Destruction of the cellular structure and treatment with alcohol or acetone do not inactivate this respiratory enzyme. A crude enzyme is similarly obtained from the leaves of the plant but its action is weaker. In the ethereal extract of the acid liquid citric acid was demonstrated; this is probably formed by the respiratory enzyme at the expense of the dextrose.W. 0. H. Formation of the Alkaloids in Tobacco. CIRO RAVENNA and Y. BABINI (Atti 22. Accud. Lincei 1911 [v] 20 ii 393-398. Com- pare Ciamician and Eavenna hbstr. 19 11 ii 76 l).-The authors have estimated the amount of nicotine produced in tobacco plants in culture solutions with a view to determining the effect of nitrates dextrose and light. No final conclusions are drawn from the experi- ments but the amount of nicotine produced was greater in all cases than the amount found in plants grown in soil and the increase was greatest where both dextrose and nitrates were supplied to plants growing iu the light. The Ammonia Content of Tobacco Smoke. WILHELM VAUBEL (Cham. Zcit. 191 1 35 1331-1332).-The chsnge in colour of the Ieaves of certain flowera when .these are exposed to tobacco smoke is due to the presence of ammonia in the smoke; when the smoke from a cigar is drawn into the mouth the ammonia is absorbed and the smoke expelled from the mouth is without effect on the flowers.The author also discusses the physiological action of tobacco smoke. w. P. s. FRIEDRICH STROHMER and OTTOKAR FALLADA (Chem. Zentr. 191 1 ii 386 ; from 0sterr.-uozg. Zeitsch. Zuchr-lnd. Lucndw. 19 11 40 426-441 ).- Experiments were carried out on the replacement of sodium nitrate R. V. S. Manuring of Sugar Beets with Sodium Chloride. 6-2ii. 84 ABSTRACTS OF CEEMICAL PAPERS with ammonium sulphate containing the same amount of nitrogen together with sodium chloride.With the exception that the beets contained more chlorine and sodium the results were nearly the same. S. B. S. The Treatment of Soil with a Strong Continuous Electric Current. JOSEF KONIG JULIUS HASENBAUMER and C. HASSLER (Zeitsch. nngew. Chsm. 191 1 24 2341-2348. Compare Abstr. 1910 ii llO4).-The soil is mixed with water and introduced into a dialysing vessel in which a platinum cathode is placed. The platinum anode is placed in the outer vessel below the parchment diaphragm. A current of 3 amperes is then passed and the inner and outer solutions are renewed whenever the temperature reaches 50'. The collected anodic and cathodic solutions are filtered and analysed. With sandy soils the organic content of the acid liquid as shown by titration with permanganate is greater than that of the alkaline solution whilst with marly and clayey soils the proportions are reversed.This is due to tbe larger proportion of humic acids which do not coagulate but pass through the diaphragm in sandy soils. Other experiuients with soils previously treated with potassium phosphate show that only readily soluble salts and those retained by colloids are dissolved by the current. A comparison of three processes heating the soil with water under five atmospheres pressure oxida- tion with hydrogen peroxide and electrolysis shows that the two former methods dissolve about equal quantities of potash whilst oxidation dissolves rather more phosphoric acid. Electrolysis dissolves much greater quantities even a single passage of the current dissolving more potash and phosphates.C. H. n. Hygroscopic Moisture of Soils. CHARLES B. LIPMAN and LESLIE T. SHARP (J. Pzjysicul Chem. 1911 15 709-'722)-In the estimation of the amount of moisture absorbed from n sa.turated atmosphere by dried soils the soil must be exposed in a thin layer. If the soil is much woi-e than one millimetre deep a very long time is necessary for the attainment of equilibrium A rise in temperature with correspondiag rise in the pressure of the aqueous vupour leads to a greater absorption of water by the various soils studied but no definite law of absorption could be found. The absorptions appeared to be lower a t a steady temperature in the incubator than with fluctuating room temperatures of about the same degree. It is suggested that plants in the arid regions are protected by the great amounts of hygroscopic moisture absorbed by the soil with rising temperatures.R. J. C. Loew ' s Lime-Magnesium Ratio. ROBERT STEWART (J. I n d . Eny. Chem. 1911 3 376-378).-The beneficial action of lime on agricultural soils is a well-known and undisputed fact but that of magnesium is not understood and according to some authorities it has beneficial results only when present in a certain ratio t o the calcium whilst others state that it has a detrimental or even toxic effect on plant life.VEGETABLE PHYSIOLOGY ASD AGRICULTURE. ii. 55 After discussing previous work on this subject the author describes the conditions prevailing on a farm belonging to the Utah experiment station where analysis of the soil at a depth of 1-8 feet shows the presence of 30-41% of calcium carbonate and 11-20% of magnesium carbonate and although the land has been continuously cropped for forty ye:irs without the addition of manure its average yield in bushels per acre is oats 82.0 wheat 50.4 and potatoes 262.The author suggests that possibly magnesium when present as the double salt MgCa(C03)2 reacts differently to the simple salt MgCO,. F. M. G. 31. Effect of Ignition on the Solubility of Soil Phosphates. GEORGE Y. FRAPS ( J . I n d . Eng. Chem. 1911 3 335).-An account OF experiments which demonstrate that the ignition of soil during ten miuutes at a dull red heat greatly increases the solubility of some OF its inorganic constituents in hydrochloric acid and therefore the experi- menters who consider the increased amount of soluble phosphoric acid found in soils after ignition to be due to liberated organic phosphorus are in error.The author finds t h a t ignition (1) increases the solubility tell times of the phosphoric acid in wsvellite dufrenite and variscite in NIB-nitric acid ; (2) it renders these minerals almost completely soluble in 12% hydrochloric acid and (3) it converts considerable quantities of iron and aluminium oxides into a soluble condition. F. M. G. M. After-effect of Palmaer Phosphate Basic Slag and Super- phosphate on Peat Soil. HJALMAR VON FEILITZEN (J. Landw. 1911 59 371-374).-Potatoes and blue lupins were grown in large boxes containing peaty soil previously manured with the three phosphates (P,O,= 50 and 100 kilos. per ha.).The after-effect with potatoes was greatest with basic slag next with Pizlmaer phosphate whilst with superphosphate somewhat lower results were obtained. The percentage of starch was highest i n the soil containing the residue of Palmaer phosphate and where the larger amount had heen applied (P,O,= 100 kilos.) the greatest yield of starch was a!so with Palmaer phosphate. I n the case of lupins the highest yield after an application of 50 kilos. of phosphoric acid was with superphosphate whilst with the higher amount of phosphates the best result was obtained from t h e residue of Palmaer phosphate. As regards after-effects Palmaer phosphate seerus therefore to be a t least equal to superphosphate on peat soil containing plenty of lime and nitrogen. The after-effect of basic slag is somewhat greater.N H. J. M. Volatilisation of Ammonia and Changes of Ammonia in Soils. JOHANN VON WLODECK (Bied. Zentr. 1911 40 729-734 ; from Inaug. Dias.).-The loss of ammonia from soils containing considerable amounts of calcium carbonate is much reduced when ammonia-superphosphate is employed instead of ammonium sulphate. A light soil manured with ammonium sulphate showed a loss ofii. 86 ABSTRACTS OF CHEMICAL PAPERS nitrogen whilst the same soil manured with ammonia-superphosphn te showed a gain. This is attributed t o increased fixation of nitrogen by soil organisms due to the application of phosphate. A loam soil containing over 10% of phosphoric acid soluble in hydrochloric acid gave the same results with ammonium sulphate as with ammonia super phosphate. As regards the fixation of the ammonia applied to soils manuring with ammonia-superphosphate as compared with ammonium sulphate seems to have a retarding effect. N.H. J. M. Origin of Creatinine in Soils. MICHAEL X. SULLIVAN (J. Awcr. ChLa~m. SOC. 191 1 33 2035-2042).-The occurrence of creatinine in soils has been demonstrated by Shorey (Science 1910 33 340). A study has now been made to determine its mode of origin. It has been found that creatinine occurs more abundantly in soil8 mhich have recently borne a crop than in those which have not been planted for some time. It has also been detected in water in which w heat-seedlings had been grown and also in wheat wheat-bran rye clover alfalfa cowpeas and potatoes. Although creatinine and creatine are o~ily present in small amounts in vegetable matter they are of importance since by the decay of plant tissues and by green manuring they collect i n the soil and exeraim a beneficial influence on the growth of the crops. E. G. Estimation of Solubility in Agricultural Chemistry. ARTHUR RINDELL (Akad. Einladungsschr. Helsingfom. 1910 67 pp.).-The difficulties in estimating the solubilities of different manures (especially phosphates) due t o varying conditions are discussed. Since the mineral constituents of plants can only be assimilated when in solution and it is probably correct to assume that the production of dry matter in crops has a constant relation to the amount of water used it is possible to calculate the concentration of the nutritive solutions taken up at different periods. The following figures are given for a normal crop of barley (2500 kilos. of grain and 3000 kilos. of straw and chaff per hectare) Period ......... I. 11. 111. IT. 1.-IV. Days ........................ 19 28 20 24 91 N mg. per litre ......... 76.6 21 *9 2 - 4 22.4 31.1 K,O ) ) ......... 108.6 35.9 (1.4) - 37 '9 P,O ......... 3 7 *7 15.9 10.0 13.1 17'3 N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9120205075

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 86 ABSTRACTS OF CHEMICAL PAPERS An aly t ical C he mist r y . A Modifled Explosion Eudiometer. F. H. CAMPBELL (Chem. News 1911 104 235-236).-A Chree-way capillary tap is fitted at the top of the eudiometer; this arrangement is convenient when it is desired to demonstrate the proportions in which various gases combine,ii. 87 ANALYTICAL CHEMISTRY as the latter may be introduced separately through the tap into the apparatus. w. P. s. Simplification of Gravimetric Analysis. ERNST MURMANN (Zeitsch. anal. CIbem. 191 1 50 742-747).-Instead of an ordinary filter a small disk of wet filter paper is placed over a perforated porcelain disk and when filtering suction is applied. A special apparatus is recommended which is figured in the original. Introduction of a minute quantity of filter-paper pulp is recom- mended.I n cases where the precipitate has t o be ignited the precipitation as sulphide is much assisted by the addition of mercuric chloride or i n the case of stsnnic oxide some mercuric sulphide may be added in order to get rz clear filtrate. The weight of the filter disk being seldom more than 0.02 gram the process is very suitable for the direct weighing of dried precipitates as it is not necessary to employ a weighing tube. Of course no pulp is then added. L. DE K. Standardising of Acids W i t h o u t the Aid of Alkali Solutions. FRIEDRICH KLINKERFUES (Chem. Zeit. 19 1 1 35 1274). -A definite volume of the acid intended for titrations is plac9d in a suitable receiver in which is then collected the ammonia evolved from an accurately known weight of ammonium sulphate.C u e should be taken that there shall be a slight excess of ammonia at the end of the distillation. After adding a suitable indicator bhe free ammonia present is titrated with the same acid and the strength of the latter is then found by an easy calculation L. DE K. The Application of Methyl-red to the Colorimetric Measure- ment of Hydrogen Ion Concentrations. SVEN PALITZSCH (Biochem. Zeitsch. 1911 37 131-138).-The substance p-dimethyl- aminoazobanzene-o-carboxylic acid is specially adapted to the measure- ment of the hydrogen ion concentrations between the zlmes pLL= 4.2 and pa= 6.3 in which the colours vary from violet-red to yellow. The author gives a table of corrections to be applied in the pre,-,encc of sdtrs and proteins in which cases the [HI*-concentratiuns were determined by him electrometrically. The corrections t o be applied are only small S.B. S. The Analysis of Chlorates. VON BuTTrAR (Chcrn. Zeit. 1911 35 137P).-Calcium carbonate is generdly used in the neutralisation of reduced chlorato solutions before reduction. Time is saved by using magnesium hydroxide made into a cream with water. Neutralisation is complete when a permanent turbidity appears and filtration is unnecessary C. H. D. Estimation of Perchloric Acid in Certain Perchlorates. HENRYK GOLBLUM (Zeitsch. and. Chem. 1911 50 741-742).-The author estimates perchloric acid in the nickel or cobalt compounds as follows About 0.2 gram of the salt is dissolved in 300 C.C. of water and electrolysed at the ordinary temperature for some seventy hours,ii.88 ABSTRACTS OF CHEMICAL PAPERS. using as cathode a platinum gauze and a very weak current up t o 0.1 ampere. The potential is rather high on account of the strong resistance and varies between 10 and 12 volts. The liquid containing the liberated perchloric acid is then titrnted Detection of Fluorine. ERWIN RUPP (Zeitsch. Nahr. Geimssna. 1911 22 496-497).-The ash of the material to be tested for the presence of fluorine (fluorides) is placed in a platinuni or lead crucible 2nd moistened with 3 drops of water and 1 C.C. of sulphuric acid. The crucible is then closed with tt rubber stopper through which passes a glass rod the end of the rod below the stopper being moistened with a drop of water. The crucible and its contents are now heated on a water-bath for about twenty minutes; during this time the water on the glass rod evaporates and should fluorides be present the rod becomes coated with a film consisting of silica sodium silicofluoride and calcium silicofluoride. When only traces of fluoride are present the portion of the glass rod below the stopper may be covered with a piece of rubber tubing leaving only the end of the rod exposed ; the action of the hydrofluoric acid is thus concentrated on a small surface G.B. VAN KAMPEN (Chem. Weekblad 1911 8 856-860).-For estimating calcium fluoride in the basic slag of the Talbot process the author recommends Penfield’s method (Abstr. 1879 829) the conversion into silicon tetrafluoride the decomposition of the fluoride with water in accordance with the equation 3SiF + 4H20 + 4KC1= H,SiO + 2K2SiF6 + 4HC1 and the titration of the hydrochloric acid formed using lacmoid as indicator.with N / 1 0-alkali with phenolphthalein as indicator. L. DE K. of the glass. w. P. s. Estimation of Fluorides. A. J. \V The Estimation of Oxygen in Iron and Steel. ALLERTON S. CUSHMAN (J. Ind. Eng. Chcm. 1911 3 372-374).-The three important methods for estimating oxygen in steel are (1) heating the sample in a stream of dry chlorine ; (2) dissolving in special solvent. such as copper sulphate or bromiDe; (3) combustion in a stream of hydrogen and the paper contains a sketch of the apparatus employed with exact details of how the author conducts the latter method The hydrogen is generated from drillings of pure iron or Lcmossy ” zinc with dilute hydrochloric acid and is passed succersively through potassium hydroxide solution concentrated sulphuric acid over a roll of platinum gauze in a strongly heated silica tube and finally over phosphoric oxide.The finely divided borings (20-30 grams) are weighed into a platinum (or silica) boat introduced into the silica combustion tube and after passing hydrogen until all air has been removed the tube is rapidly heated to about 850” maintained a t this temperature during about thirty minutes whilst the purified dry hydrogen passes at TS rate of about 100 C.C. per minute ; the apparatus is cooled in the stream of gas and the tared absorption tube which is charged with phosphoric oxide re-weighed. A correction obtained by blank experiments must be employed to ensure accurate results.F. M. G. M.ANALYTICAL CHEMISTRY. ii. 89 Estimation of Sulphur in Pyrites. ARNOLD HECZRO (Zeitsch. anal. Chem. 19 11 50 748-753).-The following conclusions are arrived at. For a rapid and safe estimation of available sulphnr in pyrites Dennstedt’s process (combustion in oxygen absorption of the gases in sodium carbonate heated a t 450’ Abstr. 1905 ii 761) is very suitable. Tubes made of quartz instead of Jenn glass are however preferable as they do not retain traces of sulphuric acid; this saves t h e trouble of rinsing the tube with hot water. When precipi tnting the sulphate with barium chloride double the theoretical quantity of the latter should be added. The results agree very well with those obtained by Lunge’s process.L. DE K. The Phenolcilulphonic Acid Method for the Estimation of Nitrates in Water. ALFRED E. JOHNSON (Chern. News 1911 104 235)-Attention is drawn to the necessiLy of heating the sulphuric acid and phenol together for eight hours (compare Abstr. 1890 ii 832) in order to obtain a reagent which will yield a red coloration with nitrates without any development of a green coloration. w. P. s. Estimation of Nitrogen in Drainage Water and Rain Water by Schloesing’s Method. (Miss) ALIDA HUIZINGA (Chm. Weekblad 1911 8 882-895).-The usual method of carrying out Schloesing’s process gives inaccurate results arising from the presence of air in the solutions employed and of nitrites and carbonates in the samples examined. The author recommends evaporation of the water with potassium hydroxide instead of magnesium oxide elimination of carbonic acid by boiling with acetic acid and oxidation of the nitrite with acidified potassium permanganate.With these precautions the error in the estimation of the nitrogen in an ordinary sample does not exceed 0.1 mg. of nitrogen A. J. W. Bacteriological Methods for E s t i m a t i n g t h e Available Nitrogen in Fertilizers. JACOB G. LIPMAN (J. Ind. Eng. Chem. 1910 2 146-:48).-That the formation of nitrates in organic substances bears a direct relationship to the proportion of nitrogen they contain and generally also t o the ease with which they ixndergo decomposition has been demonstrated previously. From the fact t h a t nitrate formation is preceded by the formation of ammonia i t would appear that a similar relationship should exist between ammonifica- tion and nitrification and the present paper contains an account of preliminary experiments for the purpose of testing this hypothesis. The nitrogenous material to be tested was mixed with 100 grams of soil and 1 gram of calcium carbonate and maintained at its optimum moisture content (18%) ; a further quantity of water was added in the ammonification experiments to ensure an organic matter containing 75% moieture; the ammonia determination was made after six days and the nitrate estimation after four weeks.The results showed that as a general rule easily ammonifiable substances are also readily nitrifiable the highest ammonia content being found in concentrated tankage ground fish solid and liquidii.90 ABSTRACTS OF CHEMICAL PAPERS. fresh manure dried blood and bone-meal whilst the nitrate content followed the order concentrated tankage cottonseed meal ground fish dried blood and solid and liquid fresh manure. The high position of cottonseed meal in the nitrate series whilst possessing low availability in the ammonia series is considered (from the result of other experimenh) to be due to the depressing effect of soluble carbohydrates on ammonification. F. M. G. M. A Bacteriological Method for Estimating Available Organic Nitrogen. J. M. MCCAUDLESS and F. C. ATHINSON (J. Ind. Eng. Chem. 1911 3 174-175).-An account of experiments to determine the available ammonia in two samples of fertilisers prepared from leather by a special process which rendered it soluble; cottonseed meal was employed for comparison. Tho total nitrogen content in the initial materials also in their filtered boiling water extracts was estimated the extracts shaken up with soil the filtered solutions incubated at 38-40' under both aerobic and anwobic conditions (the surface of the liquid in the latter being protected by a layer of oil) and the ammonia estimated a t intervals.After two hundred and ten hours the experiments were stopped by exhaustion of the flasks ; in the anaerobic experiments practically no reaction had taken place but in the others considerable quantities of soluble organic nitrogen had been converted into ammonia ; i n one case (3.35% ammonia) the action was retarded probably by the toxic effect of excess of ammonia on the organism producing it.The insoluble residues were treated with soil extract in the presence of a nutritive mixture (devoid of nitrogen) and after twenty-six days the extracts and residues separately examined when i t was found that a quantity of insoluble proteid matter had been converted into ammonia. The author concludes that two distinct processes are involved ( 1 ) the conversion of insoluble proteids into a soluble form and (2) their subsequent change into available ammonia but whether both these changes are the work of the same or of separate organisms has yet to be determined. F. M. G. M. Estimation of Phosphorus in Iron and Steel. C. REICHARD (Pharm. 2entr.-h. 1911 52 1314-1315).-0wiug to the high molecular weight of the ammonium phosphomolybdate (" yellow ") precipitate and the fact that even minute quantities of phosphorus in iron or steel still yield a precipitate that can be weighed with great accuracy it is proposed to limit the amount of iron taken for analysis to 1 gram.L. DE K. Estimation of Inorganic Phosphorus in Animal Tissues. A. C. WHITTIER (J. Ind. Eng. Chern. 1911,3,248-250).-An account of various methods employed for tbe estimation of phosphorus in animal tissue with a discussion on the difficulty (owing to the rapidity of subsequent chemical change) of determining the relative proportions in organic and inorganic combination at the time of death. The cnncliisions drawn are (1) that the determination of organicANALYTICAL CHEMISTRY. ii. 91 phosphorus by the barium method gives high results with uncoagulated extracts owing to barium phosphate passing through the filter.(2) A t the boiling temperature water has very little hydrolysing action on organic cornpourids of phosphorus in animal tissue. (3) Enzymes and bacteria have a greater hydrolytic action on organic pho3phorus compou~ids than boiling. (4) Coagulation of the proteins by boiling clears the solution giving more complete precipita.tion and also arrests the action of enzymes and bacteria. F. n!t. G. M. The Quantitative Separation of Organic Phosphorus and Phosphates iu Fodders. GUSTAV FINGERLING and A. H ECRING (Biochent. Zeitsch. 191 1 3’7 452-456).-In Stutzer’g process the inorganic phosphates are extracted from the material by dilute hydro- chloric acid and precipitated from the solution thus obtained by ammonia and calcium chloride.The precipitated phosphates are theu dissolved in nitric acid aud precipitated from this acid solution as phosphomolgbdate. The authors find that this process is in most cases satisfactory but it is not applicable to those materials which contain phytin which is precipitated with inorganic phosphates. As this substance is present in a large number of fodders a new process is necessary for estimating phosphoric acid in materials of this character. S. B. S. Comparison of Methods for the Estimation of Phosphates in Vegetable Substances. A. PONTE (Chenz. Zentr. 1911 ii 900; from Stax. sperim. ayrar. ital. 1911 44 459-461).-1ncineratiou of the substance with the addition of calcium oxide yielded results which agreed with those obtained by electrolytic oxidation whilst from 2 to 11% less phosphoric oxide was found by the ordinary method of incineration.w. P. s. A Possible Fallacy in Fleitmann’s Test [for Arsenic]. WALTER J. DILLING (Phacrm. J. 1911 [iv] 33 811).-Arsenic having been found in a urine by the Fleitmann test when its presence was thought to be highly improbable the author investigated the cause and found that when applying this test the test-tube containing the zinc and sodium hydroxide with the suspected material should be heated until a stream of hydrogen bubbles is being evolved and no longer; the tube should be removed from the flame and the silver nitrate paper then placed over the mouth of the test-tube. If as might be done unintentionally the mixture is boiled the steam escaping (which perhaps also contains volatile organic products) exerts a more or less strong reducing action and the spot obtained may be mistaken for an arsenical one.L. DE 3. The Estimation of Arsenic in Insecticides. E. B. HOLLAND (J. Ind. Eng. Chcm. 1911 3 168-171).-A review of numerous methods employed for the estimation of arsenic with a discussion as t o their adaptability to the analyses of insecticides in which arsenic tri- or pent-oxides are the active constituents. The Avory-Haywoodii. 92 ABSTRACTS OF CHEMICAL PAPERS. method (Proc. Assoc. 08. Agr. C’hm. 1905 22 27) is considered most trustworthy and from it the author carries out the following modified procedure. About 2 grams of the sample are boiled during five minutes with 50 C.C.of sodium acetate solution (1 2) cooled shaken with about 60 C.C. of dilute hydrochloric acid (1 3) filtered from insoluble matter and the volume made up to 500 C.C. About 25-50 C.C. are neutralised with dry sodium hydrogen carbonate and treated with 25 C.C. of sodium potassium tartrate (10%) (to redissolve the copper) and titrated with N/20-iodine in the presence of starch. For samples containing lead arsenate the following method is recom- mended Twograms of the sample are boiled with 66 C.C. of nitric acid (1 3) cooled filtered and made up to 500 C.C. From 50 to 100 C.C. are removed evaporated with 10 C.C. of diluted sulphuric acid (2 l) and finally heated to 150-200°; the residue is dissolved in water treated with 10 C.C.of potassium iodide (1 65 lOOO) and boiled until free iodine is expelled ; the solution is rapidly cooled neutralised with sodium hydroxide re-acidified with sulphuric acid starch paste added any remaining free iodine dostroyed with sodium thiosulphate the liquid rendered alkaline with sodium hydrogen carbonate and titrated with N/20-iodine solution. F. N. G. M. Elementary Analysis. RICHARD DOHT (Zeitsch. anal. Chem. 1911 50 756).-The author thinks that it would have been better if Kurtenacker (Abstr. 1911 ii 823) had given analytical figures t o prove why silver and iron are not suitable for the reduction of nitric oxides in the combustion of nitrogenous substances for experiments conducted by himself and Epstein (Abstr. 1908 ii 132) led to a different view.L. DE K. Detection of Carbon Disulphide in Oils. E. MILLIAU (Compt. rend. 19 11 153 1021-1023).-Vegetable oils employed as lubricants should be free from carbon disulphide. This substance may be detected by heating 25 grams of the oil with 10 C.C. of a concentrated potass- ium hydroxide solution adding 150 C.C. of water and a little sodium hydrogeu carbonate. The mixture is then poured into 20 C.C. of hydrochloric acid and the evolved gas tested for hydrogen sulphide by means of lead acetate paper. A second method consists in distilling 50 grams of the oil with 10 C.C. of amyl alcohol. The first 4 C.C. of distillate are heated in a sealed tube on the water-bath with 1 C.C. ol cottonseed oil and a few centigrams of sulphur. The presence of traces of carbon disulphide is recognised by the appearance of a red coloration.w. 0. w. Estimation of Silica in Iron Ores. FR. MOLDENHAUER (Zeitsch. anal. Chem. 1911 50 754-755).-111 order to obtain accurate silica estimations it is advisable to use platinum dishes as i t is often impossible to remove the silica rendered insolu bIe by evaporation from porcelain basins. L. DE I(.ANALYTICAL CHEMISTRY. ii. 93 Rapid Estimation of Zinc. X. VOIQT (Zeitsch. angew. Chem. 19 1 1 24,2195-2198).-The process is briefly as follows One to three grams of the zinc ore are dissolved in a mixture of 10 C.C. of nitric acid (D 1.2) and 20-30 C.C. of hydrochloric acid (D 1.9) preferably in a porcelain dish so that the siliceous mass may be broken up with a pestle. After boiling for a while on a sand-bath the whole is rinsed into a 200 C.C.flask 50-60 C.C. of ammonia are added and the solution is again boiled for a short time. When cold dilute ammonia (1 3) is added up to the mark and the solution is well shaken and filtered. One hundred C.C. of the filtrate are mixed with a little bromine water to precipitate any manganese and the turbid liquid is then boiled with about one gram of aluminium scraping8 until the copper present is all precipitated. Five C.C. of sodium sulphite solution (1 4) and a few C.C. of dilute ammonia are added the liquid is again heated to boiling and at once filtered; the residue is washed with a hot dilute ammoniacal solution of sodium sulphite. The filtrato is neutralised with hydrochloric acid and an extra 10 C.C. of dilute acid (1 3) are then added After diluting t o 150 C.C.and heating to boiling the zinc is at once titrated with ferrocyanide (2 1.63 grams of potassium ferrocyanide and 14 grams of crystallised sodium sulphite per litre) using ammonium molybdate solution (9 grams per litre) as external indicator. The end reaction is shown by the formation of a reddish-brown spot. L. DE K. Estimation of Copper. Modiflcation of the Iodide Method. E. C. KENDALL (J. Amer. Chem. Xoc. 1911 33 1947-1952).-A modification of the iodide method of estimating copper is described in which the nitrous acid formed during the solution of the copper in nitric acid is destroyed by che addition of sodium hypochlorite the chlorine thus liberated being removed by treatment with phenol. The solution of copper of volume about 50 t o 60 c.c.is placed in a flask and the acidity rendexed equivalent to about 4 or 5 C.C. of con- centrated nitric acid. The temperature should not be above 25'. Solution of sodium hypochlorite is added and about two miuutes later 5% solution of phenol is quickly introduced. Sodium hydroxide is added in slight excess to prevent the formation of nitrophenol and tlle solution is afterwards acidified with acetic acid. Potassium iodide solution is now added and the iodine liberated is titrated with standard sodium thiosulphate. This modification gives accurate results is more rapid and requires less attention than the original method. E. G. The Estimation of Manganese by the Sodium Bismuthate Method. PAUL H. M. P. BRINTON (J. Ind. Eng. Chem.2911 3 337-239).-The author has repeated tbe work of Blair (Abstr. 1904 ii 683) and others on the estimation of manganese by the sodium bis- mutbate method and corroborates the statement that for gmall amounts of manganese it is the most accurate method known. The following modifications are suggested that pure Sorensen sodium oxalate should be used t o standardise the potassium permanganate and that the empirical fwtor 0.1 656 instead of the theoretical factor 0.16024 shouldii. 94 ABSTRACTS OF CHEMICAL PAPERS. be employed in the conversion of the sodium oxalahe hgure into that of manganese; this corrects the tendency of the method to give low results although the author considers that gravimetrically standardised manganous sulphate is the most accurate standard that can be employed. The decomposition of ores by the hydrochloric and sulphuric acids method is suggested as being fully as accurate more rapid and possibly more convenient than the employment of hydrofluoric and sulphuric acids.Fusing the ore with sodium peroxide ie also recommended in the case of refractory samples. F. 34. G. 31. A New Rapid and Accurate Volumetric Method for the Estimation of Manganese and its Application to the Analysis of Iron and Steel. FLOYD J. METZGEB and L. E. MARRS (J. Ind. Eng. Chcm. 1911 3 333-335).-It has been observed that the presence of manganese disturbs the estimation of ferrous iron in rocks by the sulphuric-hydrofluoric acid method the more hydrogen fluoride employed the ;higher the percentage of iron found a fact which pointed to the possibility that manganese and permanganic acid react together quantitatively in the presence of a sufficient quantity of this acid.Solutions of carefully stsndardised munganous sulphate were titrated wit,h N/30-potassium permanganate in waxed beakers in the presence of 50% sulphuric acid (1 vol.) hydrofluoric acid (2.5 vole.) and varying quantities of ammonium fluoride (which increased the speed of reaction) and when the experiments were repeated in the presence of ferric iron identical results were obtained. The analysis of steel was conducted as follows About one gram of the sample dissolved in nitric acid was treated with ammonium per- sulphate (1 gram) and boiled during a few seconds evaporated to dryness and dissolved in a mixture of 50% sulphuric acid (20 c.c.) and 30 C.C. of water; the solution was boiled until clear transferred to a waxed beaker and treated with 5 grams of ammonium fluoride and 25 C.C.of hydrofluoric acid the volume made up to 100-150 c.c. and finally titrated with potassium permanganate. The results of numerous experiments are tabulated and the method is claimed to be simple accurate and rapid aiid a t the same time applicable to the cases-of spiegels and other manganese ores. F. M. G. M. Estimation of Ferrous Ions with Standard Iodine. GY~BEBT ROMYN (Chem. Zeit. 19 1 l,35,1300).-The process is more particularly intended for pharmaceutical preparations (Blnud’s pills syrup of ferrous iodide etc.). The preparation is dissolved in so much dilute sulphuric or hydrochloric acid that the free acidity amounts to about 20 C.C. of N-acid.The solution is then added to a mixture of 20 C.C. of iV/lO-iodine solution and 5 grams of powdered sodium pyro- phosphate and the mixture is shaken until the latter has nearly dissolved. After five minutes the excess of iodine is titrated with N/10-thiosulphate as usual; I C.C. of the latter=27*8 mg. of crgstallised ferrous sulphate. L. DE K.ANALYTICAL CHEMISTRY. ii. 95 Detection of Nickel and Gobalt in Mixtures. ANGEL DEL CAMPO and JAIME FERRER (Anal. Pis. Quini. 1911 9 201-213 272-276. Compare Abstr. 19 11 ii 825).-The value of potassium methyl xanthate as a delicate reagent for nickel and cobalt (compare loc. cit.) has been examined in respect to delicacy and in comparison with Tschugaeff’s reagent for nickel (dimethylglyoxime) and Vogel’s reagent for cobalt (ammonium thiocymate and amyl alcohol).In the case of nickel alone both reagents display about equaldelicacy detecting nickel in 1 C.C. of a 1 in 200,000 solution or in 4 C.C. of a 1 in 500,000 solution which is the limit. With mixtures of nickel and cobalt in the proportion of 1 to 100 Tschugaeff’s reagent fai!s but potassium methyl xanthate is trust- worthy arid with care may be employed to recognise nickel in the presence of even higher proportions of cobalt,. I n regard to cobalt the xanthate has about five tiuies the delicacyof Vogel’s reagent being capable of recognising the metal clearly in 1 C.C. of a solution of 1 in 250,000. With mixtures of cobalt with excess of nickel (10 to 2000 timesj the reagents display about equal value when working at the limits of sensibility oE Vogel’s test.G. D. L. Separation of Nickel and Zinc in German Silver and Other AlloyB. LA VERNE W. SPBING (J. Ind. Eng. Chem. 1911 3 255-256).-About 0.5 gram of the drillings is freed from tin with nitric acid the lead removed as sulphate copper by electrolysis and the iron by means of ammonium hydroxide. Five grams of ammonium chloride are then added and the solution just neutrslised with hydro- chloric acid aud treated with 0.4 gram of dimethylglyoxime (dissolved in alcohol) for every 0.1 gram of nickel supposed to be present; ammonium hydroxide is added drop by drop until just ammoniacal and the solution allowed to remain at just below boiling point during about half an hour.The precigitate is collected on a tarred filter washed with hot water driid at i05O and weighed C,H1,Ol,N,Ni X. 0.2031 = Ni. The filtrate is acidified with an excess of 10 C.C. of concentrated hydrochloric acid boiled to decompose the excess of dimethylglyoxime treated with 10 grams of microcosmic salt (in saturated solution) rendered exactJy neutral with ammonia and allowed to remain just below its boiling point until the precipitate has granulated; this is collected washed with hot; water ignited and weighed as zinc pyrophosphate. F. M. G. M. Estimation of Tin in Canned Foods. HERMAN SCHKEIBER and W. C. TABER (J. Id. Eng. CILenh. 1911 3 257-261).-A discussion of the difficulties experienced in obtn ining accurate results by the wet combustion methods usually employed for estimating tin in canned foods.The author gives a detailed description of an alkali fusion method which he finds gives excellent results the main procedure of which consists in mixing about 100 grams of the material weighed into an iron crucible with 50 C.C. of an aqueous solution coutaining 150 gramsii. 96 ABSTRACTS OF CHEMICAL PAPERS of sodium hydroxide and 100 grams of sodium carbonate per litre adding 75 c.c of alcoho’l (95%) evaporating carefully t o dryness with continual stirring slowly raising the temperature to about 1 60° and finally igniting in a muffle until all volatile matter is removed. The fused mass is transferred to a beaker and evaporated with 50 C.C. of concentrated sulphuric acid and 30 C.C. of nitric acid (D 1.42) until fumes of sulphur trioxide are apparent ; the mixture is cooled diluted almost neutralised with ammonium hydroxide and treated with hydrogen sulphide ; the collected precipitate is washed with a mixture of ammonium acetate and dilute acetic acid the tin re- dissolved by boiling with sodium hydroxide and after separation from other substances which may be present i t is finally re-precipitated collected ignited and weighed as stannic oxide.F. 31. G. M. Separation of Zirconium from Iron and Aluminium and the A n a l y s i s of Ferrozirconium. M. WUNDER and B. JEANNERET (Zeitsch. anal. Chern. 191 1 50 733-’735).-Se;uaration of Zirconiu’IIz h n and Aluminium.-About 1 gram of the mixed oxides is fused in a platinum crucible with 6 grams of sodium carbonate the mass is taken up with water and after addition of 1 gram of sodium carbonate boiled for a few minutes. The filtrate contains the aluminium (also any chromium) from which the alumina may be precipitated by adding excess of ammonium nitrate.If much is present it is advisable t o submit the insoluble mass t o a second fusion with sodium carbonate. The iron is dissolved by hot dilute hydrochloric acid (1 :l) and estimated as usual. The undissolved zirconium oxide is ignited and weighed as such. Analysis of ~erroaii.conium.-The alloy is heated on the water-bath with hydrochloric acid and broffiine when the zirconium and the iron pass into solution whilst the silicon is converted into oxide. After adding a little nitric acid the whoIe is evaporated to dryness and finally heated in an air-bath a t 110”.The mass is then dissolved in dilute hydrochloric acid and the silica is collected and ignited. From its weight should be deducted the small amount of zirconium oxide which is left after the usual treatment with hydrofluoric and sulphuric acid. The filtrate from the silica is precipitated with ammonia and the oxides are then submitted to the fusion with sodium carbonate as described. The process may be also applied to zirconium carbides. L. DE E( A Volumetric Method for E s t i m a t i n g Antimony in Alloys. GEORGE S. JAMIESON (J. Ind. Eng. Chem. 1911 3 250-251).-An application of Andrew’ (Abstr. 1903 ii 686) iodate method to the estimation of antimony in alloys especially ‘‘ hard leads ” and solders ; it is claimed to be rapid accurate and admissible in the presence of copper aud iron.Two other methods have been studied comparatively by the author the first which is based on getting the antimony into the quinquevalent form in dilute hydrochloric acid solution adding potassium iodide and titrating with sodium thiosulphate gave good resiilts only ind S ALY Ti C IL C HE Jl ISTLt Y ii. 97 the absence of copper or iron; the second method depends on getting the antimony into the tervalent condition in sodium hydrogen carbonate solution and titrating with iodine gave unsatisfactory results in the presence of lead owing to the co-precipitation of antimony which was found to take place even in the presence of tartaric acid. About 1 gram of an alloy containing less than 2% of antimony is weighed into a 200 C.C.Erlenmeyer flask and heated with 10 C.C. of concentrated sulphuric acid until decomposition is complete boiled gently for about two minutes after the lead sulphate has become whire cooled and diluted with 15 C.C. of water; 15 C.C. of dilute hydrochloric acid (1 1) are then added the mixture vigorously shaken and the lead sulphate collected on a Gooch crucible and washed with hydrochloric acid of the same concentration. The filtrate is transferred to a glass-stoppered bottle of about 250 C.C. capacity 5 C.C. of chloro- form 15 C.C. of concentrated hydrochloric acid and 5 C.C. of a solution of iodine monochloride added ; the bottle is shaken and after about five minutes the liberated iodine titrsted with standard potassium iodate until the chloroform in just decolorised after a vigorous shaking (which should be repeated in about a minute to ensure obtaining the correct end-point); the liquid can be poured off and the chloroform employed for further titrations.The concentration of the hydrochloric acid in the solution is of importance and the above quantities should be adhered to carefully. The iodine monochloride solution is prepared by dissolving 10 grams of potassium iodide and 6.44 grams of potassium iodate in 75 C.C. of water adding 75 C.C. of concentrated hydrochloric acid and a globule of chloroform and adjusting exactly to a faint iodine colour by shak- ing and adding minute quantities of potassium iodide or iodate until the required condition is obtained. Tne Geo-chemical Interpretation of Water Analyses.CEASE PALMER (Bull. U.S. Geol Survey 479; a Reprint 31 pp.).- A record of a large number of analyses of waters from American rivers. The results however are not given in terms of definite salts but as follows First the properties of the solution in % proportions [primary salinity secondary salinity tertiary salinity (acidity) primary alkalinity secondary alkalinity] ; second the percentage of reacting values of co-ordinate radicles irom which the properties of reaction may be directly derived accompanied by a statement of concentration values in parts per million ; third the character formula (the percentage of reacting values of the individual radicles determined) together with a statement of the concentration value ; fourth the base analyses. (1) Primary salinity (alkali salinity) is salinity not to exceed twice the sum of the reacting values of the radicles of the alkalis; (2) secondary salinity (permanent hardness) is the excess (if any) of salinity over primary salinity not to exceed twice the sum of the reacting values of the radicles of the alkaline earths group ; (3) tertiary salinity (acidity) is the excess (if any) of salinity over primary and.secondary salinity ; (4) primary alkalinity (permanent alkalinity) is F. 19. G. M. VOL. CII. ii 7ii. 98 ABSTRACTS OF CHEMICAL PAPEKS. the excess (if any) of twice the sum of the reacting values of the alkalis over salinity ; (5) secondary alkalinity (temporary alkalinity) is the excess (if any) of twice the sum of the reacting values of the radicles of the alkaline earth group over secondary salinity In distinguishing the special properties the values of racliclev of the same sign are doubled ; the positive and negative radicles which together induce their special properties thus receive their full value.I n the author’s opinion this form of stating results is more comprehensive to the geologist than the expression in definite salts which is always more or less hypothetical. L. DE K. Colorimetric Estimation of Phenols in Waste Liquors. HERMANN BACH (Zeitsch. anal. Chem. 1911 50 $36-740).-The process is based on the fact that 10 C.C. of a very dilute solution of phenol (a few rng. onlyj when heated to boiling with 0.2. C.C. of Millon’s reagent and 0.1 C.C. of nitric acid give when allowed t o cool a liquid of a permanent rose or reddish colour which may then be matched with a solution of phenol of known strength similarly treated.In order to apply the process to waste liquors 1 litre of the sample is mixed with 5-10 C.C. of strong aqueous potassium hydroxide and evaporated in a dish to 50 C.C. The contents are then transferred to a 500 C.C. Erlenmeyer flask having a mark at 150 c.c. a slight excess of sulphuric acid is added and when cold the liquid is diluted up to the 150 C.C. mark; one hundred C.C. are then distilled off. To this distillate which contains the phenol from one litre is then applied the above colorimetric test ; if the colour should be a dark red it must be suitably diluted. L. DE I(. The Estimation of Phenol and p-Cresol in Mixtures of the Two. HUGO DITZ and FRIEDRICH BARDACH (Biochem.Zeitsch. 191 1 37 272-312).-The authors maintain in opposition to Siegfried and Zimmermann and others that the original method proposed by Ditz and Cedivoda in 1899 for the estimation of phenol and p-cresol in mixtures of these substances gives accurate results provided that the details given in the description of the process are strictly adhered to. The method depends on the principal of estimating the amount of bromine taken up by the mixture and the success of the process depends on using the right excess of bromate and bromide mixture and of hydrochloric acid and on other details. The paper is largely controversial and the various points insisted on by the authors are illustrated by a large number of analyses of mixtures containing known quantities of the two phenols.S. B. S. Two Modifications of Fehling’s Solution. EDWARD FRANK HARRISON (Pharm. J. 191 1 [iv] 33 746-747).-Benedict has suggested recently that in the use of Fehling’s solution for the detec- tion and estimation of dextrose the actual reduction is effected by a substance resultirlg from the action of the alkali hydroxide on the sugar and that this change may proceed further especially in presenceANXLPTlChL CIIEXIlSTEtY. ii. 99 of substances which retard the normal action and give rise to non- reducing products. The reducing substance is produced more slowly by alkali carbonates but these have little or no further action and consequently Benedict has proposed two modified forms of Fehling:’~ solution for qualitative and quantitative use respectively in which among other changes sodium hydroxide is replaced by sodium carbonate (Journ.Amer. Med Ass. 191 1 Oct. 7). The preparation and application of these solutions to the detection and estimation of dextrose in urine are described and critically examined in this paper. The author considers that Benedict’s claim that his first solution is a far more delicate reagent for dextrose in urine than Fehling’s solution is justified. The solution for quantitative use is shown to give good results with solutions of dextrose in water but is less satisfactory when used for urine containing dextrose. WALTER F. SUTHERST (J. Ifid. Eng. Chem. 191 I 3 256).-The following is stated to be a convenient method of indicating the end-point when estimating sugar with Fehling solution.The Fehling solution is heated t o boiling and the sugar added until a faint blue colour is apparent at the edge of the porcelain vessel employed. As further sugar is added a drop of the mixture is placed on the top side of a filter paper folded in half the filtrate passes through and the spot is treated with a drop of a dilute acetic acid solution of 1% potassium ferrocyanide; on holding up to the light the faintest trace of copper ferrocyanide is plainly seen and the end of the reaction readily indicated. The Physiology and Pathology of Carbohydrate Metabolism [Colorimetric Estimation of Small Amounts of Sugar]. KARL REICHER and E. H. STEIN (Biochem. Zeitsch. 1911 37 321-344).-A method for estimating colorirnetrically small quantitiesof sugar by means of the Molisch reaction is described.Ten C.C. of concentrated sulphuric acid are placed in a graduated cylinder with glass stopper and t o this a tablet containing 0.05 gram of a-naphthol is added and then 2 C.C. of the solution to be investigated. Under these conditions the correct temperature for the development of the colour is attained. After gently mixing so that the colour is uniformly distributed the mixture is allowed to cool and is then diluted to 20 C.C. The colour is compared by means of a Plesch colorimeter or a Stein chromoscope with a solution prepared in a similar way with 0.02% dextrose solution. This is the most convenient strength when the sugar in blood is to be estimated. For the estimation of sugar in this fluid 2 C.C.of serum are titken and diluted to 10 C.C. with water and then 1-2 C.C. of concentrated potassium sulphate 6 t o 7% of dialysed ferric hydroxide solution (the method of preparing which is given in detail) and water up t o the total volume of 20 C.C. are added. Two C.C. of this filtered solution are employed for each test. S. B. S. The Eatimation of Sugars in Natural Products. CARL NEUBERG and MIGAKU ISHIDA (Biochem. Zeztsch. 191 1 37 142-169). -By precipitation with 50% mercuric acetate solution followed by T. A. H. Rapid Volumetric Estimation of Sugar. F. M. G. M. 7-2ii. 100 ABSTRACTS OF CHEMICAL PAPERS precipitation with 25% phosphotungstic acid solution all optically active derivatives of proteins as well as the proteins themselves nucleoproteins lecithin and other substances can be precipitated.The sugars remain in solution and can be accurately estimated polari- metrically in the filtrate. Glycosamine as me11 as the other carbohydrates can also be estimated in this way. The met1:od is illustrated by a large number of examples of analyses of mixtures of known sugar content with different varieties of sugar.:. A. method is also given for preparing the phosphotungstic acid reagent directly from sodium tungstate phosphoric and sulphuric acids. S. B. S. Estimation of Sugar in the Blood. DEXGO TAKAHASIII (BiochenL. Zeitsch. 1911 37 30-33).-The sugar in dog’s blood was estimated polarimetrically and after yeast fermentatiou both polarimetrically and by the methods of fhng and Bertrand. I n all cases no sugar was found after fermentation.The total sugar in dog’s blood was also estimated polarimetricitlly and by the methods of Kumagawa-Suto Bertrand and of Bang. The results by the first two methods agreed well with another and were always somewhat Iower than the results obtained by Bang’s method. S. B. S. The Estimation of Dextrose in Urine and Blood. BERTHOLD OPPLER (Zeitsch. yhysiol. Chem. 1911 75 71-134).-In order t o estimate dextrose in the urine polarimetrically before. and after fermentation the urine was treated with ghosphotungstic acid lead acetate and hydrogen sulphide ; this excludes pigment other reducing sub6tance8 and kevorotatory materials. Estimation by reduction gives too high a result. The existence of physiological glycosuria is very doubtful ; any sugar found in normal urine probably arises from other sources especially glycuronic acid.Similar conclusions are arrived at; in respect to the best method for estimating dextrose in blood. W. D. H. [Detection and] Estimation of Dextrose in Urine. G. -4. STUTTERHEIM (Yl/,arm. TPeekbZad 19 1 I 48 120 1- 1204).- The author uses an alkaline copper solution made as follows 17.32 grams of copper aulphate 100 grams of glycerol 20 grams of sodium hydroxide and water up to 250 C.C. This solution bhould be kept in brown bottles. When testing urice for dextrose 5 C.C. of the reagent are diluted with 5 C.C. of water heated to boiling in a test-tube and set aside. Five C.C. of the urine mixed with 5 C.C. of waterare also heated to boiling and then at once added to the copper solution.If dextrose is present the red copper. reduction will be noticed at the top of the liquid within one-half to one minute ; 0.5% of dextrose may thus be readily detected even when as frequently occurs the urine contains substances which interfere with the ordinary Fehling test. When estimating dext,rose in urine by the iodometric method the author recommends making an allowance of - 0°15:4 on account of dextrose orcurring naturally. L. DE I<.A S A LI’T LCA L CH E HI S1‘ it Y. ii. 101 The Detection and Estimation of Sugar in the Urine. A. C. ANDERSEK (Biochem. Zeitsch. 1911 37 262-265) -It was found t h a t the clarification of urine by charcoal in the presence of 5% hydro- chloric acid according to the method of Bang and Bohmannson leads to errors in the estimation of sugar owing t o adsorption by the charcoal especially when blood-charcoal is used.If however the clarification is carried out by charcoal in the presence of 10% of acetic acid (40c.c. urine,cliluted to 50 C.C. with50% acetic acid,and the mixture shaken with 4 grams of blood-charcoal for ten minutes) a perfectly clear colourless solution is obbained which on polarisation gives the Colorimetric Estimation of Sugar Creatine and Creaticine in Urine WJLHELN AUTENRIETH and GERHARD MULLER (Miinch. med. Wocl~. 1911 ; Reprint 12 pp.).-Whilst the process described by Autenrieth and Tesdorpf (Abstr. 1911 ii 159) yields trustworthy results when applied to colourless urines i t is recommended t h a t dark- coloured urine should be treated with blood-charcoal free from iron after the diluted urine has been boiled with Bang’s copper solution.The blood-charcoal when free from iron does not retain any of the Colorimetric Estimation of Lactose in Urine and Milk. WILHELN AUTENRIETH and ALBERT FUNK (Munch. med. Voch. 1911 Reprint Spp.).-The presence of lactose in urine may be ascertained by means of the test described by Wohlk (Abstr. 1906 ii 122); dextrose when present to the extent of not more than I% does not yield a coloration wit,h the test neither does it interfere with the lactose reaction. For the estimation of lactose 10 C.C. of the diluted urine (containing not more than 0-04 gram of the sugar) are boiled fur three minutes with 50 C.C. of Bang’s copper solution cooled diluted with potassium thiocyanate solution to a volume of 50 c.c.0.5 gram of blood-charcod free from iron is added the mixture is shaken for five minutes and filtered. The quantity of unreduced copper in the filtrate is then estimated by comparison with standard solution in a colorimeter (compare Abstr. 1911 ii 159). I n the case of milk 25 C.C. of the sample are diluted with 400 C.C. of water acetic acid is added the mixture is boiled and diluted when cold to a volume of 500 C.C. After filtration 10 C.C. of the filtrate are boiled Estimation of Sucrose and the fDetection of Dextrin in Foods. ANDRE F. VOLLANT (Ann. J’aZsifi 1911 4 504-509).-A method proposed by Lemeland (Abstr. 1910 ii lOOS) which is based on the destruction of the reducing and rotatory powers of arabinose dextrose l~vulose galactose and lactose when these sugars are heated with manganese dioxide and a1 kaline hydrogen peroxide solution.whilst sucrose is not affected may be employed for the estimation of sucrose in commercial sugars syrups confectionery dried milks and honey. It is pointed out that acetic acid should be used for neutralising the sugar solution after correct sugar values. s. B. s. copper. w. P. s. with 50 C.C. of Bang’s solution as described above. w. P. s. The results obtained are trustworthy.ii. 102 ABSTRACTS OF CHEMICAL PAPERS. treatment and not nitric acid as prescribed in the original paper. After clarification the solution must be acidified by acetic acid before being examined in the polmimeter. Dextrin may be detected when mixed with other sugars by inverting the sucrose present and then subjecting the solution to the above-mentioned treatment ; any optical activity exhibited by the resulting solution is due solely to the presence of dextrin.w. P. s. Approximate Estimation of Starch by Iodine. LESTER REED (Chem. News 1911 104 271).-A quantity of the substance con- taining about 0.1 gram of starch is heated with 5 C.C. of glycerol to a temperature of 190’ for five minutes; the mixture is then diluted to a volume of about 50 c.c. and filtered. To the filtrate when cold is added concentrated iodine solution (in potassium iodide) the precipi- tated starch-iodine compound is collected on a filter washed with boiling 90% alcohol and then rinsed into a platinum basin with a jet of boiling water. The contents of the basin are boiled to expel iodine then evaporated dried and weighed.Allowance is made for mineral matter present. The process cannot be applied to bread or cocoa or t o substances in which the starch has been heated previously. In the case of cocoa theobromine or some other substance is precipitated together with the starch. w. P. s. Estimation of the Acidity of Wine. FERNAND REPITON (Ann. PaZsif. 1911 4 578-580).-The following method is recommended for the estimation of the tota,l acidity of red wines Five C.C. of the wine are placed in a large beaker 5 drops of a cold saturated alcoholic phenolphthalein solution and 3 drops of a 1.2% alcoholic fluorescein solution are added and the mixture is heated just to boiling; 5 C.C. of cold water are then added and tbe solution is titrated with N/20- alkali solution.The red colour of the wine changes gradually to green during the titration and the end-point is taken when the red colour of the indicator appears in the green sdution. This point is readily seen if a white tile is placed under the beaker. w. P. s. Estimation of the Acidity of Milk. 0. RAMAfsTEDT (Chem. Zeit. 1911 35 121s-1219).-Soxhlet’s method (titration of 50 C.C. of milk with Nl4-sodium hydroxide solution using phenolphthalein as indicator) is the most trustworthy of the many processes which have been proposed for the estimation of the acidity of milk. I n the case of Thorner’s method (titrating a mixtnre of 10 C.C. of the milk anci 20 C.C. of water with N/lO-sodium hydroxide) the results obtained are lower than those yielded by Soxhlet’s method when both sets of results are calculated to the same basis; this lower result is due to the presence of the added water and the loss increases with the quantity of water.w. P. s. Estimation of Benzoic Acid. EDUARD REMY (Chem. Z e m t r . 191 1 ii 1379-1380 ; from Apoth. Zeit. 1911 26 835-836).-An iodo- riietric method is described. The benzoic acid is dissolved in 50% alcohol and the solution is treated with 5% potassium iodide andANALYTICAL CHEMISTRY. ii. 103 potassium iodate solutions ; the benzoic acid is converted into mono- iodobenzoic acid and an equivalent quantity of iodine is liberated. This free iodine is then titrated with thiosulphate solution; 1.22 grams of benzoic acid liberate 1.269 grams of iodine. w. P. s. Estimation of Cinnamic Acid in Aqueous Solutions by m e a n s of Bromine.ANNE W. K. DE JONG (Rec. tyau. chim. 1911 30 223-224).-The cinriamic acid is obtained in a finely divided state by solution in sodium hydroxide and precipitation by hydrochloric acid. Bromine water (N/lO) is then added until the solution does riot decolorise after five minutes. Potassium iodide is added and the liberated iodine estimated by titration. From this is calculated the amount of bromine used and thus the amount; of cinnamic acid in the solution. W. G. Estimation of Uric Acid by means of Iodine and the Action of Iodine on Creatinine. C. J. REICHARDT (Phwm. Zeit. 1911,56 922).-h the method described by Pizzorno (Abstr. 1911 ii 667) care must be taken in heating the urine with sodium carbonate as uric acid is converted into glyoxylic acid when boiled with alkalis.When the urine contains creatinine this is changed into creatine by the treatment prescribed. The author finds that creatinine is converted into creatine by the action of iodine; in this reaction the iodine at first combines with the creatinine and only after the lapse of some length of time is hydrogen iodide liberated with the formation of methylguanidineacetyl iodide. w. P. s. Estimation of Formaldehyde. ELIAS ELVOVE (Amer. J. Pharm. 1911 83 455-471).-The cyanide process was found to be trustworthy provided that an excess of cyanide is employed ; when this excess is not less than one-half equivalent the reaction is not influenced by moderate variations in temperature neither does the time during which the mixture is left appreciably affect the results obtained.This process is considered to be preferable to the hydrogen peroxide method both for dilute and concentrated formaldehyde solutions (compare Abstr. 1904 ii 98). w. P. s. Presence of Furfuraldehyde as an Indication of Adulter- ation in Some Fermented Alcoholic Beverages. V. PASQUERO and A. CAPPA (Gaxxetta 1911 41 ii 349-358).-Beer or wine gives a distillate which usually contains traces of furfuraldehyde as indicated by the coloration with aniline acetate. If however the beverage has previously been neutralised with magnesium carbonate the distillate no longer shows a furfuraldehyde reaction. The distillate from a neutralised wine or beer to which caramel or commercial alcohol has been added does give the furfuraldehyde reaction so that an indication of the presence of these adulterants can be obtained by neutralising the beverage with magnesium carbonate and testing the distillate with aniline acetate.R. v. s.ii. 104 ABSTRACTS OF CHEMICAL PAPERS. Microchemical Analysis of Plants. 111. D e t e c t i o n of Asculin by Micro-sublimation in the Examination of Rhizoma Gelsemii. 0. TUNMANN (Chenz. Zenti.. 191 1 ii 1384 ; from Apoth. Zeit. 1911 26 812-814. Compare Abstr. 1911 ii 669 1022 1023).-Asculin may be detected in the bark of Asculus Hippocu8tanurn by means of the sublimation test described by the author (loc. c i t . ) ; tbe spring is the only time of the year when the bark contains the substance. The latter is more rezdily obtained from Gelsemiurn sempervirens.The temperature employed for the sublima- tion should be from 50” t o 60° when the plucoside is obtained i n the form of prisms or rods with square ends. The crystals are soluble i n warm water alcohol and ether and the aqueous solution exhibits a bluish-green fluorescence which disappears on the addition of hydro- chloric acid. Chlorine colours the aqueous solution light red but the glucoside is best identitied by disholving the crystals in 2 drops of ammonia and adding 1 drop of nitric acid when a bluish-red coloration appears a t the point of contact. Bsculetin could not be detected in Radix Belladonnae but the seeds of Euphorbiu Lutlqris yielded a granular sublimate which became crystalline after about ten days. The subterranean portlions of Gelsemiurn elegnns which are sometimes sold as a substitute for Rhixomu Gelsemii yielded neitker aesculin nor Detection and I d e n t i f i c a t i o n of ‘‘ Saccharin ” and “ Dulcin ” in Beverages Foods Drugs Cosmetics etc.STEFANO CAMILLA and C. PERTUSI (Chew. Zents.. 1911 ii 1269-1270; from Giorn. Farm. Chim. 19 11,60 285-‘293).-“ saccharin ” (0-benzoicsulphinide) and ‘‘ dulcin ” (p-phenetolecarbamide) may be detected in solid sub- stances by heating about 30 grams of the sample with 1 gram of barium hydroxide and 50 C.C. of waher filtering the mixture and extracting the acidified filtrate with a mixture of ether and benzene. On evaporating the solvent the two sweetenirig materials a r e obtained as a crystalline residue. Liquids must be evaporated before being tested.“ Saccharin ” and ‘’ dulcin ” may be identified as follows 100 C.C. of the liquid or 10 grams of the solid substance under examination are mixed with 5 grams of magnesium oxide (in the case of solid substances 10 C.C. of water are also added) and the mixture is evaporated t o dryness. The residue is extracted with acetone contain- ing 10% of water the extract is evaporated to remove the acetone and the residual aqueous solution is shaken with ether; “ dulcin ” goes into solution in the ether. The 6‘ saccharin ” is obtained by shaking the acidified aqueous solution with a mixture of ether aiid light petroleum after the “ dulcin ” has been removed. Should salicylic acid also be present in the sample the residue of “mcchar-iri ” obtained on evaporating the ether-light petroleum solution is dis- solved in dilute sulphnric acid treated with a n excess of potassium permanganate in order to destroy the salicylic acid and the “ saccharin” then separated by again shaking the solution with a mixture of ether Estimation of Carbamide.ALEXANDRE DESGREZ and FEUILLIE (Compt. rend. 191 1 153,1007-1010).-A modification of Bouchard’s gelsemic acid. w. P. s. and light petroleum. w. P. s.A N A L Y T I C A L C HE MI STRY. ii. 105 method is described. The ureometer consists of a wide-stemmed pipette having the bulb near the point and a tap at the other end. The pipette is plunged into a narrow jar coctainiug chlorofoim when the lower part becomes filled and then 1 C.C. of urine 5 C.C. of water and 8-10 C.C. of Millon’s reagent are introduced through the tap.The chloroform is warmed to 30-35’ by heating a metal collar passing round the jar. After twenty to twenty-five minutes reaction is complete the pipette is transferred t o another vessel and the liquid displaced by water then by sodium hydroxide solution and finally by water after which the volume of the gas is measured. Under these ,conditions the ammonium salts uric acid amino-acids purine deriv- atives and undialysable substances in the urine are not decomposed. Allantoin is slowly decomposed but the amount of nitrogen from this source is iusufficient to affect the accuracy of a urine analysis. w. 0. w. Estimation of Amino-nitrogen in Polypeptides by van Slyke’s Method. ENIL ABDERHALDEN and DONALD D. VAN SLYKE (Zeitsch.ph,ysioZ. Chem. 19 11 74 505-508).-Determinations of the amino-acid nitrogen in a number of polypeptides have been made by van Slyke’s method ; these are in agreement with the theoretical values except in those cases in which the amino-group is present as glycine. When the values for the amino-nitrogen in glycyl polypeptides are multified by the factor 0-8 values more in accordance with the calculated are obtained. HERMANN FUHNER (Arch. exp. Puth. Pliarm. 19 11 66 178-190).-ChemicaI methods for the detection of aconitine give results which are not altogether iatisfactory in forensic cases ; the taste is characteristic but veratrine produces a very similar although weaker effect on the tongue The alkaloid can however be identified with certainty by its action on the isolated frog’s heart and 0*0005 mg.gives the effect. The effect in question is a characteristic peristalsis of which some tracings are given. W. D. H Reaction of Quinine and Other Alkaloids with Calomel. E. BARONI and 0. BORLINETTO (Chem. Zentv 1911 ii 392-395; Erom Giorn. Fawn. Chim. 1311 60 241-244).-Various salts of quinine give a brown colour when rubbed together with moist mer,ciirous chloride. The free base does not give the reaction. Sydrastine and heroine hydrochlorides pilocsrpine cocaine in the presence of ether and heroine in the presence of dilute alcohol give the same reaction. S. B. S. A. W. VAN DER HAAR (Pharm. Weekblccd 1911,48,1302-1307).-After criticising the official methods the author proposes the following process 10 grams of the extract are mixed with 20 C.C.of water and &hen boiled in a flask until the weight of the solution amounts to about 10 or 11 grams. Four C.C. of dilute hydrochloric acid are added and when cold she liquid is diluted to 20 grams The liquid is then shaken with E. F. A. The Toxicological Detection of Aconitine. Estimation of Hydrastine in H y d r a a t i s Extract.ii. 106 ABSTRACTS OF CHEMICAL PAPERS. 1 gram of talc and filtered. Ten grams of the filtrate are placed in a 100 C.C. flask 7 C.C. of ammonia are added and also 25 C.C. of ether when the whole is shaken for two minutes. Twenty-five C.C. of light petroleum (b. p. SO-SO0) are now added and after shaking for half a minute two grams of powder of tragacanth are introduced and the whole is again thoroughly shaken.Forty C.C. ar0 now taken off and after adding another 5 C.C. of light petroleum the solution is submitted t o distillation until 35 C.C. have passed over. The f h k is then put for eighteen to twenty-four hours in a cool place and after pouring off the liquid and washing the crystals with 2 C.C. of light petroleum Alkaloid . Reactions (Hydrastinine). C. REICHARD (Pharm. 2entr.-h. 1911 52 1253-1260).-A large number of reactions for hydrastinine are communicated of which the two following ones are the most characteristic and establish the identity of the alkaloid. A few particles of the hydrochloride are triturated with a minute crystal of potassium ferro- or ferri-cyanide and a drop of water is then added. With ferricyanide a splendid reddish-green precipitate is obtained which is characterised by its dichroism.The crystals form elongated prisms and are beautifully developed. When held up to the light they appear bluish dark green with total reflexion of the light ; the coloiirs are permanent. With the ferrocyanide crystals are obtained resembling mother-of-pearl ; these are particularly Characteristic for hydrastinine. Sodium nitroprusside gives a compound not unlike the ferricyanide. The behaviour of sulphuric acid is also noteworthy as the yellow colour given on warming again disappears on cooling and the test may Estimation of Morphine in Opium. H. WIEBELITZ (Chem. Zentr. 1911 ii 1383-1384; from Bpoth. Zeit. 1911 26 S24).- The alkaloid separated by the process described by Frerichv and Mannheim may be estimated volurnetrically by dissolving the moist precipitate in 25 C.C.of iV/lO-hydrochloric acid washing the precipitate until the filtrate and washings amount to 100 c.c. and titrating Colorimetric and Physiological Estimation of the Active Principle of the Suprarenal Gland. WORTH HALE and ATHERTON SEIDELL (Anaer. J. Pharm. 191 1,83,551-558).-0€ the various colour reactions of adrenaline that with iodic acid which has been described by Krauss and independently by Frankel and Allers (Abstr. 1909 ii 628) is the most trustworthy for the colorimetric estimation of this substance. The addition of phosphoric acid as recommended by Frankel and Allers is however not advisable a8 it causes the colour to fade. With specimens of the gland containing from 0.2 to 0.8% of adrenaline a quantity of 0.01 gram is heated just to boiling with 5 C.C.of dilute hydrochloric acid (2.5 C.C. of N/l-acid per 100 c.c.) and 5 C.C. of 0.2% potassium iodate solution. After fifteen minutes the mixture is filtered and the colour produced compared with a series of standards containing from 0.01 to 0.1 mg. of adrenaline per C.C. The standard solutions may also be prepared by mixing 1 volume of a solution they are dried on the water-bath and weighed. L. DE K. be repeated over and over again. L. DE K. 50 C.C. of this solution in the usual way. w. P. s.ANALYTICAL CHEMISTRY. ii. 107 containing 20 grams of potassium platiriichloride and 100 C.C. of hydro- chloric acid per litre with 3 volumes of a solution containing 12 grams of crystallised cobaltous chloride and 100 C.C.of hydrochloric acid per litre; quantities of this mixture are diluted so as to yield colora- tions corresponding with those given by definite amounts of adrenaline. The results obtained by this colorimetric process are lower than those found by determining the relative rise in blood-pressure as compared with that produced by a given amount of the pure substance when the solutions were injected into dogs. w. P. s. Catalytic Action of Light in the Oxidation of Phenolphthalin to Phenolphthalein. GIUSEPPE ROSSI (Chem. Zentr. 1911 ii 1659; from Giorn. Farm. Ci~im. 1911 60 433-436). -Phenolphthalein is reduced to phenolphthalin by the action of nascent hydrogen whilst the reverse reaction takes place in the presence of hydrogen peroxide and may be employed for the detection of blood.In the absence of the latter the oxidation proceeds very slowly and may take days but when blood is present the action is much more rapid. The test is carried out as follows An alkaline solution of phenolphthalein is shaken with zinc dust until colourless filtered and the filtrate mixed with the solution to be tested to which a few C.C. of 12% hydrogen peroxide have been added previously. If blood is present a red coloration develops within three hours (compare Abstr. 1909 ii 195). Exposure t o bright light such as an arc-light also increases the rapidity of the oxidation of phenolphthalin. w. P. s. Estimation of Methzemoglobin. JOSEPH BARCROFT and FRANZ MULLER (Proc. physiol. Xoc. 1911 xx; J . Physiol. 43).-See this vol. i 58.Use of Aniline Dyes as Reagents for Bile Pigments in Urine. OTTO V. C. E. PETERSEN (Chem. Zemtr. 1911 ii 1490; from Deutsch. rned. Woch. 1911 37 1891-1892).-Methyl-violet methylene-blue Nile-blue as well as indigo-carmine and Prussian-blue yield a green coloration when added to urine containing bile pigments. The green coloration is also obtained in the case of urine free from bile pigments and the intensity of the colour increases with the quantity of urine used. The test is therefore not a chemical reaction but the result of mixing blue and yellow colouring matters; it is not very sensitive but as a rough test a dye solution containing 1 part in Detection of Albumoses in Urine. EMIL HUGO FITTIPALDI (Chem. Zentr. 1911 ii 3489-1490; from Deutsch. med. Woch.1911 37 1890-1891).-Twenty C.C. of the urine are mixed with 120 C.C. of absolute alcohol and after the lapse of twenty-four hours the precipitate foi.med is collected on a filter; the precipitate is then dissolved in the least possible quantity of 32% sodium hydroxide solution and treated with freshly-prepared ammoniacal nickel solution (equal volumes of ammonia and 5% nickel sulphate solution). If albumoses or peptooes are present in the urine a reddish-orange colora- tion develops immediately. Other proteins uric acid cyanuric acid 10,000 may be employed. w. P. s.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. xanthine hypoxanthine sarcosine and urobilin do not give a reaction. The test may also be used for the detection of albumoses in blood after the latter has been heated with animal charcoal cooled and filtered.w. P. s. The Different Methods for Estimating Pepsin and Trypsin with a Description of a New Simple Method. WILHELM WALD- scHmDT (f"22yer'~ Archiv 191 1 143 189-229).-The very numerous methods devised for the purpose are described discussed and classified. The new method is ft modification of Griitzner's carmine-fibrin process ; if diphenylrosaniline (spirit-blue) is substituted for carmine the fibrin so stained can be employed for the estimation of both pepsin and try psin. W. I?. H. J. DUMONT (Compt. rend. 191 1 153 889-891).-'l'he following method is stated to be rapid and accurate. Two to five grams of the dried soil are treated with about an equal weight of oxalic acid; the volume of carbon dioxide liberated gives the amount of carbonate present. The mixture is diluted until the solution contains 2% of acid boiled for thirty minutes filtered the residue washed with dilute nit,ric acid and finally with water. Calcium etc. may be estimated in the filtrate. The residue is washed with 75-80 C.C. of dilute ammonia and boiled with 20 C.C. of ammonia to remove humic acid. After two hours the liquid is decanted the residue suspended in dilute ammonia and the coarse sand separated by centrifugation and weighed. The colloidal clays in the decanted liquid are again centrifugated at two different speeds i n order to separate two deposits of different degrees of coarseness. Colloids remaining in suspension are coagulated by ammonium carbonate and removed after a third centrifugation. The final liquid is employed for determination of soluble extract and ash. New Method for the Physical Analysis of Soil. w. 0. w. The Application of Bio-chemical Methods in the Analysis of the Bilberry (Whortleberry). (Mlle.) A. FICHTENHOLZ (J. Pharm. Chinz. 191 1 [vii] 4 441-446).-The glucosides arbutin and methyl- arbutin are estimated in the dried leaves of the bilberry (Arctostaphylos Uva ursi) by the changes in rotation and reducing power produced by the action of emulsin on an extract of the leaves allowance being made for the reducing power of the quinol and methylquinol also pro- duced by the hydrolysis. The dried and powdered material is repeatedly extracted with boiling 90% alcohol and the extract after evaporating off the alcohol and dissolving in water purified with basic lead acetate the excess of lead removed and the liquid made to a known volume. It is then treated with yeast invertase for several days to remove the sucrose the amount of this substance present being determined by the change in rotation and reducing power which the liquid undergoes during this time. The invertase is then destroyed by boiling a pre- pnxation of emulsin is added and the rotation and reducing power determined a t intervals of several days until hydrolysis is complete. W. J. Y.

ISSN:0368-1769    

DOI:10.1039/CA9120205086

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

ii. 109 General and Physical Chemistry. Spectrochemistry of Unsaturated Compounds. KARL AUWERS (Bev. 191 1 44 3679-3692. Compare Eisenlohr this vol. ii 2).-In part polemical. Eisenlohr has failed to acknowledge sufficiently the work of Briihl on the influence of conjugation 011 optical properties. Exception is taken to the statement that the introduction of several disturbing groups turn8 an optical exaltation into a depression which is claimed to be especially the case in crossed conjugations ; the experimental evidence is not considered suficient to justify this view. The optical effect when a simple conjugation is converted into a crossed conjugation depends on two factors the depression produced by the influence of the entering group on the conjugation and the exaltation due to the new double bond.The final result depends on the magnitude of each of the opposing factors. I n the case of crossed con jugations with partial valencies the new valencies compensate t o some extent for the disturbing influence of the substituent. The original must be consulted for the further criticisms of Eisenlohr’s argument. E. F. A. Refractive Indices of Mixed Liquid Crystals. PAUL GAUBERT (Con@. rend. 1911 153 11\58-1160. Compare Abstr. 1911 ii 949),-The refractive indices of optically positive mixed liquid crystals follow fairly closely the ordinary ,law of mixtures fur isomorphous solids. p-Azoxyphenetole and p-azoxyanisole influence in the same way the values of the indices for cholesterol octoate. Anomalous results with optically negative crystals are explained by supposing that these two substances exist in a hitherto unknown negative phase and that crystals of the latter form mixtures with negative crystals of cholesterol salts.w. 0. w. Heterogeneous S t r u c t u r e of ‘‘ Fluid Crystals ” of Par- azoxyphenetole. HELENE DEISCHA (Zeitsch. Krt~st. Man. 191 1 50 24-32).-The pecularities of structure and the birefringence shown by fused parazoxyphenetole under the microsLope are regarded as due not to any crystalline structure but to the capillary attractions and tensions in a colloidal solution forming a frothy mass or emulsion. L. J. S. [Spectroscopy of Oxygen.] WALTER STEUBING (Ann. Phy~ik 191 1 [iv] 36 1077-1080).-Polernical against Kayser (Abstr. 1911 ii 785). H. &I. D. C. PORLEZZA (Atti K.Accad. Lincei 1911 [v] 20 ii 584-58’7).-l’he paper gives the results of the author’s measurements of the line spectrum of nitrogen from the red to the green the nitrogen being enclosed in Geissler tubes at a pressure of about 100 mm. Line Spectrum of Nitrogen in a Geissler Tube. R. V. S. VOL. c11. ii. 8ii. 110 ABSTRACTS OF CHEMICAL PAPERS. Line Spectrum of Nitrogen in a Geissler Tube. C. YORLEZZA (Atti R. Accad. Lincei 1911 [v] 20 ii 642-645. Compare preceding abstract).-The author concludes his tables of wave-lengths for this spectrum giving here those of the blue and ultra-violet regions. R. V. S. Spectrum of Boron. SIR WILLIAM CROOKES (Proc. Roy. Soc. 1911 A 86 36-41).-The spectrum of the spark passing between electrodes of crystalline boron has been examined.Certain lines on the photographs have been traced to calcium and aluminium and wheu these are eliminated it is found that the ultra-violet spectrum of boron consists of three lines of wave-lengths X = 3451.50 2497.83 and 2496.89. The fourteen other lines given by Eder and Valenta and the five other lines recorded by Exner and Haschek could not be detected on any of the photographs in spite of excessively long exposures. H. M. D. Spectrum of the Magnesium High-frequency Arc. ELLEN O’CONNOR (Phil. itfag. 1912 [vi] 23 94-101).-The spectrum obtained from an arc between magnesium electrodes has been examined with a high-frequency oscillatory discharge consisting of undamped oscillations. Photographs have been obtained which show the influence of the inductance capacity and frequency on the nature of the spectrum.A comparison of these indicates that the spectrum becomes richer in lines as the frequency increases and the continuous background which is seen in the case of the low-frequency discharge gradually disappears as the frequency is increased. H. M. D. Measurements of the Wave-lengths of Normal Lines in the Iron Spectrum. P. EVERSHEIM (Ann. Physik 1911 [iv] 36 1071-1076. Compare ibid. 1909 [iv] 30 815).-Further measure- ments of wave-lengths of iron lines have been made between X = 4482 and X = 3371. The data are in excellent agreement with the correspond- ing measurements made by Fabry and Buisson the maximum differ- ence amounting to 0 4 0 3 Angstrom units. H. Ilil. D. Influence of the Solvent on the Position of Absorption Bands in Solutions. T.H. HAVELOCK (Proc. Roy. Soc. 1911 A 86 15-20).-,41i attempt has been made to measure the effects which can be ascribed to the operation of Kundt’s rule in referenw to the displacement of the absorption bands of dissolved substances towards the longer wave-lengths in virtue of the refractive or dispersive power of the solvenf. H. M. D. Absorption Spectra of Phosphorescent Substances. BERN- HARD WALTER (Physikal. Zeitsch. 191 2 13 6-1 I).-Photographs have been obtained of the absorption spectra of the phosphorescent alkaline earth metal sulphides containing bismuth as ‘‘ active impurity.” The spectra are characterised by strong absorption bands and i t has been found that only those lines which are absorbed are capable of producing a well developed phosphorescence effect.GENERAL AND PHYSICAL CHEMISTRY.ii. 112 By reference to Lenard's obsorvstione it is showu that tlie wave- lengths of those rays which excite the phosphorcscence of the alkaline earth metal sulphicles are nearly independent of the nature of the active metallic impurity but vary considerably according to the particular alkaline earth metal present. This cannot be reconciled with Lenard's electronic explanation of phosphorescence but appears to favour the older chemical theory. H. M. D. The Fluorescence of Anthracene. LOUISA STONE STEVENSON (J. Physical Chem. 1911 15 845-865).-From :t chemical point of view the fluorescence of anthracene may be due to the following circumstances (1) A continuous reaction generating i1 small amounf of light the intensity or wave-length of which is sufficiently altered by incident light to render the emitted light invisible.(2) 'l'automerio change incident light beiug absorbed aud fluorescent light emitted during the formation of one or both isodynamic forms. (3) Dissocia- tion under the influence of light fluorescent light being generated either in the dissociation or i n the re-association of the molecule. A number of highly fluorescent substances in solution failed t o produce any effect on the photographic plate under the most favourable conditioris. Heme the conclusion is drawn that explanation (1) is improbable although the plate was also unaffected by the gradual dehydration of quinine sulphate in which it is supposed light of very low intensity is emitted.The tautomeric hypothesis (2) in the form suggested by Hewitt is discredited by the fluorescence of dihydroanthracene which has no para- bond. A ,consideration of all the known anthracene derivatives shows however t h a t the meso-ring is undoubtedly concerned with the fluorescence. Anthraquinone and its derivatives are not fluorescent but oxanthrol derivatives may exhibit fluorescence. A tautomerism due to the oscillation of an hydrogen atom or equivalent group between the y-position and some other part of the molecule is considered improbable in the case of dichloroanthracene tetrachloride where all the immediately available positions for chlorine atoms are filled. Hypothesis (3) cau be applied to all the known fluorescent derivatives of anthracene.The author finds t h a t the chlorination of molten anthracene to y-dichloroanthracene is accompanied by the emission of a bluish-white light. The marked fluorescence of y-dichloro- anthracene is well explained by the dissociation of the compound with absorption of light and its re-formation with emission of light of a different wave-length. Tesla rays and P-rays from radium excite antbracene dichloroanthracene and dihydroanthracene to luminescence whilst even anthraquinone may be rendered fluorescent in a powerful cathode beam. The formation of dianthracene under the influence of light probably has no connexion with the fluorescence of anthracene. Anthracene derivatives which have no para-bond and which cannot polymerise to dianthracenes are often fluorescent.Light has no appreciable influeuce on the oxidation of arithracene a t 140-150" by gaseous oxygen. The cfiloriiiatiori of anthracene in the dark yields dichloroanthra- 8-2ii. 112 ABSTRACTS OF CHEMICAL PAPERS. cene. produced. product is hexuchloroanthritcene tetrachloride. obtained in the dark with red phosphorus as catalytic agent. I n presence of iron filings dichloroanthracene tetrachloride is I n direct sunlight with or without halogen carrier the The same product is R. J. C . CkgStalliUe Liquids. H. VON WARTENBEKG (Physikd. Zeitsch. 19 1 1 12 1230. Compare Abstr. 1911 ii 952).-The fact that crystalline liquids behave like uniaxial crystals when examined in an electrical fieid at right angles t o the linesof force has also been demonstrated by Mauguin (Compt.Tend. 1911 152 1680). H. M. D. Chemical Action of Ultra-violet Rays Synthesis and Decomposition of Water. IWAN I. ANDHEEFF (J Ru88. Phys. Chem. Xoc. 1911 43 1342-1364).-After discussing recent work on the chemical effects of ultra-violet light the author debcribes his own experiments which have been carried out with a mercury lamp at various voltages and currents. With a voltage of 220 hydrogen and oxygen combine to form water with moderate rapidity. The velocity of the reaction which terminates in from five to twenty hours is independent of the concentrations of the reacting substances and is in good agreement with the expression dxldt = C ; it increases almost proportionately with the intensity of the light. The mean value of the temperature-coeflicient of the reaction is 1.1.Also water decomposes under the influence of ultra-violet light in the field of action of which an equilibrium is estitblislied between hydrogen oxygen and water this equilibrium differing from the thermal equilibrium at the corresponding temperature. When the initial product is a mixture of hydrogen (2 vols.) and oxygen ( 1 vol.) the final position of equilibrium is the same as when water is employed. With increase of the intensity of the ultra-violet light the equi- librium is displaced in the direction of the dissociation and the percentage of water decomposed increases proportionately with the increase of intensity. T. H. P. Action of Ultra-violet Light on Sodium Thiosulphate. LOUIS MARMIER (Compt. rend. 19 12 154 32-33).-Af ter exposing a solution of sodium thiosulphate to the rays from a quartz-mercury lamp for five minutes sulphur is deposited and the liquid found to contain sodium hyposulphite.The latter however is completely destroyed after a further exposure of seventy minutes. The formation of a hyposulphite can only be detected in solutions containing less than w. 0. w. HANS EULEH (Arkiv. K e m . Nin. Geol. 1911 4 No. 8 l-lO).-The degradation of lactic acid to carbon dioxide and alcohol takes place in pure aqueous solution under the influence of ultra-violet radiations. The rate of decomposition of the lactic acid does not depand on the concentration of the acid within 0.6% of thiosulphate. Biochemical Reactions in Light.GENERAL AND PHYSICAL CEEMISTRY. ii. 113 the limits studied 095N to N.The condensation of acetaldehyde t o aldol also takes place without a catalyst on exposure to ultra-violet light. The bearing of these results on the degradation and synthesis of plant acids is discussed. E. F. A. The a-Particles Emitted by the A c t i v e Deposits of Thorium and Actinium. E. MARSDEN and T. BARRATT (proc. Physical L!OC. 1911 24 i 50-61. Compare this vol. ii 6).-Probabilitp con- siderations have been applied to the a-particles emitted by the C-members of the thorium and actinium active deposits. For a single disintegration the probability of occurrence of a time interval of length between t and t+8t is p ~ - ~ t S t where the a-particles are emitted at the mean rate of p per second. If more than one a-particle is emitted simultaneously or if a product of very short period exists there will be an excess of short intervals above t h a t calculated from the formula.The method of two observers simultnneonsly observing two zinc sulphide screens between which the radioactive substance was placed or in the case of an emanation diffused was adopted each observer recording the observations seen. For the actinium active deposit the agreement between the observed and calculated intervals was good the short intervals being only about 1% of the whole in excess. With the thorium active deposit good agreement was also obtained and as before only a slight excess in this case about 2% of the whole of short intervals occurred. It is possible that this may be explained by imperfections in the experimental arrangement.A determination of the number of scintillations from thorium-C of ranges 4% and 8.6 cm. respectively showed that the number of t h e longer range is 0.646 of the total so that thorium-C2 gives 1.83 times the number of a-particles given by thorium-C,. This ratio held unaltered as the active deposit decayed. The period of the change in which the longer range a-particle is expelled calculated from the range is only second. The distribution of the time intervals shows that if thorium-C bucceeds thorium-C1 its period should be greater than a few seconds and it should be separable by recoil methods which however fail. The conclusion is drawn that thorium-C and -C2 must be simul- taneous products of thorium-B. However there is t h e possibility that the ratio in the number of a-particles given by the two C- members should be as 2 1 but the assumptions necessary in this case to avoid the introduction of branch series seem out of the question. The conclusion of Geiger and Kovarik (Abstr.1911 ii 954) that thorium-D gives two P-particles per atom disintegrating depends on the assumption that thorium-C1 and -C2 give two a-particles per atom disintegrating and is therefore no longer justified. F. S. The /3-Rays of the Radium Family. J. DANYSZ (Compt. rend. 1911 153 1066-1068. Compare Abstr. 1911 ii 840; Baeyer Hahn and Meitner ibid. 567).-The speeds of the separate bundles of P-rays from a tube containing the emanation have been determined with the greatest possible accuracy and many more have been recog-ii.114 ARS'I'RACTS OF CHEMICAT PAPERS. nised. The table gives in the first line the number of the bundle in the second its velocity in terms of that of light calculated according to the Lorentz formula and in the third the relative strength of the bundle ( 8 = strong nz = medium f= feeble v.f = very feeble). 1. 2. 3. 4. 5 . 6. 7. 8. 0.615 0'634 0.660 0'682 0.705 0.718 0-735 0.748 *< . f. 1;. f. 9 f. V f . S . m. 9. 10. 11. 12. 13. 14. 15. 16. 0.i60 0786 0.790 0'862 0'882 0.897 0'920 0.940 f. Y. f. Y. f. f. f. S. 17. 18. 19. 20. 21. 22. 23. 0.943 0.946 0'949 0.957 0,962 0.988 0'996 - - f. .f. In. S. f. The seven strong bundles apparently correspond with those before measured the velocities being more accurately determined. From Nos. 1 to 9 the bundles appear tlo consist of rays travelling a t veloci- ties differing by about 1% from the mean value on either side.The more rapid bundles are perfectly sharply defined. Bundle No. 22 consists of from three to five separate bundles travelling with velocities between 0.98 and 0.99. These extremely fast @-rays like the 7-rays only slightly affect tho photographic plate. The last bundle No. 23 is for this reason very little known. The value given for the velocity 0.996 which corresponds with a value of R p (H= strength of magnetic field p = radius of curvature) of 18,100 com- prises certainly some rays with a value of H 26,000 and of the velocity 0.998. The emanation from 0.3 gram of radium chloride was employed. F. S. Radiant Emission from the Spark. ROBERT W. WOOD (Physikal.Zeitsch 1912 13 32-34. Compare Abstr. 1910 ii 915). -Polemical against Steubing (Abstr. 19 11 ii 838). Further photo- graphs are reproduced which confirm the view that the spectrum under discussion is due to a spectral radiant emission and not to a scattering of the light from the spark discharge by condensed particles of the vapour of the metal as maintained by Steubing. Charges on Thermions Produced in Air and Hydrogen at Atmospheric Pressure. J. (2. POMEROY (Phil. A v c q . 1922 [vi] 23 l'i3-182).-The magnitude of the charge carried by the ions emitted by a strip of heated platinum has been examined by observa- tions on the distribution of the ions when subjected to the action of a uniform electric field. At x temperature which is only just sufliciently high to give positive ions some of the ions from a fresh strip carry charges which are double the atomic charge.When however the strip is heated for some time a gradual change takes place and as the poRitive leak diminishes the proportion of ions carrying a double charge gets smaller and smaller until a steady state appears to be i.eachetl when the average charge is nearly eqaal to the atomic charge. No such change in the average charge occurs in the case of the H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 115 negative ions and at temperatures which are sufficiently high to give negative ions it is found that the average charge of the positive and negative ions is about the same. This result suggested that the negative ions might also be found to carry single charges only if obtained from a strip at a sufficiently low temperature and experiments in hydrogen showed that this is actually the case.H. M. D. Ionisation Produced by Carbon at High Temperatures. JOHN N. PRING and A. PARKER (Phil. Mag. 1912 [vi] 23 192-200). -The emission of ions by carbon has been investigated at tempera- tures between 1300" and 2050" and at different pressures. The negative leak at a given temperature diminishes with the progressive purification of the carbon and with reduction in the pressure. ampere per square centimetre of carbon surface whereas Richardson found 1.3 x 1 0 - 4 at this temperature. Above 1800" the increase in the ionisation with the temperature is very small and the lowest value of the current observed at 2000O was 4 x lo-' ampere.The data obtained in these experiments are incompatible with Richardson's formula and indicate that the large ionisation currents hitherto obtained with heated carbon cannot be ascribed to the emission of electrons from the carbon itself. They are probably due to some interaction between the carbon or the impurities contained in it and the surrounding gases which involves the emission of electrons. The smallest ionisation current cbtained at 1300" was 1.6 x H. M. D. The Emission of Positive Charges by Heated Metals. G. REBOUL and E. GR~GOIRE DE BOLLEMONT (Le Radium 1911 8 406-41 l).-Sur€aces of copper and platinum separated to defiuite distances from one another are heated to various temperatures under various conditions. If the copper surface is in the shape of a cross the deposit on the platinum assumes the same form.The thickness of the deposit increases to a maximum and then decrease8 as the time of heating is increased so that after a certain time no deposit is left. The maximum deposit results in a time the shorter the higher the temperature. The deposit is most abundant in oxygen but occurs and has a grey colour turning black on heating in air in nitrogen and carbon dioxide. The nature of the surface receiving the deposit is not of great import'ance and the platinum may be replaced by other metals and even by porcelain. I n addition to copper a projection of metallic particles occurs with silver as may be put into evidence by opposing it with a gold plate which becomes coated with a white deposit of silver of the form of the silver surface.The maximum in the amount of deposit with copper is explained by the '' fatigue" of the copper. All metallic surfaces are regarded as projecting metallic particles when heated due to the liberation of occluded gas and the mechanical carrying away of the metal by the bursting of the bubbles a process which accounts also for the positive ionisation from heated metals which in every respect is analogous to the phenomena investigated. A t first the projection from the copper surface to the opposed surface is regarded as greater than that of the projection of particles from this A black deposit forms on the platinum.ii. 116 ABSTRACTS OF CHEMICAL PAPERS. surface but afterwards when the gas has been liberated ‘‘ fatigue ” of the copper takes place and the deposit on the opposed surface is again removed by the projection of particles from that surface.F. S. Positive Thermions from the Salts of the Alkaline Earths. CLINTON J. DAVISSON (Phil. Mag. 1912 [vi] 23 121-139).-The nature of the ions emitted a t high temperatures and low pressures by the chlorides fluorides sulphates and phosphates of barium strontium calcium and magnesium has been investigated by the method employed by Richardson. From observations on the influence of a known magnetic field it is found that the truly characteristic thermions emitted by the salts of these metals consist of single atoms of the elements carrying-utiit positive charges. Experiments with zinc sulphate lead to the same conclusion. The R61e Played by Gases in the Emission of Positive Thermions from Salts.CLINTON J. DAVISSON (Phil. Mag. 1912 [vi] 23 139- 147. Compare preceding abstract).-The emission of positive ions by heated strontium chloride strontium sulphate and aluminium phosphate has been examined with reference to the part played by gases in the phenomenon. The results indicate that the increased emission of thermions which is observed when the heated substance is in contact with air carbon dioxide or hydrogen is not due to the emission of molecules of the gas which have been absorbed by the salt and emitted in a charged condition. I n reference to the suggestion that the traces of carbon monoxide or dioxide which are sometimes emitted by heated salts are responsible for the observed ionisation it has been found that the emitted gas is not electrically charged.H. M. T). The Production of Chemically Active Rays in Chemical Reactions. J. MATUSCHEK and NENNING (Chern. Zeit. 1912 38 2l).-A beaker containing zinc and sulphuric acid is placed on a photographic plate in a light-tight case a tinfoil star being int’er- posed. After several hours’ exposure a distinct image is obtained on development. The best results are obtained when the zinc is in the form of a sheet with ribs on the lower surface. Similar results are obtained with hydrochloric and nitric acids and with copper tin and lead the intensity of the photographic action varying considerably. Copper oxide and hydroxide and potassium hydroxide also give chemically active rays when dissolved in acids. Other active reactions are the slaking of lime the setting of Portland cement and plaster the decomposition of calcium carbide by water and the formation of ammonium amalgam.The most active reaction observed is t h a t between sodium silicate and dilute hydrochloric acid which gives a distinct image in less than an hour. The Detection of Actinium Emanation in Minerals containing Actinium. GEORG VON HEVESY (Physihd. Zeitsch. 191 1 12 1213-1214).-An investigation has been made of the point H. M. D. C. H. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 117 noticed by Boltwood (Abstr. 1908 ii 454) that actinium emanation cannot be detected in a uranium mineral by passing air through its solution into a n electroscope. It was found that by the use of vessels of sufficiently small capacity and by filling these as com- pletely as possible with the solution or drying liquid employed the actinium emanation could be readily detected from a solution of pitchblende.One gram of pitchblende in 2.5 C.C. of solution contained in a washing-bottle of 3.5 C.C. capacity gave when an air stream of 0.4 C.C. per second was passed through a leak in the electroscope due t o actinium emanation of two divisions a minute. F. S. The Solubility of A c t i n i u m Emanation in Liquids and Charcoal. GEORG VON HEVESY (Physikal. Zeitsch. 19 1 1 12 1214-1224).-By means of the differences in the ionisations pro- duced in an electroscope wheu the actinium emanation is passed through various liquids at various rates on its way to the electroscope the solubility of the emanation has been indirectly calculated in various liquids.These show the same relative absorbing powers as in the case of the other emanations. In increasing order of absorbing power the liquids examined were saturated aqueous potassium chloride solution water sulphuric acid ethyl alcohol amyl alcohol acetone benzaldehyde benzene toluene petroleum and carbon disulphide. The solubility coeficient of actinium emanation in water is 2 as compared with 1 for the thorium and 0.33 for the radium emanation. Cocoanut charcoal also absorbs the actinium emanation strongly at the ordinary temperature F. S. Radium Emanation Contained in the Air of Various Soils. JOHN SATTERLY (Proc. Camb. PhiZ. SOC. 1911 16 336-355. Compare Joly and Smyth (Abstr. 1911 ii 1048).-The radium emanation contained in the underground air of various soils and at various depths in the neighbourhood of Cambridge has been found on the average to be 2500 times as great as that in the atmospheric air of the same locality.Low barometer usually decreases the amount in the air probably because of the rainfall accompanying it which chokes the pores of the soil. In the tests of the influence of depth the greatest amounts of radium emanation were found at the greatest depths. Continuous withdrawal of the air from the ground did not exhaust the supply of emanation. F. S. A n Attempt made to Detect the Electric Conductivity of Radium-D. L ~ O N KOLOWRAT (Le Radium 191 1 8 401-404).- If the radium emanation is stored in a vessel all of the same potential i t is to be expected that the radium-D formed will be deposited as a uniform film.From the manner in which the resistance of films of platinum or silver suddenly augments when the thickness is decreased between and 10-6 cm. and on the assumption that the density and electric conductivity of radium-D are the same as that of lead it is calculated that the emanation accumulating in six days from 0.25 gram of radium should produce in a capillary tube 5 mm.ii. 118 ABSTRACTS OF CHEMICAL PAPERS. long and 0.2 mm. diameter a film of radium-I) about 4 x 10-6 cm. thick with a resistance of 40 ohms. Capillary tubes of this size provided with two platinum wire electrodes and silvered internally except for the space between the ends of the electrodes had an initial resistance greater than a megohm.Filled with the emanation from 0.27 gram of radium the silvering was rapidly attacked and rendered transparent which was ascribed t o the presence of oxygen. I n one experiment a ring of brown deposit midway between the electrodes and brilliantly metallic when seen by reflected light was seen three or four days after the emanation was introduced but this deposit after three days more gradually and cotnptetely disappeared and was hardly visible even under the microscope. The deposit is supposed to have been radium-U oxidised i n course of time by the presence of a trace of oxygen. I n the second experiment no deposit formed but in a third n non-uniform discontinuous deposit appeared. IKI all cases the re5istance of the tube remained greater than a megohm.The formation of the active deposit appears not to take place uniformly but over certain areas determined by the position of the electrodes aud the shape of the tube. F. S. The Decay-constant of Polonium. ERICH REGENER (Rer. Daut. pJtysikal. Ges. 1911 13 1027-1033; Le Radium 1911 8 458-46 1 ).-The half-period of polonium determined by counting the scintillations produced on a zinc sulphide or diamond screen was 129.5 days the total number of scintillations counted being 16,800. This period is less than that usually given which varies in different measurements from 134.5 to 143 days. An examination was made of the effects of unsaturation on the period of decay in ionisation measure- ments. The ionisation of a strong polonium preparation was measured by a galvanometer at different voltages over a period of nearly a year.A t insufficient voltage to produce saturation the period found was higher than when higher voltages were employed The true half-period deduced from these measurements was 136 days (+_ 0.5 day). F. S. Radioactivity of Marsh Gas. JOHN SATTERLP (Proc. Carnb. Phil. SOC. 1911 16 356-359).-The inflammable gas drawn from stagnant backwaters and ditches around Cambridge during a long spell of fine weather was rich in radium emanation to the same extent approximately as the air drawn from depths of three to five feet in the soil of the same locality. F. S. The Radium Content of Various Fresh and Sea Watere and Some Other Substances. JOHN SATTEBLY (Proo. Can& Phil. SOC. 1911 16 360-364).-The amount of radium present in various fresh waters in the neighbourhood of Cambridge was usually less than gram of radium per litre which is some hundreds of times less than accounts for the quantity of emanation found in the water in the case of the tap water and spring waters.The water of the Cam contains much less dissolved emanation than these. Three specimens of coastal sea water contained about gram of radiumGENERAT AND PHYSICAL CHEMIS’I‘RY. ii. 119 per litre which is in agreement with Eve’s and much smaller than Joly’s results. F. S. The Apparatus Used f o r the Determination of the Radio- activity of Springs. FERDINAND H.ENRICH and FRITZ GLASER (Zeitsch. angew. Chem. 1912 25 16-19).-The ‘; fontaktoscope” of Engler and Sieveking has been compared with its improved form the ‘‘ fontaktometer ” of Mache and St.Meyer. Similar results were obtained with the two instruments and it is held that the former is advantageous on account of its cheapness its ease of working and its transportability. F. S. Electrical Resistance of‘ Special Steels. OCTAVE BOUDOUARD (Compt. rend. 1912 154 1475-1478).-The influence of different percentages of carbon on the electrical conductivity of nickel manganese chromium and tungsten steels of varying composition i s shown in tabular form. I n nickel steels the coefficient of resistance increases with the percentage of carbon. The curve showing the variation of the coefficient with the proportion of manganese shows a maximum corresponding with the compound NiFe,. I n manganese steels the resistance shows a maximum when 12-13% of manganese is present the amount of carbon having little influence on the value.The resistance varies in a very irregular way with chromium steels whether they are rich or poor in carbon. Tungsten steels show an increase up to a certain concentration then a minimum followed by a further increase. Benedick’s formula for the conductivities of steel expressing the conductivity as a linear function of the sum of the concentrations of the different elements present expressed in terms of their carbon equivalents is found t o hold good for the special steels studied. w. 0. w. Conductivity of Pure Ethyl Elther. J. CARVALLO (Com.pt. rend. 191 I. 153 1144-1145).-‘l’he author considers that tjhe ether employed in Schroder’s experiments (Abstr.1909 ii 462) was not pure and that his values for the conductivity were too high. With ether purified over sodium and in the absence of air a current of 0.93 x 10-10 amperes traversed the liquid on establishing a difference in potential of 425 volts but this diminished progressively owing to the experiment being conducted in glass vessels. It will be neces- sary to employ metallic apparatus with para5n insulation to obtain accurate values. w. 0. w. Influence of Temperature on the Density and Ellectrical Conductivity of Aqueous Salt Solutions. HEINRICH CLAUSEN (Ann. Physik 1912 [iv] 3’7 51-67. Compare Heydweiller Abstr. 1910 ii. 106 398).-Tho influence of temperature on the increase of density due to the ionised and un-ionised portions of the electrolyte has been examined in the case of aqueous solutions of twelve salts and of nitric acid by measurements of density and electrical conduct- ivity at 6O 18” and 30°.From these data the constants A and B in the formula As=- &i + &( 1 - i) have been calculated A being theii. 120 ABSTRACTS OF CHEMICAL PAPERS. difference between the density of the solution and that of water and i the degree of ionisation. The constant A decreases with rising temperature whilst B also decreases for most of the salts examined but to a much smaller extent. I n the case of potassium chloride bromide and iodide and of nitric acid B increases as the temperature rises. From this i t follows that tbe influence of the ionisation on the change in density diminishes as the temperature is raised and the alteration is such t h a t the values of A - B for the different electrolytes become more nearly equal.H. M. D. Dependence of the Conductivity of Binary Normal Electro- lytes on the Concentration. PAUL HERTZ (Ann. Physik 1912 [iv] 37 1-28).-A theoretical paper in which the author deduces a relationship between the conductivity and the concentration of the form A - X -function of ,qc where X is the molecular conductivity of the electrolyte at concentration c and A the Conductivity at infinite dilution. By euitable variation of the dimensions of the system of co-ordinates from case to case it is shown that the relationship between conductivity and concentration can be represented for all binary electrolytes by a single curve. H. M. D. Conductivity of Certain Salts in Methyl and Ethyl Alcohols at High Dilutions. HENRY R.KREIDER and HARRY C. JONES (Amer. Chem. J. 1911 46 574-585).-1n continuation of earlier work (Abstr. 1911 ii 362) on the conductivity of very dilute solution8 of salLs in methyl and ethyl alcohols measurements have now been made of the conductivities at 0' and 25' of similar solutions of sodium bromide lithium bromide potassium thiocyanate and cobalt bromide. The values of pa were found in most of these cases. The ratio of the vahe of pa for a certain saIt in one solvent to that for the same salt in another solvent is nearly constant for salts which are solvated to approximately the same extent. When one salt is solvated very much more than another the value of pa is generally less for the former.The ratios of poo for certain salts in t w o different solvents deviate from the ratios of the fluidities of the solvents since the value of pa in the solvent which has the greater molecular mass is always less than would be expected from the ratio of the fluidities. The greatest difference between these ratios is shown by the most highly solvated salts. E. G. Afflnity Measurements in Alcoholic and Aqueous Alcoholic Solutious. ERIK HAQULUND (Arkiv. Kern. Mil.&. Geol. 1911 4 No. 11 1-31).-By means of conductivity measurements the author has investigated the ionisation of various acids and bases and the hydrolysis of certain salts in 80 and 99.8% alcoholic solutions. At 18' the mobility of the ammonium ion was found to be 17.9 in 80% alcohol that of the hydroxyl ion 26.1 in 80% alcohol and 16.5 in 99.8% alcohol.Conductivity data were obtained for salicylic cinaamic and acetic acids and for p-nitrophenol ; also for piperidine ammonia,GENERAL AND PHYSICAL CHEMISTRY. ii. 121 piperazine mil diethylamine in both SO% and 99.8% alcohol. For small variations of concentration i t is found that the iouihation of both acids and bases is in harmony with the requirements of the law of mass action. The degree of hydrolysis was examined in the case of aniline salicylate a-picoline salicylate piperidine salicylate a-picoline acetate ammonium acetate and ammonium p-nitrophenoxide. The extent to which these salts are hydidysed iu aqueous alcoholic solutions increases with increase in the alcohol content of the solvent. Conductivity determinations were also made in order to ascertain whether salt formation occurs when certain ketones and aromatic nitro-compounds are brought into contact with sodium hydroxide in alcoholic solution.I n the case of P-nitrophenylethylene salt formation takes place at a sufficiently slow rate to allow of the process being followed by means of conductivity nwasurements. The rate of progress in 80% alcohol indicates that the reaction is bimoleculnr but in 99.8% alcohol the corresponding values of the velocity coefficient diminish appreciably as the reaction progresses. Measurement of Electrical Conductivity. ALFONS KLEMEKC (Clbem. Zeit. 19 11 35 1420).-A rapid and sufficiently nccurate method is described of making up solutions containing 1 grmu- equivalent or one mol.in 32 64 . . . . . litres (the usual dilutions in which electrical conductivity data are tabulated). Electric Properties of Substances in Relation to their Allotropic State. NICOLAUS A. HESEHUS (J. Buss. P h p . Chm. Soc. 191 1 43 Yhys. Part 365-371).-Study of the three allotropic forms of carbon-diamond graphite and charcoal-is in accord with the view previously advanced (J. Russ. Phyrr. Chern. Soc. 1901 33 Phys. Part 19 ; Abstr. 1911 ii 13) and indicate3 that the differences between the contact electrifications of allotropic forms of a substance depend not only on the surface density but also on the capacity of the atoms for ionic dissociation. Surface Effects between Mercury and Certain Solutions and a n Electrochemical Method of Estimating Dissolved Oxygen. SAMUEL W.J. SMITH and WILLIAH F. HIGGINS (Trans. Faraday Soc. 1911 7 64-77).-The influence of sodium sulphide on the difference of potential between mercury and certain salt solutions has been investigated (compare Smith and Moss Abstr. 1908 ii 343). The cells are connected in turn with a constant electrode and the X . M . P . of the combination determined with an electrometer. Uaing i V / l O - solutions of potassium chloride bromide snlphate aud hydroxide and pure water a sudden change of slope of the E.M.F.-concentration curve occurs at about 0.0004 equivalent of sodium sulphide. This break slowly disappears even when air is excluded from the solutions and is replaced by one between 0.0005 and 0.0006 equivalent. This is the point at which oxygen is completely removed from the solution by the oxidation of sulphide to thiosulphate.This is contirmed by further experiments with old solutions. ‘l’he method may be used tor the eetimation of dissolved oxygen. H. M. I>. G. S. T. H. P.ii. 122 ARBTRACTS OF CHEMICAL PAPERS. The initial breakobserved a t 0.0004 equivalent is atkibuted to t h e formation of mercury sulphide which is a maximum at this concen- tration further additions of sodium sulphide diminishing the thickness of the film. This is confirmed by observations of the colours of the tarnished films. The surface adsorption of sodium sulphide must be greater than that of oxygen. C. H . D. Anode and Cathode Falls of Potential and the Minimum Potential in Chlorine. R. RAISCH (Ann. Physik 1911 [iv] 36 907-Y28).-Measurements of the fall of potential at the electrodes have been made in tubes filled with chlorine a t different pressures and provided with electrodes of aluminium platinum mercury and magnetite.In the case of magnetite electrodes which are only slowly acted on by chlorine the observed potential diEerences are not much larger than those obtained with other gases. With these electrodes tho fall of potential at the anode was found to be independent of the strength of the current but increased slightly with increasing pressure. When such Cubes were left filled with chlorine for several weeks in an undisturbed condition the anode potential a t a pressure of 2.41 mm. was found to have risen from 41 t o 300 volts. On passing a current through the tube the potential difference fell rapidly however to its original value.These observa- tions indicate that the large potential falls which are exhibited by tubes containing sluminiutlr platinum or mercury electrodes are due to the formation of a surface layer by the action of the chlorine on the metals. When such electrodes are pulverised by the paspage of N strong current the anode and cathode falls of potential are found to undergo considerable diininution as a consequence of the reuoval of the surface film. H. M. D. Deposits Obtained f r o m Flames by Electricity. BRUNO “HIEME (Zeitsch. physikcd. CILem. 191 2 78 490-499).-When ttwo electrodes between which a considerable difference of potential subsists are brought near togeLher in a coal gas or candle flame carbon 1s immediately deposited on t.he cathode. In certain circumriltances tohe deposited carbon forms long.narrow growths extending some distance into the flame. The smallest potential giving rise to these structures is 12 volts; they increase in size up t o about 25 volts and beyoud that yoinc do not undergo much further chmge. Similar deposits are obtained when the electrodes are connected with au induction machine giving a short spark. When the poles are reversed the carbon separates in large flakes from the electrodes. It is suggested that very finely divided soot might be prepared in this way and a continuous arrangement for this purpose is described. By means of the following arrangement metals can be deposited in small amount from their salts. Two iron wires were connected with the poles of an induction coil and held at right angles to each other in the flame.A platinurn wire on which were some copper sulphnte crystals was held so as to touch t h e positive pole and after the spark had passed nietallic copper was found on the platinum wire. In a similar way uiinute arriouuts of mercury and apparently also of sodium,GENERAL AND PHYSICAL CHEMISTRY. ii. 123 have been obtained from their salts in the flame. g!he investigatioii is being continued. G. s. Potentials of the Most Important Standard Electrodes. FRIEDRICH AUERBACH (Zeitsch. Eluktrochem. 191 2 18 13-1 8). -As zero for electrode potentials should be taken that of the normal hydrogen electrode at the same temperature as the electrode in question and with a hydrogen partial pressure of 1 atmosphere.For the calculation of the electrode potentials eh referred t o the hydrogen electrode as zero the ternperature-coefficients of the calomel electrode found by Richards (compare Abstr. 1898 ii 7) should not be used more particularly as they are of uncertaiu value from the effect of thermo-E.iW.F.'s which cannot be accurately allowed for. The dependence of Eh on the temperature can be determined directly or can be calculated from the heat of reaction by means of the Helmholtz formula. For the decinormal potassium chloride-calornel electrode eh is practically independent of the temperature between 0' and 30". The following are the most probable values of ch for the more important standard electrodes (concentrations in gram formula weights per litre) eh in volts at Electrode.IIg I Hg,Cl I KC1 0.1 ......... Hg 1 HgO I KOH 1.0 ......... Hg 1 Hg,Cl 1 KC1 1.0 ......... Hg I H#,SO 1 H$O 0'1-0*5 Hg I HgO I NaOH 1-0 ......... Hg I HgO I NaOH 0.1 ......... 7 ~~ ~ 7 0". 18". 25". t- 0.337 -t- 0 *337 + 0.337 + 0.289 + 0'286 + 0.285 + 0.130 - + 0.107 + 0.133 - + 0.111 + 0.184 - + 0.166 - + 0.68 - 0. s. Aluminium Anode-Films. G. E. BAIRSTO and 11. MERCER (Trans. Furadccy Xoc. 1911 7 1-29).-An examination of the results of previous workers shows that the aluminium anode-film is made up of two layers an outer thick conducting film which varies in thickness with the electrolyte and an inner thin dielectric film the thickness of which is independent of the electrolyte. The electrolytes now etudied include potassium ferro- and ferri- cyanide ammonium arsenite and arsenate and ammonium moly bdate of which only the last gives good results giving a high resistance very little affected by temperature.The capacity i n sodium phosphate solutions decreases with rise of temperature whilst in ammonium borate it increases considerably a large part of the increase persisting after cooiing. The addition of chlorides bromides and other salts which have little or no valve action to a phosphate electrolyte produce a very large increase in the leakage current. The capacity decreases slowly with the time of formation. The higher the voltage a t which the film irJ formed the longer is the time required for. the capacity to fall to its minimum value. The product of capacity and voltage of formation decreases wlth increasing voltage.ii.124 ABSTRACTS OF CHEMICAL PAPERS. Experiments with alternating currents using an oscillograph show that the asymmetrical conductivity only becomes marked a t high voltages. C. H. D. Configuration of Equipotential Line8 in an Electrolyte. ANDRE BBOCHET (Compt. rend. 1911 153 1150-1152).-Lines of eyuipotential surfaces in a copper sulphate solution have been deter- mined and are reproduced in the form of curves. The method employed in mapping them was to plunge a copper wire into the liquid to different depths; the sound being connected to a potentiometer was not traversed by a current so long as the fall of potential between it and the t.wo electrodes was the same as the resistances of the two branches of the potentiometer.A Deprez-d’ Arsonval galvanometer was found most suitable for the purpose. w. 0. w. Configuration of Equipotential Lines in an Electrolyte. J. DELVALEZ (Compt. rend. 1912 154 1474-1475. Compare ibid. 121 492).-A claim for priority against Brochet (preceding abstract). w. 0. w. Study of the Hydrogen Electrode of the Calomel Electrode and of Contact Potential. N. E. LOOMIS and SALOMON F. ACREE (Amer. Chem. J. 1911 46 585-620).-The methods usually employed for determining hydrogen ion concentration in the study of organic reactions such as the hydrolysis of esters present serious difficulties in their general application. A study of the hydrogen electrode has therefore been undertaken in order to ascertain whether it can be satisfactorily used for the purpose.The relative efficiency of the various forms of apparatus hitherto used has been investigated and new forms have been devised to eliminate various sources of error. As the accuracy of the work depends largely on the constancy and ease of reproduction of the calomel electrodes used with the hydrogen electrode a large number of calomel electrodes have been prepared and measured against each other in order to obtain an average value of the potential. Many platinum electrodes have also been prepared and compared with one another. The hydrogen electrode has been compared directly with the calomel electrode and experiments have been made to determine the efticiency of various solutions in eliminating contact potential. All the experiment8 were carried out at 25’.The following results were obtained. Calomel electrodes N/’lO-KCl-HgCl-Hg can be prepared of which the variation does not exceed 0.10 millivolt during the first three weeks but afterwards slowly increases. Platinum electrodes can bo prepared which when used as hydrogen electrodes in H/ 1 0-hydrochloric acid show a deviation from the mean value of less than 0.10 millivolt. The E.M.P. of the system H,-Pt-N/ 10-HCl-N/lO-KCl-HgCl-Hg is 0.4266. Potassium chloride was found to be by far the most efficient of the salts tried for eliminating contact potential. A saturated solution of this salt eliminates almost completely the contact potential of systems cousisting of potassium chloride and hydrochloric acid.GENERAL AND PHYSICAL CHEMlYTRY. ii.125 The value of the potential of the electrode N/lO-KCI-HgCl-Hg is 0.3390 if the dissociation of N/lO-hydrochloric acid is 92*2% as found by Noyes; i t is 0.3373 if the dissociation of the acid is 86% and 0.3355 if the contact Dotential is assumed to be 0.0284 a value calculated from Lewis ahd Rupert's data (Abstr. 1911 ii 364). E. G. Application of the Hydrogen Electrode to the Measure- ment of the Hydrolysis of Aniline Hydrochloride and the Ioniaation of Acetic Acid in the Presence of Neutral Salts. N. E. LOOMIS and SALOMON P. ACREE (Arne?.. Chem. J. 1911 46 621-637. Compare preceding abstract).-The hydrolysis of aniline hydrochloride has already been studied by means of the hydrogen electrode by Denham (Trans. 1908 93 48). The results he obtained are now discussed and an account is given of a further investigation.It has been found that if the value of the electrode N/lO- KCl-HgC1-Hg is taken as 0.339 the hydrolysis of a N/16-solution of aniline hydrochloride is 2.19% and that of a N/S%solution is 3.05%. If the value 0.3355 is employed the hydrolysis becomes 1.81% for the N/16- and 2.56% for the N/3%solution; these values agree closely with bhose of Bredig (Abstr. 1894 ii 229) and Tiszard (Trans. 1910 07 2492). It is evident therefore that the hydrogen electrode is of service for the accurate determination of the relations between conductivity and hydrolysis. It is shown that the addition of N/lO-potassium chloride to N/4- acetic acid increases the hydrogen ion conductivity by about 4.5% of its original value. A bibliography is appended.Difflculties in the Use of the Hydrogen Electrode in the Measurement of the Concentration of Hydrogen Ionls in the Presence of Organic Compounds. L. JUNIUS DESHA and SALOMON F. ACKEE (Anzer. Chern. J. 1911 46 638-648. Compare preceding abstracts).-When an oxime is formed by the reversible reaction between a csrbonyl compound and a hydroxylamine salt the oxime may exist in the solution as the free oxime oxime salt and oxime cation. The concentration of the oxime cation can be measured by determining the amount of free hydrogen ions which disappear in its formation. Only two methods seemed likely to prove satisfactory for estimating the hydrogen ion concentration during the reaction namely sucrose iuversion and the potential of the hydrogen electrode.The former method has given good results in experiments which will be described in a siibseyuent paper. An account is now given of the difficulties attending the use of the hydrogen electrode. It has been found that some organic compounds are decomposed in presence of the hydrogen electrode and especially when oxygen is present and the h!.Jf.F. observed may not correspond with the con- centration of the hydrogen ions present. I n several cases in which hydroxylamine hydrochloride and acetone were both present the maximum potential obtained indicated a hydrogen ion concentration about twice as great as was possible if the hydroxylamine and acetoxime hydrochlorides had been completely hydrolysed. E. G. VOL. CII. ii. 9ii 126 A HYTRACTS OF CHEMICAL PAPERS.In most experiments with the hydrogen electrode the true E.Jf.Ii’. can be ascertained within thirty minutes but if the platinum electrode and the reacting liquid are previously saturated with hydrogen the E.M.F. can be measured within a millivolt in five to ten minutes. Ammonium nitrate does not entirely eliminate contact potential. Capacities of the Electrolytic Valve Effect .in Fused S a l t s and in Absolute Sulphuric Acid. GUNTHER SCHULZE (Zeitsch. Elektrochem. 1912 18 22-29. Compare Abstr. 191 1 ii 365).-In continuance of the experiments on electrolytic valve action the thick- nesses of the active layers formed on aluminium and tantalum in the presence of fused salts have been calculated on the assumption that the dielectric constant is unity. The capacity measurements were made by a method which is fully described after the cells had been formed for thirty minutes at a potential of 50 volts.The thickness of the layer formed on tantalum which in aqueous solutions is independent of the nature of the electrolyte and the con- centration attainable a t Oo increases regularly a t higher temperatures as the proportion of water is further diminished until the fused salt is reached. The same phenomenon is observed in the transition from dilute to absolute sulphuric acid both with tantalum and aluminium. For tantalum the thickness in dilute electrolytes at 0’ is 4*10pp in absolute sulphuric acid a t 10’ 6*69pp in fnsed silver nitrate 7*12pp and in fused potassium nitrate ll.1p.p. With the different fused salts the thickness of the layer is the greater and the capacity the smaller the higher the melting point of the salt and when the capacities are plotted against the melting points a straight line is obtained which on extrapolation cuts the axis at 510° as if above this temperature no valve effect was possible. E.G. G. S. The After-glow of Electric Discharge and Kindred Pheno- mena. (Hon.) ROBERT J. STRUTT (Proc. Physical Soc. 1911 24 1-8).-It has been found previously that the ozone obtained from a Siemens’ ozoniser supplied with oxygen a t atmospheric pressure does not give any after-glow when mixed with nitric oxide although this effect is obtained when the ozone is obtained from a low pressure dis- charge. Further experiments have shown however that the absence of the after-glow in the first case is due to the very considerable dilution of the ozone by the oxygen for if the ozonised oxygen from the Siemens’ tube a t ordinary pressure is concentrated by fractional distillation the greenish-yellow af ter-glow is readily obtained.Under similar conditions a blue glow appears when the ozone is mixed with hydrogen sulphide. The increased brilliancy of the after-glow which has been found when ordinary or fuming sulphuric acid or sulphur were present along with air in the discharge tube is now shown to be due to the removal by these substances of organic matter which is prejudicial to ozone. When these organic impurities are removed the sulphur compounds have no influence on the after-glow.QENERAL AND PHYSICA I CH ICMIS'I'RI'. ii. 127 Pure dry oxygen exhibits no after-glow and the white glow observed with imperfectly dried oxygen is probably due to the interaction of ozone with soulo substance produced by the action of the discharge on water vapour.The luminosity which is emitted when spring water is shaken up with ozone has been traced to oxidation of the peaty matter present. H. M. D. This substance is not however hydrogen peroxide. Decomposition of Nitrogen Peroxide in the Electrical Glow. J. ZENNECK and B. STHASSER (f'hysjhd. &tsch. 1911 12 1201-1204. Compare this vol. ii 1G).-Spectral observations have been made of the light emitted by the diEerently coloured layers which are obtained when a current of nitrogen peroxide is passed through a long narrow discharge tube. The orange-yellow greenipb- yellow and bright red glows of the first.third and fourth stages exhibit spectra which have been recognised as due to nitrogen peroxide nitric oxide and nitrogen respectively. In the fourth stage some oxygen lines are also present. The violet-blue glow of the second stage is probably due to an intermediate labile oxide its spectrum differing from that of the peroxide by the absence of the continuous portion and from that of nitric oxide by a difference in the relative intensities of the lines. As a result of the investigation of the different regions for after-glow effects it is found that these are readily observed in the case of the first third and fourth stages but the seoond stage does not appear to show any after-glow. H. M. D. Magnetic Temperature-coefficients of the Ferro-magnetic Elements in Corresponding States.J. K. ASllWORTH (Phi[. Mag. 1913 [vi] 23 36-45).-Experiments have been made on the varia- tion of the residual magnetic intensity of magnots made of nickel iron and cobalt for variations of temperature between that of the room and the magnetic critical temperature. If the fractional magnetic. intensity (Z/Io) where I. denotes the intensity a t absolute zero is plotted against the temperature measured as a fraction of the magnetic critical temperature it is found that the experimental data for the three metals can be represonted by a single curve. The critical temperatures of nickel and iron were found to be 388" and 785" respectively and 1090' was adopted as the value for cobalt. From this result i t follows that the characteristic tomperature-coefficients of magnetic intensity of the pure annealed ferro-magnetic elements in corresponding states are inversely proportional to the absolute magnetic critical temperatures The law of variation of the magnetic intensity of t h e ferro- magnetic elements with temperature is therefore of the same kind as that which expresses the variation of the density of a liquid and it is shown that the coefficients involved are of the same order of magnitude.H. M. D. Dependence of the Coefficient of Expansion on the Tem- perature. CHARLES L. LINDEMANN (Physikul. Zeitsch. 19 1 1 12 1197-1 199).-The thermal expansion of rods of aluminium copper 9-2ii. 128 ABSTRACTS OF CEEMICAL PAPERS zinc silver and lead has been measured at low temperatures over the separate ranges afforded by the use of liquid hydrogen liquid air liquid oxygen and ordinary room temperatures When the mean expansion coefficients thus obtained are divided by the mean atomic heats calculated from Nernst and Lindemann's equation (compare Abstr.1911 ii 466) numbers are obtained for each metal which are approximately independent of the temperature. This result is in accordance with the relationship anticipated by Griineisen (Ve.rh. deut. phys. Ges. 19 11 13). H. M. D. The Linear Expansion of Solid Elements as a Function of the Absolute Melting Point. A. STEIN (Zeitsch. anorg. Chenr. 1913 73 270-273).-Lf u is the linear coefficient of expansion of a solid element and v its atomic volume the quantity u O / 2 ) may be considered as the linear expansion of the atomic volume.h e product u gGT where T is the absolute melting point is practically constant over a large range OF melting points being however high for elements of very low melting point (P K Na S) and low for the infusible platinum metals. The regularity becomes more pronounced when the expansion is measured a t low temperatures the coefficient of the more fusible elements being more variable. The relation may be expressed in the form that the atomic heats of solid elements being equal the force resisting the separation of the atoms with increase of tempera- ture is proportional to the absolute melting point. Cubical Expansion of Fused Silica and the Variation of the Boiling Point of Aniline with Preesure.FREDERICK J. HARLOW (Proc. Physical Soc. 191 1 24 30-39).-Neasurements of the cubical coefficient of expansion of fused silica have been made by the weight thermometer method the data being referred to the absolute coefficient of expansion of mercury. For the interval 0-loo3 the cubical expansion coefficient is given as 99.8 x and for 0-184" as 144.7 x lo-*. The former value is considerably smaller than that calculated from previous measurements of the linear expansion but the fact that the coefficient has been shown to change in sign a t about - 80' points to its probable correctness. From measurements of the boiling point of aniline a t pressures from 74 to 78 cms. of mercury it is found that the temperature rises 9-49" per cm. of mercury. C. H. D. H. M. D. Change of Volume Accompanying the Fusion of Crystals. The Thermal Expansion of Grysfals and of their Products of Fusion.HEINRICH BLOCK (Zeitsch. physikal. Chem. 19 12 78 385-425).-The changes of volume which occur in the fusion of crystals was determined by drawing the fused substance into a capillary tube not more than 1.5 mm. wide sealing one end of the tube and allowing the substance to solidify slowly a t a temperature very little below its melting point whereby the occurrence of air spaces is excluded. The position of the upper surface of the solid is then carefully noted as is that of the upper surface after fusion. The tube is then carefully calibrated with mercury and from the data thusGENERAL AND PHYSICAL CHEMISTIIY. ii. 129 furnished the change of volume on fusion is obtained.When impure substances are used the impurities rise t o the surface of the liquid in the capillary tube and can be removed after which the d e k i t e read- ings are taken. The thermal expansion of the crystals was obtained by determining the density at different temperatures by the floating method and the density of the liquid was taken in a special form of dilatometer. These observations gave a n alternative method of obtain- ing the change of volume on fusion and the results are in very good agreement with those obtained directly. The physical constants in question were found for thirty-one substances (organic compounds with one exception) and the results are given in tabular form. ‘They are in most cases in good agreement with those of previous observers.The available data for changes of volume on fusion including those for a number of inorganic compounds are also tabulated. No relationship has been found between tho molecular weights of substances and the changes of volume on fusion. On the other hand Tammann’s formula 6v = I\(d,v’/dT- dpv”/dI’) where 6v is the change of volume on fusion in C.C. per gram 26 the absolute temperature of fusion and dtv‘/dT and d,v”/dT the change in volume of liquid and solid respectively (in C.C. per gram) for a change in temperature of 1’ (compare Krystnllixieren und Schmelzen Leipzig 1903) is valid for the great majority of substances examined. Thermodynamics of the Equilibria in One Component Systems. I. GUSTAV TAMMANN (Ann. Physik 191 1 [iv] 36 1027-1054).-Frorn a consideration of the theory of thermodynamic potential in its application to one component systems it is shown that two forms of equilibrium curves are possible.One of the two groups of curves is characterised by a critical point but such a point is absent in the second group. From this it follows that the limits of existence of the two phases corresponding with an equilibrium curve of t h e first type are incompletely defined whereas the conditions of existence of the phases corresponding with curves of the second type are completely determined by closed systems of curves on the equilibrium diagram. Similar results have already been obtained on the basis of molecular considerations and the theoretical deductions are in agreement with experimental observations.A Correlation of the Elastic Behaviour of Metals with Certain of their Physical Constants. JOHN JOHNSTON (J. Wash- ington Acud. Xci. 1911 1 260-267).-When pressure acts OLI a solid phase but not on the liquid phase produced from it the effect is always to lower the melting point. By means of a thermodynamical equation (Lewis Abstr. 1908 ii 465) t h e pressure required t o pro- duce melting at 25” is calculated for a number of metals for which the densit’y and the latent heat of fusion are known. The values obtained increase from 64 atmospheres for potassium to 21300 for platinum. The order is found bto be the same as that of decreasing ease of flow and compressibility and of increasing Young’s modulus and modulus of rigidity. This indicates that the flow of metsls is due t o conversion into liquid ,under the influence of pressure in accordance with the views of Beilby (Abstr.1904 ii 647). G. S. H. M. D. C. H. D.ii. 130 ARSTRACTS OF CHE.MICXL PAPERS. Neutral Salt Action as Exhibited in the Freezing Points of Mixtures in Aqueous Solution. ALBERT C. D. RIVETT (&fed. A'. Vetenek. Nobelinst 191 1 2 No. 9,1-32).-Measurements of the freezing points have been made for aqueous solutions of fourteen different salts and mixtures of these with (1) ethyl acetate and (2) sucrose. The freezing-point depressions for the two series of mixtures are always greater than the sum of the individual depressions due to the salt and the non-electrolyte. This departure from additivity is attributed to mutual influences operating between the salt and the non-electrolyt e and in the absence of evidence as to the relative erttents of these influences the relative increases in the freezing-point lowering are calculated on the assumption that the effect is entirely due (1) t o the action of the salt (2) to the action of the non-electrolyte.The data thus obtained show that the influence of the salt (or non-electrolyte) is independent of the concentration of the non-electrolyte (or salt) and is in general directly proportional to its own concentration. The pro- portionality doesnot hold in the case of sucrose and the more concen- trated solutions of lithium chloride magnesium chloride and magnesium nitrate. The order of the salts is not the same for the two non-electrolytes and this is considered t o furnish a strong argument against any explanation of the observations which is based entirely on the formation of hydrates.I n tbe case of sucrose there appears to be no connexion between the influence of the different salts on freezing-point depression and on t. he veloci t,y of inversion. H. M. D. 2 8-Dimethylpyrone as a Solvent. G . POMA (Gaxxetta 191 1 41 ii 515-538).-From determinations of its latent heat of fusion (56.0 calories) the cryoscopic constant of dimethylpyrone is found to be 58.7 whilst the mean deduced from cryoscopic measurements with stable organic substances (azobenzene mthracene phenanthrene and phenanthraquinone) is 64.6. The molecular weights of benzoic acid and thymol in dimethylpyrone are slightly below the normal. The molecular weights of some electrolytes in dimethylpyrone solution were found to be much lower than the theoretical values These results accord with those obtained from the measurement of the electrical conductivities of the solutions in some cases but not in others. Measurements of the molecular surface energy and its temperature- coefficient show that dimethylpyrone is slightly associated.It also has considerable dissociating power but this is not manifested in the same sense as that of water so t h a t in the series of alkali halides the degree of dissociation is greatest for sodinm iodide and least for lithium chloride the dissociation of lithium bromide being intermediate between these two. The following other constants have been determined D137 0.9953 DfS3 0 9483; specific heat 0-looo (solid) 0.368; specific heat 152*3-183O (liquid) 0.550 ; surface tension at 137" 30.76 a t 1S3O 26.31 ; molecular surface energy at 137" 767.1 at 183" 677.5 ; coefficient of molecular association 1.21 (9).R. V. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 131 Capillary Force of Evaporation. CARLO DEL LUNGO (Nuovo Cim. 19i1 [vi] 2 ii 425-430). -According t o Laplace's theory the molecules of a liquid in the surface layer are subjected to an attractive force directed towards the interior. This force must naturally be greatest on the molecules quite at the surface. From considerations of the work done in evaporation the author deduces mathematically the formula P=EpC/2 where P is the force a t the extreme outermost layer p is the density of the liquid C is the internal heat of vaporisa- tion and E is the mechanical equivalent of heat.From this it is calculated that at 0" P for water is 11,928 atmospheres for alcohol 3733 atmospheres for ether 1320 atmospheres and for carbon disulphide 2214 atmospheres The results are in fair agreement with those obtained by van der Waals by an alternative method. At looo the calculated value of P for water is 9852 atmospheres. I n the second part of the paper an alternative deduction is given of Sir J. J. Thomson's formula connecting the saturation pressure of a vspour and the curvature of its surface. G. S . Relations betwsen Critical Temperatures Boiling Points and Expansion Coefficients of Liquids. PHILIPPE A. GUYE ( Z'rans. Fm+adcq SOC. 19 1 1 7 11 9-1 21 Compare Prideaux Abstr.1911 ii 368).-The formulae of Mendel6eff and of Thorpe and Rucker (Trans. 1884 43 126) are only approximations and when several values of a are determined for the same liquid the differences found are greater than the errors of observation. The absolute boiling point T may be substituted for the critical temperature TC and the relation YJV2 = D,/D = (a'T - I',)/(a'Ik - TI) in which a' is a new constant =3-09 ives good results over a wide range of temperature. The three constants in the equation log Y= c - d log ( A - t ) may be found as shown by Mallet and Friderich (Arch. Sci. phys. r u k 1902 14 50) and good results are obtained for temperature intervals of from 150" to 300". The expansion coefficient may be found by the relation dvldt = ( d log e)/(A - t ) and the results thus obtained are in close agreement with experiment.The constant A is very nearly the observed critical temperature exceeding i t by 5' or loo; c represents the critical density and cld = 3.78. C. H. D. ,s The formula ot Avenarius expresses a more exact relation. Energy Relationships in Vaporisation and Electrolytic Dissociation. SVANTE ARRHENIUS (Medd. K. Vetensk. Nobelirtst 19 1 1 2 No. 8,1-34).-From a thermodynamic consideration of the changes in free and total energy which are involved in the process of vaporisa- tion it is found that the change in free energy A can be represented by the formula A = A + BT+ CT2 in which A represents the molecular heat of vaporisation a t absolute zero and B and C are constants. The change in total energy V can similarly be expressed by U = A - CT2.I n the case of water the constants involved give rise to the special equation A = - 11 394 + 48.742'- 0*00927T2 and it is shown that the values of A calculated from this are in excellentii. 132 ABSTRACTS OF CHEMICAL PAPERS. agreement with the experimental data between - 20’ and + 2 5 0 O . A t higher temperatures deviations occur which are ascribed to wide divergences from the simple gas laws at the high pressures corre- sponding with these temperatures. A similar agreement between theory and experiment is exhibited in the case of n-hexane and acetic acid. The constants A B and C have been calculated for a large number of substances. It is further shown that the free energy changes associated with dissociation processes (electrolytic and non-electrolytic) can be represented by formuJae of the same type and for these the corresponding constants are also tabulated.I n a11 cases the second term ST has a very important influence on the magnitude of the free energy change and on the other hand the formula for U indicates t h a t dUjdT becomes very small in the neighbourhood of absolute zero. A detailed examination of the values of U/T shows that Trouton’s rule does not hold at all accurately in the case of a large number of liquids and that it map lead to erroneous conclusions when applied to determine whether liquids are associated or not. Vapour Pressure of Nitrogen Peroxide. F. E. C. SCHEFFER and J. P. TRE~JB (Proc. R. Akacd. Wetensch. Amsterdam 1911 14 536-549).-Whilst liquids give the same vapour pressure by either the statical or the dynamics1 method solids which dissociate on passing into vapour give different results by the two methods (Ramsay and Young Abstr.1886 ii 410,965). The results obtained for nitrogen peroxide by Guye and Drouginine (Abstr. 1910 ii 1056) by a statical method differ considerably however from those found dynamically by Ramsay and Young and the vapour-pressure curve also shows a point of inflexion a character hitherto unknown. I n order to avoid contact with mercury a glass manometer of the form devised by Jackson (Trans. 1911 99 1066) is used. The statical measurements coincide almost exactly with those of Ramsay and Young and the vapour-pressure curve is of normal form without inflexion. The under-cooled liquid has been compared with the solid and the intersection of the two curves observed.The boiling point is found to be 21*2O and the melting point - 10%’. An approximate estimation of the degree of dissociation is also made. Composition and Vapour Pressure of Solutions. V. Change of the P a r t i a l Pressures of Vapours of Solutions and Mechanical Mixtures with Temperature. 31. S. VREVSKY (J. Russ. Phys. Chem. SOC. 1911 43 1446-1457. Compare Abstr. 1911 ii 256).-When the two liquids do not mix the change of the ratio of their partial pressures with change of temperature is expressed by H. M. D. C. H. D. d y - l - d P 1 dP 1 - --.--2.- dt y dt P dt Y,’ where P and P are the vapour pressures of the two liquids a t tem- perature t and y=p,/p that is the ratio between the partial pressures.The same expression holds for the case when the liquidsGENERAL AND PHYSICAL CHEMISTRY. ii. 133 mix assuming that the addition of the second liquid t o the first lowers the vapour pressure of the latter in the solution according t o -Raoult’s law p = P1x x being the number of gram-mols. of the first liquid per 1 gram-mol. of the mixture. ’\f7hen the formation of the solution of the two liquids is accompanied by a heat effect the change in composition of the vapour with temperature is expressed by where Q is the heat-effect produced on mixing x gram-mols. of the first liquid with (1 -x) gram-mols. of the second and R is the gas constant in heat units; hence in the general case change of the equilibrium between vapour and solution is the result of the combined action of two factors one of them physico-mechanical and the other physico-chemical.With solutions formed with either development or absorptionof heat these two factors act in the same direction in one region of concentration and in opposite directions in another region the limit between the two regions being the solution for which the heat of mixing is a maximum or minimum that is I n the first two cases considered above if between t and t’ the rate of increase of the vapour pressure of the first liquid does not change in the solution the same will hold for the second liquid. But in the general case where a heat-effect is observed on mixing and the temperature-coefficient of the partial pressure of the vapour is not equal to the temperature-coefficient of the vapour pressure of the liquid in the free state the change of composition of the vapour with temperature is expressed by dQ/dx = 0.Various pairs of liquids have been studied the results confirming qualitatively the theoretical deductions. Tbe Distillation of Difficult Boiling Substances. Huao DUBOVITZ (Seifeensied. Zeit. 191 1 38 529-530).-An enquiry into the distillation of mixtures under varying pressures with superheated steam; the author suggests the following formula as a means of estimating the vapour tension of a contained substance of high boiling point (M2P2)/(MlP1) =a where M and I’ are the molecular weight and vapour pressure respectively of the substance of lower and M and P the corresponding-data for that of the higher boiling point.T. H. P. I?. M. G. M. Heat of Formation of Titanium Dioxide. WILLIAM G. MIXTER (Amer. J. Sci. 1912 [iv] 33,45-48. Compare Abstr. 1909 ii 644). -The heat of formation of titanium dioxide has been redetermined by combustion of the finely divided metal in oxygen. The most trust- worthy observations give Ti + 0 = TiO (crystalline) + 218.4 Cal. This is about 1.1% higher than the value obtained previously by the sodium peroxide method. Both values are in complete disagreementii. 134 ABSTRACTS OF CBEMICAL PAPERS. with t h a t given by Weiss and Kaiser (Abstr. 1910 ii 302) which ia only 97.77 cal. H. M. D. Use of Dewar's Vessels in Calorimetry. ALEXIS J. BOGORODSKY (J. Russ. Phys. Chem. Soc. 3 91 1 43 1262-126S).-Dewar flasks which have been used recently by Mathews and Germztnn (Abstr.1911 ii 187) and by Luginin and Dupont (Abstr. 1911 ii 369) as calorimeters were employed by the author for this purpose as long ago as 1901 (Protokol Phil. SOC. Kaxan Univ. 1901 No. 197). The values then obtained for the heats of solution of KCIO and Na2B,07,10H,0 were - 10051 ( - 10040) and .- 26008 ( - 25859) cals. respectively the numbers in brackets being those given by Thomsen. The apparatus used is described and the results of further measurements made with it given. For Na2HP0,,12€€,O the molecular heat of solution gave the vdues 22836-22925 cals. the mean being 22880 (22830). T. H. P. Heats of Solution of Mono- and Di-hydrated Lithium Chlorides. ALEXIS J. BOGORODSKY (J. IZuss. Ph,ys. Chem. Soc.1911 43 1268-1374).-The experiments here described were carried out by means of the apparatus mentioned in the preceding abstract. The mean of the values obtained for the molecular heat of solution of LiCl,H,O at the mean temperature 20.3" is +4121 cals. the value of + (Thomsen) the change of the heat of solution with temperature being 29.02 cals. per degree. For LiCI,ZH,O the mean value of the molecular heat of solution is +9Sl cals. a t the mean temperature 22*2O (b having the value 12.3. From these results together with the value 8444 given by Thomsen for the heat of Solution of LiCl a t 20*7O the following equations are deduced Tic1 + H,O = LiCI,H,O + 4323 cals. ; LiCI,H20 + H20 = LiC1,2H,O + 3162 cals. On account of the lorn transition temperature ( - 15') of the trihydrate the heats of formation and solution of this hydrate were not investigated.The existence of such a hydrate if this were unknown would be indicated by the positive sign of the heat of solution of the dihydrate. The proposition advanced by Thomsen to the effect that the heat of solution of haloid compounds in water is negative when they are completely saturated with water possesses no general significance. T. H. P. A New Method of Determining Vapour Densities. IX. PHILIP BLACKMAN (J. Physical Chern. 1911 15 869-870. Compare Abstr. 1908 ii 157).-The improved apparatus consists of a graduated tube closed by a ground-in stopper carrying a capillary U-tube. The tube is filled with mercury and after the weighed amount of liquid has been introduced is closed and inverted.When the liquid has been vaporised its volume and pressure can be read off. XI. The Dehydration of Copper Su lphate Pentahydrate. PHILIP BLACKMAN (J. Phpsical Chem. 191 1 15 871-S73. Compare Abstr. 1909 ii 643).-Experiments made with the author's apparatus R. J. C. Simple Method for Vapour Density Determinations.GENERAL AND PHYSICAL CHEMISTRY. ii. 1.35 indicate that the dehydration of copper sulphate takes place pro- gressively as a function of temperature and pressure there being no sudden increase in stability as each molecule of water is removed fi,om the hydrate. Tbe dehydration was not carried as far as the monohydrate stage. H. J. C. Dilatometric Researches. New Form of Dilatometer for M i x t u r e s of Liquids. FILIPPO BOTTAZZI and GIUSEPPE EUGLIA ( A t t i R.Accad. Limei 1911 [v] 20 ii 683-627).-The authors describe a dilatometer intended tor measuring the change of volume occasioned by the mixing of two liquids. The mixture of the two liquids is brought about by the removal of the partition separating them the removal being due to the fusion of the wax which holds i t in position I n its original form the apparatus consists of a stomach- shaped glass bulb which has two openings at the ends of the upper surface. To one of these a graduated capillary is fiised whilst the other aperture consists of a wide tubulure ground on the inside. Into the tiibulure fits a glass tube which is open a t the bottom and is closed at the top by a glass stopper-. This tube serves to hold one of the liquids whilst the main bulb contains the other.I n filling the apparatus a suitable quantity of one liquid is placed in the bulb. The tube just mentioned is closed at the bottom by means of a circular glass plate attached to i t by mesns of a little wax of suitable melting point. To facilitate the introduction of the stopper into this tube the glass plate is provided with a small hole which is kept closed with the finger during the filling and is finally sealed with a spot of wax. The tube thus constructed is filled with the second liquid R glass marble is introduced into it the stoppcr is inserted and the hole in the glass plate sealed as described. The whole is then inserted in the tubulure of the bulb as though it were a stopper. All the joints are well covered externally with wax of high melting point and the apparatus is immersed in a thermostat. When a sufficient tempera- ture is reached the glass plate may be shaken off and the change of volume due to the mixing of the liquids may then be observed.A simplified form of the apparatus differs only in being cylindrical and in having the graduated capillary attached to the top of the tube instead of a stopper so that one of the ground surfaces is dispensed with. This form is recommended. R. V. S. Dilatometric Researches. 11. Preliminary R e s u l t s Re- gardihg Non-colloidal Solutions. FILIPPO BOTTAZZI and GIUSEPPE BUGLTA (Atii 12 Accad. Lincei 2911 [v] 20 ii 627-633. Compare preceding abstract).-The paper gives the chmges of volume observed on mixing solutions of sodium chloride sodium hydroxide sulphuric acid and hydrochloric acid with pure water.The changes in volume were always the same for the same liquids and calculations in the case of sodium chloride solutions showed t h a t the observed changes agreed with those calculated from the specific gravities before and after mixing. R. V. S.ii. 136 ABSTRACTS OF CHEMlCAL PAPERS. Law of Molecular Attraction. DAN TYRER (Phil. Mag. 1912 [vi] 23 101-113. Compare Kleeman Abstr. 1910 ii 22 492 600 932; 1911 ii 34 97).-According to Kleeman the magnitude of the force of molecular attraction is dependent on the distance of separation of the molecules and on the temperature but the author shows that so far as latent heat considerations are concerned it is unnecessary t o assume t h a t the law of attraction includes a tempera- ture function.From the data for the specific heat of various substances at constant volume it is found that the specific heat is considerably greater in the liquid state as compared with the gaseous and from this the conclusion is drawn that the change of energy which accompanies the isothermal expansion of a liquid is not entirely due to a change in the potential energy of molecular attraction but t h a t a liberation of intra-molecular energy must be involved. If it is assumed that the law of attraction can be represented by K2/Sn in which K 2 is constant for a given pair of molecules and S is the distance between them then the author's reasoning leads to the result that n cannot be less than 5 and is probably greater than 7.It is however impossible t o determine completely the lam of attraction from the consideration of the energy changes which accompany the change of volume of a liquid or a gas. Internal Molecular or Intrinsic Pressure. A Survey of the Various Expressions Proposed f o r i t s Determination WILLIAM C. McC. LEWIS (Trcms. Fu~uday ~ o c . 1911 7 94-115).- The expressions proposed by various authors for the internal pressure are reviewed and the assumptions underlying them criticised. I t is shown that all involve one or other of the assumptions ( 1 ) that the pressure K is independent of temperature (2) that K may be repre- sented by a / v t in van der Waals' equation and that a is independent of temperature that is that K/S2 is independent of temperature where 6 is the density.Neither of these assumptions is justifiable although the second is nearly true. The general thermodynamic equation does not allow K to be calculated wit,hout some further assumption. Assuming t h a t the fractional change of K per degree is the same as that of the latent heat per unit volume Li per degree the relation is found K= Li/l - (T/Ll).(8Ll/ST) by the use of which probable values are obtained for ether etbyl alcohol and carbon disulphide. C. H. D. Simplest Example of the Diagram of Hardness [System KBr-KF]. NICOLAI s. KURNAKOFF arid I. B. 17RSHESNEVSKY (J. Buss. Phys. Chem. Soc. 191 1 43 1392-1397).-The existence of eutlectics for the melting curves of binary mixtures of the type MF-MX (where M = K or Na and X = C1 Br or I) was shown by the work of Ruff and Plato (Abstr. 1903 ii 588).In order t o obtain information concerning the composition of the solid phase separating on solidification OF mixtures of potassium bromide and fluoride the authors have investigated the cooling curve by means of the registering pprometer previously dePrcri bed ( Abstr. 1905 ii 10). The melting-point curve consists of two branches meeting in an eutectic point corresponding with the temperature 580" H. M. D.GENERAL AND PEYSlCAL CHEMISTRY. ii. 137 and the composition 40% mol. KF. The addition of as little as 3% of one salt to the other CituEeS a marked eutectic arrest in the cooling curve this indicating that solid solutions are either absent or of very low concentration. I n agreement with this conclusion are the results of the hardness measurements. I t was found that potassium bromide and fluoride like other halogen salts of the alkali metals are plastic substances so that the measurement of hardness was carried out by determining the pressure required to produce flow ; i t has been shown by Kurna- koff atid Schemtschuschny (Abstr.1909 ii 855) that this method gives results in correspondence with those yielded by Brineil's ball test. Measurements of the pressures required to produce flow with potassium chloride bromide iodide and Biloride give values diminish- ing with the atomic weight of the halogen. Similar measurement with mixtures of potassium bromide and fluoride give values lying almost exactly on a straight line joining those for the separate salts this curve exhibiting no peculiarity.at a position corresponding with the eutectic point. These results show that when crystallised from the fused condition the system KBr-KF yields only superposed mixtures of the two salts. T. H. P. Fusion and Pressure of Flow of Mixtures of Isomorphous S a l t s . B. VHSHESNEVSKY (J. Rusa. PIiys. Chem. Soc. 191 I 43 1364-1398).-The investigations here described were made with the view of ascertaining how the hardness and the pressure necessiry to produce flow (compare Kurnakoff and Schemtschuschny Abstr. 1909 ii S55) with salts vary with respect to their capacity of forming solid solutions this being studied thermally. The melting-point diagram of the system KCNS-NaCNS consists of two branches meeting in an eutectic point corresponding with 30% mol.NaCNS. An arrest occurs at 143" owing to the conversion of the a-modification of potassium thiocyanate-stable above 143O-into the /3-form this change being accompanied by considerable develop- ment of heat (compare Gossner Zeitsch. Kryst. Min. 1904 38 136 ). A number of inferior arrests occur between 10 and 40% rnol. NsCNS the most probable cause of these being the formation of a new solid phase XaCNS,3KCNS. Calorimetric investigation of the heat of solution of these fused salts shows the maximum absorption of heat to take place with the composition NaCNS,3ECNS. On solidi tication of their fused mixtures potassium and ammonium thiocyanates form an uninterrupted serios of solid solutions. Owing to tho polyruorphisu of the ammonium salt the cooling curve exhibits four arrest5 (1) at 1 4 P corresponding with the conversion of the liquid t o the a-solid phase; (2) a t 120° indicating the change of the a- into the p-form ; (3) a t looo an eutectic point and (4) at 90° this being accompanied by a marked heat-effect and corresponding with the transformation of the p- into the y-modification (compare Gossner Zoc.cit.). At high temperatures these potassium and ammonium salts give a continuous series of isomorphous mixtures. In order to explain the origin of the two middle arrests the cooling curves of mixtures of I.ii. 138 ABSTRACTS OF CHEMICAL PAPERS. ammonium thiocyanate with the isomeric thiocarbamide were investi- gated. The cooling curve of thiocsrbamide also exhibits a n arrest at looo this being similar in character to that occurring at the same temperature with mixtures of potassium and ammonium thiocyanates.The melting point diagram of ammonium thiocyanate and thio- carbamide is characterised by a eutectic point at 100Oand by two other arrests at 120' and 90° so that the salt undoubtedly exists in the three modifications referred to above. Potaesium and rubidium thiocyanates form an uninterrupted series of solid solutions the system showing a minimum freezing point and being of Roozeboom's third type (Abstr. 1900 ii 132). The system KC1-KI on passing from the fused to the solid condition gives a continuous series of isomorphous mixtures this being confirmed by calorimetric investigation. A t the concentrations 10 and 70% mol. of the iodide the cooling curve shows arrests indicating the breaking-down of the solid solutions the curves characterking this process kiaring the nature of waves.The systems KCI-KBr and KBr-KI giva continuous melting- point curves each exhibiting a minimum which lies at 716" (60% mol. KBr) and 589O (50% mol. K1) respectively. I n either case the cooling curve shows only a n arrest corresponding with the conversion of t h e liquid into the solid phase; hence when the fused mixtures a r e cooled even to lorn temperatures no decomposition of the solid solutions occurs. Calorimetric measurements show however that such decomposition does take place with lapse of time. It is found that the pressure necessary to produce flow in the pure potassium halogen salts varies considerably with the rate at which they have been cooled.The rapid cooling referred t o in the following table was effected by pouring the fused salt into a cold platinum dish and medium cooling by means of a platinum dish previously heated ; for slow cooling the platinum crucible containing the substance is placed in a wider clay crucible situate i n a Fletcher furnace surrounded by asbestos cloth. The pressures are given in kilo:. per sq wm. Rs[~id hlediuni Slvw cooling. cooling. cooling. KCl ............ 28 35 50 -5 1 -8 KBr ........... 36 38 40.5 1 *13 K I ............ 20.5 24 31 '0 1.5 PI - p,. P3. P3 Pi. With fused mixtures of salts the effect of variation of the rate of cooling is more complex; with KC1-KI for example this effect is opposite in direction to that obtained with the pure salts.I n tho following experiments '' rapid " cooling was always employed. The maximum pressure required t o cause flow corresponds in the case of KQl-KBr with 40% mol. KBr and in that of KBr-KI with 60% mol. KBr. I n both systems this pressure is more than double t h a t required by the constituent salt which flows t h e less readily. After the cooled masses have been kept at the ordinary temperature for five weeks tho pressures required are considerably less than the original ones. It is hence evident that as the process of decomposi-GENERAL AND PHYSICAL CHEMISTRY ii. 139 tion of the solid solutions approaches its 6nal state the curve of pressures approaches the straight line joining the pressures for the two constituent salts. With KCI-KJ the pressure of flow curve shows two maxima and a minimum.The stibility and slight amount of decomposition of t h e solid solutions of low concentrations condit,ion a very rapid rise in the pressure in passing from 0 to 10% mol. KI and from 100 to 90% mol. KI. When the concentration of the solid solutions is increased con- tinuous decomposition of these solutions occurs until a state of mechanical mixture is approached this corresponding with a rapid fall in the pressure of flow. It is remarkable that the minimum pressure which corresponds with about 50% mol. is lower than the pressure for either of the two salts. With KCNS-NH,CNS the pressure of flow curve consists of two branches (1) that from 0 to 20% mol. KCNS being almost a straight line which corresponds with mechanical mixtures of y-NH,CNS with a definite concentration of the P-solid solution (20% mol.KCNS) ; (2) that from 20 t o 100% mol. KCNS showing a maximum a t about 70% mol. KUNS and corresponding with solid solutions of the P-modifications of the two components. With KCNS-RbCNS the curve shows a maximum a t 20% mol. KCNS which greatly exceeds the pressure for either component. Owing t o the occurrence of the new solid phase mentioned above the pressure diagram of the system KCNS-NnCNS is complicated by the presence of a maximum at 20% mol. NaCNS. Further increase of the latter results in the fall of the pressure to a minimum (intermediate to the values for the separate conitituents) a t 40% mol. NaCNS. T. H. P. Chief Law of Adsorption Phenomena. SVANTE ARREIENIUS (Medd.K . Vetensk. Nobelinst. 1911 2 No. 7 1-44).-The recent work of Homfray (Abstr. 1910 ii 771 1041) and Titoff (ibid. ii 1041) 0x1 the adsorption of gases by charcoal and that of G. C. Schmidt (ibid. ii 1041) on the adsorption of acetic acid from its aqueous solutions by charcoal indicates that the ordinary exponential formula a = k@ cannot be valid between wide limits. The formula is devoid of theoretical foundation and should be regarded at most as an empirical formula the applicability of which is limited to a comparatively narrow range of concentrations. By taking into account the fact that the quantity of adsorbed substance reaches a maximum value the adsorp- tion is supposed to be determined by the equation k.dx/dc = (s - x)/x which on integration gives log s/(s - x) - 0-4343.x/s = l/k.c where x represents the quantity of adsorbed substance per gram of charcoal s the maximum value of x c the pressure of the gas or the osmotic pressure of the dissolved substance and k a constant.For a given kind of charcoal the values of s (expressed in gram-molecules) are of the same order of magnitude for different substances. It is shown that the above formula affords a satisfactory representa- tion of the adsorption of gases and of acetic acid by charcoal within wide limits of concentration. At high temperatures and small con- centrations deviations are found between the calculated and observedii. 140 ABSTRAC'I'S OF CHEMICAL PAPERS. results which are ascribed to the variation in the heat of adsorption with the quantity of substance adsorbed.From the fact that the adsorption of a gas increases with increase in the attraction between the gas molecules the author infers that the phenomenon of adsorption is essentially determined by the attractive forces between the molecules of the adsorbed substance. In support of this view it is shown t h a t the changes in volume which occur when a liquid is compressed can be represented by the above adsorption formula. I n this case x represents the density of the liquid c the pressure (internal plus external) and s the maximum density. By reference to the compressibility data for ethyl ether and ethyl alcohol it is shown that experimental observations can be adequately represented by this formula. I n comparison with the exponential formula which contains two arbitrary constants the author points out that this formula contains only one for the quantity s is in every case directly determinable from experimental observations.H. M. D. Absorption of Gases by Porous Materials. JACQUES DUCLAUX (Conzpt. rend. 1911 153 1217-1230. Compare Abstr. 1911 ii 479).-An attempt to calculate the absorption coefficient of carbon for carbon dioxide on the basis of the hypothesis put forward in an earlier communication. Comparison of the result with the known value suggests that local differences in temperature have a greater effect ou absorption than local differences in pressure within the minute cavities of which the porous material is composed. w. 0. w. Adsorption in Solution. 11. Dualistic Nature of Adsorp- tion Phenomena.GEOHG vON GEORGIEVICS (Monatsh. 191 1 32 1075-1087. Compare Georgievics and Pollak Abstr. 1911 ii 1070). -The adsorption of acids from solution by wool also includes the dis- solution of acid in the wool arialogous to that shown in the adsorption of gases by charcoal. Once equilibrium between acid and wool is attained there is no slow further retention of acid. The velocity with which equilibrium is attained depends not only on the nature of the adsorbed and adsorbing substances but also on the conceutration of the solutions employed. Until a concentration of roughly 0.05 gram of acid per 250 c.c. hydrochloric and sulphuric acids are dissolved by wool ; in more concentrated solutions the phenomenon is one of adsorption i t being impossible to say whether there is any diffusion into the interior of the thread. Sulphuric acid is somewhat more easily soluble in wool than hydrochloric acid the ratio being approximately 9 7.The statement previously made that sulphuric acid is adsorbed more than hydrochloric acid in dilute solution and less in concentrated solution is now explained as owing to the excess of solubility of the sulphuric acid actually hydrochloric acid is the more adsorbed. Tha speed with which a substance is adsorbed is no criterion of adsorption as it is shown that from concentrated solutions very rapid diffusion into the inside of the solid material takes place. The facts mentioned afford an explanation of some anomalies in theGENEKAL AND PHYSICAL CHEMISTRY. ii. 141 results obtained on dyeing silk with picric acid (Georgievics Abstr.1911 i 537). I n dilute solutions containing 0.01 gram of picric acid per 100 C.C. and less the retention of picric acid is due t o solution; in more concentrated solutions of picric acid the retention is due to adsorption. I n concentrations of 0.01 to 0.02 gram per 100 c.c. there is a rapid increase of the retention of acid which is regarded as due to chemical processes. Picric acid and silk afford a case of retention due t o solution chemical action and adsorption in turn. Similarly solution of the dye in the fabric takes place in the case of dyeing in dilute solution ; there is some chemical action between dye and fabric but in stronger dye solutions tho retention is chiefly caused by adsorption. E. F. A. The Nature of S o l v a t e s and the Relationships between Adsorption and Dissociation. KURT GEBHAED (Zeitsch.Chenz. Ind. Kolloide 191 1 9 263-265. Compare Ostwald Abstr. 191 1 ii 1068).-The relationships between adsorption comporinds and solvates are discussed from the point of view of a theory of partial valencies with special reference to the explanation of the formation of complex compounds between dyes and fibres. H M. D. Mechanism of Osmosis. IEUGBNE FOUARD (Compt. rend. 19 1 1 153 1152-1155. Compare Girard Abstr. 1909 ii 537 ; 1911 ii 861).-A polemical paper against Girard and Henri drawing attention to the importance o€ absorption by the membrane in the mechanism of osmosis. Osmotic pressure can only be measured when this absorption is complete and when equilibrium has been established the osmotic effect is independent of the nature of the membrane.Objection is raised against De Vries’ definition of isotonic solutions on the ground that the protoplasm of a vegetable cell maintaining constaut volume in a solution is in osmotic equilibrium not with the external solution but with a liquid between the two cell membranes this liquid differing in composition from the first owing to the absorption of dissolved substance by the exterior envelope. w. 0. w. Behaviour of Edges and Corners in C e r t a i n Diffusion Experiments. KAPHAEL E. LIESEGANG (Zeitsch. Chem. I n d . Xolloide 1911 9 296-298).-Tf irregularly shaped pieces of jelly obtained by the solidification of a 10% solution of gelatin containing a small quantity of silver nitrate are placed in a saturated solution of potassium dichromate it is found that silver chromate is preferentially formed on those parts of the surface which are approximately plane.The portions of the surface in the neighbourhood of hollows and pro- tuberances are unaffected by the surrounding reagent. The importance of this observation in connexion with certain processes employed by histologists is referred to. H. 31. D. Diffusion of Oxygen and Carbon Dioxide in Water. TOR CARLSON (Medd. K . Vetensk. ivobelinst. 1911 2 No. 6 1-8).-The coefficients of diffusion of carbon dioxide and oxygen in water a t 18.2O VOL. CII. ii. 10ii. 142 ABSTRACTS OF CEEMICAL PAPERS. have been found to be 1.479 and 1.720 respectively. These values when corrected for difference in temperature are in fairly good agree- ment with the coefficients determined at 16” by Stefan and Hiifner.The ratio of the coeflicients is 1.166 which approximates closely to t h a t calculated from measurements of the rates of dissolution of the gases. The rates of diffusion are very nearly in t h e inverse ratio of the square- roots of the densities which requires 1.1 73 instead of the observed ratio of 1.166. H. 11. D. Velocity of Diffusion and Size of the Particles in Disperse Eystems. THE SVEDBEKG (Arkiv. Kern. Min. Geol. 1911 4 No. 12 1-7).-The author has carried out further experiments to decide between the Sutherland-Einstein and the Smoluchowski formulae for the rate of diffusion of a particle using a colloidal gold solution for the purposes of experiment.The velocity of diffusion of the gold particles was measured by means of the apparatus used by Svedberg and Andreen-Svedberg (Abstr. 191 1 ii 375) the concentrations being determined by measuring the extsinction-coeficients of the solutions. From the velocities of diffusion so determined the radii of the diffusing particles were then calculated by mems of the above-mentioned formulae and found t o be 1 . 2 5 ~ ~ and 297pp respectively. The size of the particles was then determined by Zligmondy’s ‘‘ nucleus method ” (Keimmebhode) and found to be 1*33pp which agrees with the first of the above two values. The Sutherland-Einstein formula may there- fore be taken as the correct one. 11. T. S. P. The Alleged Colour of the Ions. GAETANO MAGNANINI (Gaxzetta 1911 41 ii 425-429).-The author re-asserts his views on this subject (see Abstr.1893 ii 570 ; 1894 ii 226 ; 1897 ii 14). S y s t e m a t i c s of the Aggregated States of Matter. R. V. S. P. P. YON WEIMARN (J. ~ U S S . Yhys. Chan~ soc. 1911 43 1477-1502).- Principally a discussion of the author’s orientation or vectorial theory of matter (compare Abstr. 1910 ii 1048 and elsewhere). T. H. P. The Dependence of the Brown-Zsigmondy Movement on Temperature. 31. SEDDIG (Zeitsch. anorg. Chem. 1912 73 360- 384).-If the molecular explanation of the Brownian movement is correct the displacements should be proportional to the square-root of the absolute temperature and inversely proportional to the square- root of the internal friction of the liquid used (Einstein Ann.Physik 1905 [iv] 1’7 549). The values hitherto obtained from visual observation dift’er widely from theory owing to errors of measure- ment and t o the relatively long time of observation which allows currents in the liquid to form. An arrangement for preparing kinematographic records at a magnification of 3000 is described but quantitative measurements have not been made satisfactorily. The best results are obtained by using an ultra-microscope in which the rays are focussed in the object by a n oblique concave mirror and are prevented from reaching the eye-piece by a small lateral stop.GENERAL AND PHYSICAL CHEMISTRY. ii. 143 Two successive short exposures are made by ineans of a special shutter and the distance separating pairs of images is measured.The stage is electrically heated to a constant temperature which is measured by a thermo-couple placed in a layer of paraffin immediately below the thin glass carrying the liquid under examination. The suspensions used are cinnabar and freshly-prepared lamp black both of which give good contrasts and are uniform in size. As the displacements thus observed are only projections of the actual displacements on a horizoutal plane the absolute values are only found with difficulty but relative values for a range of tem- perature from 5.5” to 90” are obtained and show divergences which do not differ from those calculated by Einstein’s formula by more than 6% being always too high probably owing to absorption of heat from the source of light during the short exposure. The Brownian Movement of Particles in Colloidal Solu- tions 111.THE SVEDBERG and KATSUJI INOUYE (Arkiv. Kern. Mzn. Geol. 1911 4 No. 19 1-20).-!I!he method of measuring the Brownian motion of colloidal particles referred to in a previous paper (compare Abstr. 1910 ii 772 1017) is now described in detail. It consists in tracing the movements of individual particles over a considerable period of time (five to twenty seconds) and registering the positions occupied at successive times during such periods on R moving photographic plate. From the records obtained for a number of particles the displacements which occur as the result of the Brownian motion can be calculated. Experiments made with gold hydrosols prepared by direct reduction of gold chloride solutions with hydrazine show that the movements are in agreement with Einstein’s molecular kinetic formula.For Avogadro’s constant the data obtained with such hydrosols consisting of small sized particles give the value 6.2 x 1023. Determination of the Dimensional Distribution of the Colloidal Particles in a Disperse System. THE SvEDBERa and KNUD EsmuP (Zeitsch. Chern. fnd. Kolloide 1911 9 259-261).- The degree of uniforn-ity in the size of the colloidal particles in various dispersoid systems has been investigated by microscopic observations of the changes which occur in the spacial distribution of the particles when these are allowed to fall under the influence of gravity. Experiments were made with aqueous suspensions of mercury and gamboge with the milk juice of Chelidonium Eaciniatum cow’s milk cream from cow’s milk and cocoanut milk.Curves are plotted which show the numerical distribution of the particles accord- ing to their dimensions. I n this way curves are obtained which are more or less symmetrical and convex to the dimensional axis and the closeness with which the symmetrical branches of the curve approximate affords a measure of the degree of uniformity of the size of the particles. Coagulation of Prussian-Blue. NIGOLA PAPPAD~ (Gaxxetta 1911 41 ii 454-460. Compare PappadA and Sadowski Abstr. 1910 ii 593).-Ferric ferrocyanide differs from silicic acid in that C. H. D. H. M. D. H. M. D. 10-2ii. 144 ABSTRACTS OF CHEMICAL PAPERS. its coagulation is instantaneous so that the effect of different coagulating agents has to be measured by comparing the minimum quantities of them required to produce coagulation.The results obtained are identical with those for silicic acid. Undissociated organic substances do not cause coagulation. Coagulation is produced by electrolytes and the colloid has a negative charge. The coagulat- ing action of the salts of univalent cations increases with increase in the atomic weight of the cation whilst a comparison of univalent bivalent and tervalent cations shows that the coagulating power increases with the electrical charge of the cation. R. V. S. Stability of Emulsions of Water in Hydrocarbon Oils. ERICH GROSCHUFF (Zeitsch. Chem. Znd. Rolloide 19 11 9 257-259)- Observations relative to the stability of emulsions of water in benzene petroleum (D 0.792) machine oil (D 0-864) and paraffin oil (D OW32) have shown that the stability is not determined by the difference in density between the disperse phase and the dispersive medium or by the solubility of water in the hydrocarbon.It is more probable that the stability is to a large extent dependent on the surface tension at the surface of separation of t-he two phases increasing as the surface tension diminishes. The water emulsions examined increase in stability in the order benzene petroleum paraffin oil machine oil and the pronounced difference in the stability of the two last emulsioris is attributed to the presence of colloidal impurities i n the machine oil. H. M. D. Plant Colloids. I. The Solution Swelling of Starch in Presence of Crystalloids. MAX SAMEC (Koll.Chem. Beihefte 19 11 3 123-160).-Measurernents have been made of the temperatures at which starch granules lose their characteristic form by a process of swelling in which highly viscous globules of a starch solution are formed when the starch is heated in contact with water or aqueous solutions. An optical method is described by means of which the accompanying change in the transparency and refractive index of the granules can be employed for the accurate determination of this temperature. For a given solution the separlite observations agree to about 0*2-0.4°. I n all experiments the same sample of starch was used the swelling solution temperature of this being 59.7'. This temperature is altered in presence of salts acids bases and non-electrolytes and the effect of these different substances is qualitatively the same as in the case of the swelling of gelatin.Whether the temperature is raised or lowered is essentially deter- mined in the case of salts by the anion the cation having a much smaller influence. A t low concentrations bases exhibit the largest effect in lowering the swelling temperahre and in accordance with this it is found that kalts formed by a strong base and a weak acid have in general a depressant effect at moderate concentrations. I n certain cases such as chloral hydrate and carbamide the influence of non-electrolytes on the sweiling temperature is very considerable. H. M. D.GENERAL AND PRYSICAT CHEMISTRY. ii. 145 The Ultramicroscopic Structure of Jellies WILHELM BACH- MANN (Zeitsch.aqzorg. Chem. 1911 73 125-172).-Tbe internal structure of organic jellies may be studied by means of the cardioid condenser whilst t h e finer structure of silicic acid gels requires the ultramicroscope. The process of gel-formition is the same in gelatin agar-agar and silicic acid gels. The amplitude of the movements of the ultramicro- scopic particles diminishes and the size of the particles increases during the ageing of the gel. The process resembles that of the separation of two liquid phases from a solution (Lepkowski Abstr. 1911 ii 95). Solutions containing less than 1% of gelatin which do not set on cooling show a gradual formationof separate flocculent particles or aggregates of su bmicrons. With increasing concentration the structure becomes less distinct and at last 1x1 tramicroscopically homogeneous owing to the closeness of packing of the “ jelly-elements.” There is no evidence of a honeycomb or foam structure and these structures where previously observed are due to diffraction effects in the micro- scope and are much coarser than the submicronic structure.After treating with alcohol or chromic acid a new coarser structure is obtained due to the formation of capillary cracks following on partial coagulation. The clearest colloidml silica is obtained by dialysis with a collodion membrane. The mass dried over sulphuric acid polarises light when viewed in the ultramicroscope indicating a very minute heterogeneity. The changes observed during the passage through the opaque stage after immersion in benzene correspond with those described by Zsigruondy (Abstr.191 1 ii 880). C. H. D. Application of the Kinetic Theory of Gases to Chemical Problems. OTTO SACKUR (Ann. Physik 191 1 [iv] 36 958-980).- A theoretical paper in which the relationship betmeeu the entropy of a system in a given Condition and the ‘‘ probability ” of this condition is applied to the consideration of irreversible chemical changes. This leads t o the conclusion that molecules of different substances which are contained in an adiabatically closed space will only react together if the reaction leads to an increase in the “probability” of the system. The condition of equiiibrium is characterised by a maximum value of the “ probability.” H. M. D. Equilibrium in the Adsorption by Graham’s Ferric Oxide Hydrosol.P. MAFFIA (KolL. C‘hem. Beihefte 1911 3 85-122) - The relationship between the quantity of chloride adsorbed by colloidal ferric hydroxide prepared by Graham’s method and the chloride con- centration of the aqueous solution in equilibrium with it has been investigated by two series of experimenth in one of which the colloidal solution was filtered through a membrane of collodion and in the other was subjected to dialysis. The results obtained by each method indicate that the adsorbed chloride varies with the chloride concentra- tion of the dispersive medium in accordance with the requirements of the exponential equation q’m = p.cl/p. H. M. D.ii. 146 ABSTRACTS OF CHEMICAL PAPERS Reduction of Mercuric Chloride by Phosphorous Acid and the Law of Mass Action.JAMES B. GARNER (Amer. Chern. J. 1911. 46 648).-Garner Foglesong and Wilson's interpretation of the data obtained in their study of the reduction of mercurous chloride by phosphorous acid (Abstr. 1911 ii 972) was erroneous. New calcula- tions are being made and will be presented in a subsequent communication. E. G . A Special Case of Heterogeneous Equilibrium. P. P. FEDOTPEFF (Zeitsch. anoyg. Chem. 19 11 73 173-199).-Following on the study of the cuprous iodide equilibrium (Abstr. 1911 ii 42) the equilibrium Cu(NO,) + P b I Z? Pb(NO,! + CuI + I has been investigated. Neither cuprous iodide nor iodine reacts with lead nitrate but a mixture of the two readily forms lead iodide. The solubility of lead iodide in pure water a t 20' is 0.015 mol. per litre and this is increased to 0.216 in a saturated solution of iodine owing to the formation of the tetraiodide.I n a solution saturated with copper and lead nitrates the concentration of copper nitrate is almost the same as in pure water but that of the lead nitrate is reduced from 1.523 t o 0.052 mol. per litre. When Cu(N0,),,6H20 and CuI itre both present in the solid phase an irreversible reaction sets in with the formation of oxides of nitrogen and a basic salt. P b( N 0,) 2 P b I C u I I is realisable. The value of K= SCu/8Pb is not constant but varies with the total concentration 8(NO,) increasiDg with the dilution. The equilibrium has also been studied electrolytically by means of the cell Pt I solid PbI,,I I Pb(NO,) solution 1 KNO solution I CU(NO,)~ solution I solid Cu1,I I Pt the solutions used being in different experiments 3N/2 N / 1 and N/2 as regards S(NO,),.The observed E.M.F. is in good agreement with the calculated. The results are applied to the theory of fractional precipitation as in tho addition of a soluble iodide to a mixture of lead and copper nitrates C. H. D. The system with solid phase Colorimetric Investigation of Neutral Salt Action. BOHDAN VON SZYSZKOWSKI (Zeitsch. physiknl. Chem. 1912 78 426-489. Compare Abstr. 1908 ii 761).-The measurements were not made in a coloi-imeter but with two glass cyliuders which for comparison were held in the hands and examined with a background of white paper some cms. away. Methyl-orange was exclusively used its indicator. When solutions of acetic acid and of hydrochloric acid are compared the former acid gives the deeper tint with methyl-orange up to a H' ion concentration of 1 x 10-3 mols.per litre but with higher concentrations hydrochloric acid gives the deeper colour. The tints produced by the two acids are not quite identical. Neutral salts enter into reaction with methyl-orange and render i t more sensitive t o H' ions. This effect is mainly due to increased dissociation of the indicator as an acid and partly to the formationGENERAL AND PHYSICAl. CHEMIS’I’RY. ii. 147 of complex compounds with the salts. That the latter is not the sole factor is shown by the observation that sodiiim chloride is much more effective than potassium chloride in intensifying the colour. The interpretation of the results is complicated by the fact that methyl-orange is an amphoteric electrolyte.The effect of salts i n deepening the colour of solutions containing acetic acid and methyl-orange is due partly to an increase in the dissociation of the acid and partly to increased sensitiveness of methyl- orange. The “neutral salt action” of sodium salts is greater than that of potassium salts and that of bromides greater than that of chlorides. Non-electrolytes are practically without influence on the sensitiveness of methyl-orange. An estimate of the influence of potassium and sodium chlorides on the degree of dissociation of hydrochloric acid is given but the results are only approximate. Aqueous solutions of methyl-orange alter slowly in sensitiveness for some hours after preparation b u t then remain constant for weeks.Solutions of methyl-orange containing acids and salts slowly undergo an irreversible chemical change whereby the colour becomes much paler. G. S. Hydrolysis of Esters of Substituted Fatty Acids. WILLIAM A. DRUSHEL (Amer. J. Sci. 1912 [iv] 33 27-31).-From measurements of the rate of hydrolysis of ethyl acetate chloroacetate and cyano- acetate in presence of O*lN-hydrochloric acid a t 2 5 O i t is found that the velocity coefficients are in the ratio 67.7 45.8 10.25. The rate of hydrolysis of the cyanoacetate is smaller than would be expected from the relative ionisation constants of the three acid,.. The relative amounts of hydrolysis for a given time interval were also compared in a series of experiments with 0.1 molar solutions of the three esters in the absence of acid.The data show that the chloroncetate and cyano- acetate are hydrolymd much more quickly than ethyl acetate and the velocity for the chloroacetate is considerably greater than for the cyanoacetnte although cyanoacetic acid is a stronger acid than chloro- acetic. It is suggested that the observations may be explained if it is assumed that the cyanoacetic acid is to some extent polymerised in its aqueous solutions. H. 1%. D. Conflgurtttion of Ring Systems. JACOB BOESEKEN and A. VAN ROSSEM (Rec. trav. chim. 1911 30 392-406. Compare Abstr. 1911 ii 197).-Magnani (Abstr. 1890 1357 ; 1891 251) has studied the behaviour of boric acid i n solution towards mannitol and dulcitol by determining the conductivities of solutions of various strengths OF mixtures.The authors have extended the research to nine other alcohols and phenols. Glycerol pentaerythritol catechol and pyrogallol are found t o increase the molecular conductivity of boric acid whilst the other alcohols and phenols studied either have no action or else cause a diminution of the conductivity. Comparison of the enormous influence of catechol with the indifference of ethylene glycol shows that it is not sufficient that the hydroxyl groups should be in the ortho- or a-position to one another but that these two hydroxyl groups should be in theii. 148 ARSTRAC rs OF CHEMICAL PAPERS. same plane thus permitting the formation of ring combinations with the boric acid W. G. Velocity of Saccharification of Starch. VI. HENRI VAN LAER (Bull.Acad. Boy. Relg. 1911 795-830. Compare Abstr. 1910 ii 839; 1911 ii 28 478).-This part deals with Kjeldahl’s law of pro- portionality and the retarding action of the products of reaction on the activity of diastase. The results obtained by previous investigators are first critically considered notably those of Kjeldahl (Med. Cn~lsberg Lab. 1878 French edition) Brown and Heron (Trans. 1879,35,596) Ling (Abstr. 1902 ii 636) Ford (Trans. 1904 85 980; 1906 89 76) and Wohl and Glimm (Abstr. 1910 i 799) and a large number of new results are recorded. From all the results available the following conclusions are drawn. Even in feeble concentrations maltose exerts a small but nearly negligible inhibiting action on the activity of diastase but this retardation does not mask the appreciable rise in the coefficient of velocity of saccharification.The adsorption of diastase by maltose appears to result in the combination of minute quantities of the enzyme with a large excess of the sugar. All the peculiarities of the reaction appear to be explained by the adsorption compounds formed by the ferment with ( a ) starch ( b ) the dextrins and ( c ) maltose; thus the increase or decrease in the velocity of saccharification depends on the adsorption or release of new quantities of ferment by non-hydrolysed material. When the conditions are such that the enzyme is all adsorbed by the maltose a t the moment of its formation the reaction follows the logarithmic law. Observations on the reaction should not be made near the limits of saccharification.Kjeldahl’s law is followed in t h e reaction below and above the limit of 45% of maltose laid down by its author. Apart from the inhibiting action of maltose there are a series of retarding and accelerating influences capable of altering the limits within which the law holds; of these the most important is that due t o the rapid lowering of concentration of starch in liquids containing much diastase. The effect of the quantity of diastase used on the velocity of sacchari- fication is expressed by the equation X=nFm. In reactions in which the logarithmic law for unimolecular reactions is followed m = I but it becomes greater although always remaining nearly 1 when any departure from this law is made. Such increases in the value of m are not occasioned by greater adsorption of enzyme in solutions rich in diastase. I n hydrolysis of starch by acids the velocity depends on the number of ions per unit of volume whilst in hydrolysis by diastase it depends at each instant on the relation between the mass of enzyme adsorbed and that of the maltose which remains to be formed.T. A. H. Dependence of the Influence of Neutral Salts on the Concen- tration of the Acid in Catalytic Reactions. HARALD LUNDEN (Medd. K. Vetensk. Nobelinst. 1911 2 No. 3 1-5).-To express the influence of neutral chIorides on the catalytic action of hydrochloric acid in the inversion of sucrose the formula k = A.[H](l+ a [ H ] + b[K] +c[ClJ> is suggested. I n this ?c is the velocity coeficient [HI [R],GENERAL AND PHYSICAL CHEMISTRY. ii. 149 [Cl] the concentration of the hydrogen salt cation and chlorine ion respectively and A a b and c are constants.It is shown that the experimental data obtained by Trey for the influence of sodium and potassium chloride can be satisfactorily represented by means of this formula. The constants cb + b and b + c represent respectively the influence of the acid and of the neutral salt on the catalytic activity of the hydrogen ions. Since these have the same value for varying concentrations of the catalysing acid it follows that the relative neutral salt action is independent of the concentration of the acid. Since this is also independent of the concentration of the hydrolyte it seems probable that the neutral salt action is dependent on physical rather than on chemical factors.H. M. D. A New and Simple Method f o r Comparing Molecular Weights. I. PHILIP BLACKMAN (J. Physiccd Chem. 1911 15 866-868. Compare Thovert Compt. rend. 1902 134 564).-The method is based on Riecke’s theory which requires that the rate of diffusion should be inversely proportional to the square-root of the molecular weight. When solutions of equal (weight) concentration of the two substances the molecular weights of which are to be compared are connected by a tube of pure solvent the position in the tube a t which the diffusing solutes meet enables their relative diffusion velocities and hence their relative molecular weights to be calculated. A suit- able apparatus is described for use with pairs of solutes which give a coloration or precipitate when they meet in the tube.The result is independent of the state of ionisation of the solutes. R. J. C. Determination of the Molecular Weight of Crystalline Substances GUSTAV TAMMANN (Bey. 191 1,44 3618-3628).-From a consideration of the pressure-temperature ( p 5”) curves the author divides crystalline substances into two classes ~v hich are distinguished by use of the term ‘‘crystal group.” Substances of the first class which correspond with monotropic substances form only one crystal group but to each crystal group there belong a stable and a series of unstable thermally different forms. Substances belonging to the second class which correspond with enantiotropic substances form two crystal groups and each of these groups consists of a stable and a series of unstable forms.Comparison of the association of different liquids as measured by the Eotvos-Ramsay and Shields method shows that the normal liquids on crystallisation give only one crystal group whereas the associated liquids often give two crystal groups. From t h i s the author draws the conclusion that the molecular weight of normal liquids does not alter during crystallisation and consequently that gas liquid and crystals have the same molecular weight. Further considerations lead him to the conclusion that. the molecular structure of a crystal deposited from an associated liquid is simpler than that of the liquid itself. Rules are given by means of which from a consideration of the specific volumes and heats of fusion of unstable forms the crystal group to which they belong may be determined. T. s. P.ii. 150 ABSTRACTS OF CHEMICAL PAPERS. The Effect of Continued Grinding on Water of Crystal- lisation. C. E. GILLETTE (Chem. News 1922 104 313-314. Com pare Bleeker Abstr. 1910 ii 235).-0n continued grinding of 3 grams of the salt in an agate mortar barium chloride lost from 0.01 to 0.51% of water the loss being lessened by recrystallisation. The loss is chiefly due to superficial water which is again taken up when the ground salt is exposed to air. Potassium and ammonium alum lost over 2% of water on continued grinding. Strontium chloride lost 1 *5-2% borax 3*3-3*7% manganous chloride 1*92% and disodium hydrogen phosphate 28-30% of water. 0. H. D. An Electrical Laboratory Furnace Wound with a Non- noble Metal. LEO UBBELOHDE (Chem. Zeit. 1911 35 1403-1404). -The disadvantage of a furnace wound with nickel wire is that after a time the nickel changes its structure and readily oxidises. The author prevents this oxidation by imbedding in charcoal the wire which is previously protected with a fire-resisting but porous insulating layer made from kaolin alumina and asbestos. A t tbe temperature of the furnace a sn?all quantity of the charcoal burns giving a mixture of carbon monoxide and dioxide which protects the wire from oxida- tion. An arrangement is made for adding charcoal from time to time to replace that which burns away. The wire used in the furnace is an alloy (the composition is not given) the resistance of which a t 1000" is only slightly higher than a t 20'. The furnace may therefore be directly connected with the heating voltage without i t being necessary to insert rheostats and thus offers many advantages over furnaces supplied with platinum resistances (Herseus furnaces). T. S. P. Two Simple Forms of Gas-Pressure Regulators. EDGAR STANSFIELD (Trans. Fayaday Soc. 1911 7 116-118).-A glass cylinder open below is fixed in an outer vessel containing water. A beaker moves easily within this as a float and carries a glass rod at the upper end of which is in one form of apparatus a glass bulb in the other a cap to serve as a valve. The seating for the bulb is provided by an outer short glass tube with ground top whilst the cylindrical cap of the second form nearly fits the inlet tube. The delivery pressure is equal to the difference of level in the inner and outer vessels when the valve is just on the point of closing. The first form is the more sensitive but is occasionally liable to set up a continuous vibration. C. H. D. A New Funnel. 111. PHILIP BLACKMAN (Chem. News 1911 104 312. Compare Abstr. 1911 ii 796 1081).-The funnel has a wide lower aperture and no stem so that the cone of the filter-paper projects freely. C. H. D. Exact Reading Device for the Mohr-Westphal Balance. VON HEYGENDORFF (Chern. Zeit. 1912 36 5-6).-1n order to facilitate bringing the point of the swinging arm of the specific gravity balance into coincidence with the stationary point two glass microscope slides,INORGANIC CtfEMJSTRY. ii. 151 each with an etched horizontal line are attached to the stationary arm by rubber bands so that the swinging point lies between thern. C. H. D.

ISSN:0368-1769    

DOI:10.1039/CA9120205109

出版商:RSC    

年代:1912

数据来源: RSC

摘要:

i. 149 Organic Chemistry. Catalysis and the Formation of Petroleum. CAHL ENGLER anti E. SEVERIN (Zeitsch. angew. Chern. 1912 25 153-158).-Re- petition of Kunkler’s experiments on the distillation of crude oleic and stearic acids at atmospheric pressure (Chern. Zent~. 1910 i 2031) shows that decomposition begins a t 340° and 358’ respectively and that the formation of hydrocarbons is small and commences at about 400O. The suggestion of Kunkler and Schwedhelm (Abstr. 1909 i 281) that soaps may first be formed by the interaction of lime or alumina with fats and that these under theinfluence of heat may give rise first to ketones and eventually to the hydrocarbons of petroleum is untenable since ketones have not been found either in bitumens or petroleum and no indication of the existence of soaps in bitumen could be found by the authors.Various investigators have suggested that rock-forming materials by their action on organic remains may play some part in the formation of petroleum and some support to this view is afforded by the work of Sabatier Senderens and Mailhe on the catalytic decomposition of aliphatic acids and their esters by metallic oxides (compare Ipatieff Abstr. 1904 ii 644 645 ; 1911 i 937) and Grafe (Petroleum 1910 6 71) has pointed out that Lycopodium spores distilled with fuller’s earth afford a distillate similar in character to Scottish shale oil. The authors have therefore examined the distillates obtained from mixtures of oleic or stearic acid with diatomite fuller’s earth quartz sand and finely powdered quartz and find that these materials lower the temperature of decomposition and give rise to distillates richer in hydrocarbons than are obtained when the acids are distilled alone.Powdered quartz is the most efficient of the four followed by fuller’s earth which is better than either diatomite or sand (compare Hviid Petroleum 1910 6 429). The distillates full details of which are given in the original in general resemble those obtained by distillation of fatty acids under pressure (Abstr. 1888 928) but contain more undecomposed acid and less low-boiling hydrocarbons. The conclusion is drawn that in the conversion of organic remains into petroleum the influence of rock- forming materials as well as of time temperature and pressure must be taken into account. T. A.H. Presence of Cholesterol in Java Naphthas. CARL ENGLER and WILRELM STEINKOPF (J. Russ. Phys. Chem. Soc. 19 11,43 1820-1825). -The work of Koss (Abstr. 1911 i 761) which was carried out partly under the supervision of the authors and also its unauthorised publication are severely criticised. T. H. P. Valency of Carbon in So-called Unsaturated Compounds. ALEXEI E. TSCHITSCHIBABIN (J. Russ. Fhys. Chem. Xoc. 1911 43 1690-1735).-A discussion of the various explanations which have VOL. CII. 1. mi. 150 ABSTRACTS OF CHEMICAL PAPERS. been advanced of the unsaturated character of the carbon atom in different classes of organic compounds. T. H. P. PPy-Trimethylpea tane. LATHAM CLARKE and WEBSTER NEWTON JONES (J. Amer. Chem. Xoc. 1912 34 170-174).-1n continuation of a study of the octanes (Abstr.1911 i 354 and earlier abstracts) PPy-trimethylpentane has now been synthesised. By the action of magnesium ethyl bromide on pinacolin PPy-trimethylpentan-y-ol was produced and was converted into y-iodo-PPy-trimethylpentane by the action of iodine and amorphous phosphorus. On treating this carbinyl iodide with alcoholic potassium hydroxide /3/3-dimethyl-y-methylene- pentane was obtained and on passing this over finely divided nickel at 160° in a current of hydrogen PPy-trimethylpentane was produced. PPy-Trimethylpentalrz-y-ol CMe3*CMe(OH)*CH2Me b. p. 149-152'1 760 mm. is a colourless liquid with a camphor-like odour. The octyllene (PP-dirnethyll-y-methylenepentane) C:Me,*C( :CH,)*CH,Me b. p. 110~4-110~8°/760 mm. is a colourless mobile liquid with a faint musty odour.@Py-TrimethyZpentane CIMe,* CHMe* CH,Me b. p. 110~5-110~8°/760 mm. Di 0.7219 n$' 1.4164 is a colourless mobile liquid with a very faint odour. E. G. PG-Dimethylheptane. LATHAM CLARKE and SYDNEY A. BEGGS ( J . Amer. Chem. Xoc. 1912 34 60-62).-1n continuation of the work on the nonanes (following abstract) PG-dimethylheptane has been synthesised. When P-methyl-&pentanone (methyl isobutyl ketone) obtained by the hydrolysis of ethyl isopropylacetoacetate is treated with magnesium n-propyl iodide the nonylene (/3-methyZ-G-methyZeneheptane) CH,Me*CH2-C(:CH2)*CH2*C€€Me? b. p. 132-133' is obtained as a colourless liquid with an odour resembling that of petroleum. The position of the double bond was not established but there is little doubt that the formula assigned to the compound is correct.On passing a mixture of the nonylene and hydrogen over freshly reduced nickel /3G-de'methyt?heptane CH,Me*CH2*CHMe*CH2* CHMe b. p. 132*9-133'/752 mm. Di 0,7206 n z 1.4014 is produced as a colourless liquid witjh a petroleum-like odour. E. G. /kDimethylheptane. LATEIAM CLARKE and SYDNEY A. BEGGS ( J . Amer. Chem. Xoc. 1912 34 54-60).-1n a study of the octanes (Abstr. 1 91 I i 354 and earlier abstracts) certain relations have been discovered between the chemical constitution and physical properties. An investigation has been undertaken in order to ascer- tain whether similar relations occur in the nonane series and an account is now given of the synthesis and properties of fiedimethyl- heptane which has been obtained previously in an impure state by Welt (Abstr.1896 i 332). ,&Methyl-€- hexanone obtained by the hydrolysis of ethyl isobutylacetoacetate was converted into pcdimethyl-E-heptanol by means of magnesium The synthesis was effected in the following manner.i. 151 ORGANIC CHEMISTRY. ethyl bromide. The iodide of this alcohol was prepared and when boiled with alcoholic potassium hydroxide yielded ,!%methyl-r-methylene- heptane which was then reduced to PE-dimethylheptane. Pr- Dinaethyl-r-~LeptunoZ CH2Me*CMe(OH)*CH,*CH2*CHMe2 b. p. 172-1'74° is a colourless liquid with an odour of musty apples The non $en% ( p-me t h y I- E-nae t h y Zenehe pt m e ) CH2Me-C(:CH,)*CH2*CHz*CHMe b. p. 139-140° is n colourless liquid with a sweet petroleum-like odoiir.PE-Dimethylheptane CH~Me.CHRle.CH,*CH,*(=HMe b. p. 135.6-1 35.9"/760 mm. Dii 0.7 190 92 1 *4O20 obtained by passing a mixture of the nonylene and hydrogen over freshly reduced nickel at 160-1 SOo is a colourless liquid with a petroleum-like odour. E. G. Conjugated mi-Nitro-compounds. ARTHUR HANTZSCH and KURT VOIGT (Bey. 1912 45 85-117).-A number of nitro-compounds chiefly aliphatic substances containing NO attached to carbon have been examined spectrometricnlly to determine how the absorption spectrum is affected when the real nitro-group is changed to an mi- nitro-group. The chief result of the investigation has been the discovery of a new type of nitro-compound which is called a conjugated mi-nitro-compound. The nitro-group may be present in a substance in three forms each of which has its characteristic absorption curve.Aliphatic real nitro- compounds show very feeble selective absorption the curves exhibiting a very flat band or a kink beginning at oscillation frequency 3413. It is inmaterial whether the nitro-group is the only negative substituent in the molecule or whether another (NO NOH CO CO,EI CO,Et CO*NH CN Ph) is present provided that the intmduction of the latter does not produce a constitutive change in the nitro-group. A simple aci-nitro-group >C:XO*OH causes weak general absorption; such groups are present only in the salts of the nitropnraffins CHR:NO*OM. When however an aci-nitro- group is present together with another negative group X (one of those mentioned above) then without exception the substance exhibits very strong selective absorption the curve exhibiting a very deep band for thicknesses corresponding with 10 to 100 mm.of N/lO,OOO solution. Since the introduction of a negative group into a real nitro-compound has little optical influence whilst n simple aci-nitro-group alone causes general absorption it follows that the strong selective absorption exhibited by a substance containing both an nci-nitro- and another negative group must be conditioned by the influence of these two groups on one another. This influence i s represented by a peculiarly constituted six-membered ring . pro- duced by the union by a supplementary valency of a metallic or hydrogen atom or of an alkyl group with a negative atom of the __ negative (unsaturated) group X R*CqN0.-X- O;>(Na,H,Me). For examples X is a nitro-group in aci-dinitro-compounds (salts of di- and tri-nitromethane) an R*CO group in a-aci-nitroketones (the nitro- barbituric acids ; ethyl uci-nitrornalonate) and a cyano-group in a-cyano- 2i. 152 ABSTRACTS OF CHEMICAL PAPERS. aci- ni t ro- compounds ( f ulmi n uric esters ; aci-ni t rocyanop he u y lrnet hane). A n aci-nitro-group in this state is called a conjugated mi-nitro-group. I t s presence explains why the introduction of a third negative group into the molecule exerts so slight a n optical influence ; the third group can only have a feeble auxochromic effect. aci-Nitrophenylmethane and its salts contain a conjugated aci-nitro-group ; consequently the benzene nucleus by means of a supplementary valency (in the ortho- or para-position) can form part of the six-membered complex. Certain conjugated aci-nitro-compounds (fulminuric acid and the nitrobarbituric acids) are so stable that they cannot be converted even by concentrated sulphuric acid into real nitro-compounds.Further- more substances containing a simple aci-nitro-group together with another unsaturated group are incapable of existence ; therefore when a real nitro-compound containing another unsaturated group is trans- formed into an aci-nitro-compound a conjugated mi-nitro-group is always produced. The chromoisomerism of certain conjugated aci-nitro-compounds for example the yellow and the colourless salts of the nitrobarbituric acids cannot be explained by regarding the yellow salt as containing a conjugated aci-nitro-group and the colourleas salt as containing a simple mi-nitro-group because the latter group cannot exist in such compounds.Both salts contain the conjugated aci-nitro-group. The colour of the yellow salt is due to a shifting of the absorption band towards the red end of the spectrum. Chromoisomerism in such cases therefore is merely valency isomerism and is represented thus -E*O-M -C*NO:O * and -Q:"--- -C:NO*d When the ionisation of a substance containing a conjugated aci- nitro-group is unaccompanied by secondary changes the ions are optically identical with the undissociated acid and therefore contain the peculiar Pix-membered ring. This result leads to Werner's theory that the formation of ions is in the first step a case of hydrate formation.For the particular examples under discussion the ionisa- tion is represented by the scheme --X.. R * c < ~ ~ . ~ > H + R*c<G.:>H-- -OH 2 -+ I n conclusion attention is drawn to the extensive optical and chemical analogies between negatively substituted nitro-compounds on the one hand and negatively substituted ketones (ethyl acetoacetat,e) on the other. c. s. Aliphatic Nitro-compounds. XII. Constitution of aci- Nitro-compounds. WILHELM STEINKOPF and BORIS J URGENS (J. p r . Chem. 1911 [ii] 84 686-713. Compare Abstr. 1911 i 530).-The formation of hydroxamic chlorides by the action of hydrogen chloride on aliphatic nitro-compounds is referred by the authors to the decom- position of the mi-nitro-compound into the corresponding aldebyde and nitroxyl which then combine t o form a nitroso-alcohol (I); the latter compound reacts with hydrogen chloride yielding a ehloronitroso-ORGANIC CHEMISTRY.i. 153 couipound (Il) which then undergoes transformation into the hydrox- aniic chloride (III) RS shown in the following scheme R*CH:NO*OH -+ R*CHO+ :NOH -+ (I) R*CH(NO)*OH -+ (11) R*CHCl*NO -+ (111) R*CCl:N*OH. This view is supported (1) by the observations of Nef (Abstr. 1895 i 3) and also of Hantzsch and Veit (Abstr. 1899 i 401) who find that mi-nitro-derivatives of hydrocarbons readily decompose into aldehyde nitrous oxide and water; (2) by the formation of hydr- oxamic acids by the direct combination of aldehydes and nitroxyl (Angeli) and (3) by the production of blue o r green colorations due to the formation of chloronitroso-compounds R*CHCl*NO when salts of the nitro-derivatives of aliphatic hydrocarbons are acidified in aqueous or ethereal solution.Attempts have been made to isolate these coloured compounds in the case of nitromethane nitropropane and nitro- ethane but only with the last-mentioned compound were the attempts successful. When a suspension of the sodium salt of aci-nitroethane in a large volume of ether is treated with an excess of hydrogen chloride and the resulting solution after removal of the sodium chloride rapidly evaporated chloronitrosoettiane (Piloty and Steinbock Rbstr. 1902 i 735) was obtained. If a small volume of ether is used and excess of hydrogen chloride avoided the product consists of ethyl- nitrolic acid. The formation of the latter compound is due to the action of nitrous acid produced by the decomposition of the intermediately formed nitroso-alcohol NO*CMeH*OH on unchanged nitroethane.Salts of nitro-compounds such as nitroacetic acid and nitroaceto- nitrile which contain strongly negative groups do not give blue or green colorations when treated with acids and the conclusion is there- fore diawn that in these cases decomposition of the mi-nitro-compound into aldehyde and nitroxyl does not take place. This view is supported by the behaviour of w-nitroacetophenone which on treatment with hydrogen chloride in ethereal solution yields w-chloro-w-oximinoacetophenone !Thiele and Haeckel Abstr. 1903 i 160) without the intermediate formation of a coloured nitroso- compound. aci-Phenylnitromethane which contains the feebly negative phenyl group occupies an intermediate position ; with ethereal hydrogen chloride it develops the blue coloration very slowly instead of instantly as in the case of the nitro-derivatives of aliphatic hydro- carbons and this coloration gradually disappears owing to the formation of benzhydroxamic acid.These differences in the behaviour of nitro-compounds are best explained on the assumption that the mi-nitro-derivative has the constitution CRH-N*O€I proposed by Hantzsch and not the \/ 0 Michael-Nef formula CHR:NO*OH now generally accepted. The stability of the carbazoxy-ring depends on the nature of the sub- stituents. When R=H or alkyl the ring is unstable and readily suffers complete rupture as indicated in the following scheme R-CH-/-N*OH 0 \)< -+ R*CHO + :N*OH.i.154 ABSTRACTS OF CHEMICAL PAPERS. On the other hand when R is a strongly negative group the stability of the ring is greatly increased so t h a t rupture occurs only at one point either between C and 0 with the formation of a nitro- compound as shown in (I) below or between N and 0 with the formation of a hydroxamic acid as indicated in (11) t- R*CH-NOOH \)< -3 R*CH2-N<<E or R*CH,*N< 0 I 0 (I.) o The evidence furnished by Nef in favour of the formula R*CH:NO*OH for mi-nitro-compounds is subjected to a critical examination and the conclusion is drawn that Hantzsch's formula affords a simpler and less forced explanation of the behaviour of these compounds. Numerous examples of the reactions of nitro-corn pounds and of a large number of other classes of compounds containing the carbazoxy-ring are cited in support of the authors' view.Speciflc Gravity Table of Alcohol-Water Mixtures at 17.5". WILHELM FRESENIUS and LEO GRUNHUT (Zeitsch. unal. Chem. 1912 51 123-124).-A useful table giving DiP5 for a number of mixtures of alcohol and water together with the corresponding alcohol % by weight and by volume and also alcohol in grams per Action of Potassium Hydroxide on Secondary Alcohols ; Diagnosis of Primary and Secondary Alcohols of High Molecular Weight. MARCEL GUERBET (Compt. rend. 1912 154 222-225. Compare this vol. i 67).-W hen secondary alcohols are heated at 230' with potassium hydroxide some oxidation occurs with production of potassium salts of acids but the greater part of the alcohol forms condensation products ; thus isopropyl alcohol yields formic and acetic acid together with P-methylpentan-8-01 and /3G-dimethylheptan-(-ol.The corresponding higher homologues are obtained from sec.-butyl alcohol and octyl alcohol. The ease with which the reaction is carried out renders it suitable for distinguishing w. 0. w. Specific Gravity and Hygroscopic Power of Glycerol. ANTON KAILAN (Zeitsclh. anal. Cliem. 1912 51 81-lOl).- Anhydrous glycerol has DY 1.26413. The density between 14' and 2OOLcan be calculated by the expression D:= 1.26413 + (15 - b) 0.000632 and a table is given of densities from 14.3' to 20.6'. Boiling points under various pressures bebween 9 and 32 mm. are also recorded. Glycerol rapidly absorbs moisture from the air and a number of determinations of the hygroscopic power of anhydrous and hydrated samples are given.It appears that a mixture containing 80% of glycerol is in equilibrium with air containing an average amount of moisture. The author also noticed that alcohol containing but little water absorbs in the same circumstances water four times more rapidly F. B. 100 C.C. L. DE K. between secondary and primary alcohols. than does a similar glycerol. L. DE K.ORGANIC CHEMISTRY. i. 155 Preparation of Epichlorohydrin from Dichlorohydrin and Alkalis. FARBENFABRIKEN VORM. FRIEDR. BAYER & Go. (D.R.-P. 239077).-'rVhen dichlorohydrin (129 parts) in 200 parts of water is slowly treated with 133 parts of 30% sodium hydroxide solution it yields 85 parts of epichlorohydrin; the sodium hydroxide may be replaced by its equivalent of potassium or ammonium hydroxide but the above concentrations must be carefully maintained.Tautomerism of the Dialkyl Phosphites. THADDEUS MILOBENDZKI (Bey. 1912 45 298-303).-Previous investigations (Abstr. 1807 i 391 ; 1908 ii 488; 1903 i 733; 1907 i 8 1899 i 659) bave indicated that dialkyl hydrogen phosphite in the free condition has the constitution (I) O:PH(OR),. From the behnviour of the esters in aqueous solution the author shows that they also exist in the tautomeric form (11) OH*P(OR),. Silver salts of the composition Ag*PO(OR) are precipitated from aqueous solutions of diisopropyl hydrogen phosphite (b. p. 74-75O/ 9 mrn.) and diethyl hydrogen phosphite (b. p. 66-67'/9 mm.) by the successive addition of silver nitrate and aqueous alkalis (ammonia sodium hydroxide and barium hydroxide); the addition of the reagents in the reverse order produces no precipitate.According to the author the silver salts OAg*P(OR) are readily soluble in water and the non-formation of a precipitate when the alkali is added before the silver nitrate is due to the transformation of the keto-ester (I) into the enolic form (11). The silver salts Ag*PO(OR) dissolve in excess of alkali owing to change into the tautomeric form induced by the hydroxyl ions; on acidifying the alkaline solutions the original salt is precipitated. Dialkyl hydrogen phosphites show the phenomenon of gradual neutralisation. The percentage of the ester (I) present in aquoous solutions has been determined by adding the equivalent amount of aqueous ammonia followed immediately by the addition of silver nitrate ; the amount of silver salt Ag*PO(OR) precipitated cor- responds with that of the ester of the formula (I) originally present ; with diethyl hydrogen phosphate the amount is 35%.That the enolic modifications of the esters are capable of existing in aqueous solution has also been shown by neutralising with aqueous barium hydroxide and then adding the equivalent amount of sulphuric acid; the solutions thus obtained do not show the phenomenon of gradrial neutralisation nor yield insoluble silver salts. Triethy 1 phosphite is hydrolysed by excess of aqueous sodium hydroxide to sodium diethyl hydrogen phosphite ; dialkyl hydrogen phosphites are not hydrolysed by alkalis.Experiments are also described showing that sodium diethyl phosphite prepared from sodium and diethyl hydrogen phosphite in ethereal solution exists in aqueous solution in the form NaO*P(OEt),. F. M. G. M. F. B. Constitution of Glycerophosphoric Acid Prepared by Eeteriflcation of Phosphoric Acid or Sodium Dihydrogen Phosphate. PAUL CARRE (Compt. rend. 1912 154 220-222,* Compare Abstr. 1904 i 133 215).-Sodium glycerophosphate * and Bdl. SOC. chirn. 1912 11 169-172.i. 156 ABSTHAC’l’S OF CHEMICAL PAPERS. prepared by Poulenc’s method was converted into glycerophosphoric acid by the process previously described. The product is identical in every respect with the acid formed in the direct esteritication of phosphoric acid by glycerol.The same acid is obtained when glycerol bromohydrin (3 mols.) is heated with silver phosphate and the resulting unstable ester OP[O*CH,*CH(OH)*CH,*OH] submitted t o hydrolysis. Poulenc’s compound must therefore be a salt of a-glycerophosphoric acid and not of the P-acid as stated by Paolini (Abstr. 1911 ii 774). The author has been unable to obtain Paolini’s Preparation of Glycol and Gly colhydrin Esters of Phosphoric Acid Glycerides ADOLF GHUN and FRITZ KADE (D.K.-P. 240075). -Cornpounds of general formula X*C,H,*O*PO(OH)*O*C,H,(O.CO. k)2 where R is an alkyl group and X halogen or hydroxyl can be rcadily prepared by the action of phosphoric oxide on distearin and etliylcne- glycol or halogenhydrins. brucine salt crystallising with 7H20. w. 0. w. The following products are described the compound C2H,C1*O*PO(OH)*0*C,H,(O-CO*C1,H35)2 w.p. 65-66’ ; the compound OH* C2H,*O* PO( OH)*O* C,H,( 0 *CO* C17H,,) 2 from ap-distearinphosphoric acid ester ethylenechlorohyclrin and glycol. The trirnetltyllamine salt C2H,C1*O*PO(O*NHlMes;.0.C,H,(O*CO*C17H35)~ m. p. 69”; and by the interaction of another molecule of trimethyl- amine the salt N Me,C1 C,H,*O*PO( O*N H Me3)*O*C,H,(0 *Corn C17Hs&. The Agglutination of Lecithins and Lecithin-protein Mixtures by Acids. J. FEINSCHMIDT (Biochem. Zeitsch. 1 9 12 38 244-251).-Aqueous susi ensions of lecithins of various origins have agglutination optima a t definite hydrogen ion concentrations which are identical with the isoelectric point. This varies in the different preparations between lo- and lo-* that is in somewhat strongly acid solutions.Neutral salts increase the turbidity of the solutions but make the actual agglutination point less sharp When lecithin and protein are mixed a new complex is formed in which the agglutination point shifts towards the less acid side; in this case the precipitation PAUL SABATIER and ALPHONSE MAILHE (Cornpt. rend. 1912 154 49-52. Compare Abstr. 191 1 i 258-416).-The catalytic decomposition of alkyl formates below 400’ is somewhat complicated and follows a different course from that of esters of higher acids. I n general two principal reactions occur represented by the equations (1) 2H*CO,R = H0CH.O + CO + R,O followed by the dehydration of the aldehyde with production of an unsaturated hydrocarbon ; (2) H*CO,R = CO + R*OH followed by dehydration or dehydrogenation of the alcohol.The water set free may effect hydrolysis the resulting formic acid then decomposing in the manner already described. F. M. G. M. is more energetic and coarser. s. B. s. Catalytic Decomposition of Formic Esters.ORGANIC CHEMIS'I'liY. i. 157 'i'ho nature of the catalyst considerably influences the course of reaction; thus in the case of methyl formate and titariiurn oxide reaction (1) predominates whilst with zinc oxide reaction (2) occurs almost exclusively. Both reactions take place with thorium dioxide. Finely divided platinum nickel and copper readily effect catalysis principally in accordance with equation (2). w. 0. w. C a t a l y t i c Formation of Saturated Aliphatic Esters from Formic EYters.PAUL SABATIER and ALPHONSE MAILHE (Compt. rend. 1912 154 175-177. Compare preceding abstract).-When ttm vapour of methyl formate and isobutyric acid in equimolecular proportions is pasmd over tit'anium oxide at 250' carbon monoxide is liberated and the condensed liquid contains 20% of methyl isobutyrate together with methyl alcohol and some isobutaldehyde. The esterification is explained by the decomposition of the methyl formate in the manner previously described whilst the aldehyde arises from reduction of the acid by formic acid. Thorium oxide acts in the same may but requires a higher temperature ; thus at 300-330° isovaleric acid and methyl formate give 40% of methyl isovalerate by volume and 16% of iso- valeraldehy de. Under these conditions the amount of ketone formed is inconsiderable but at 370° the condensed liquid contains 50% of ester 10% of isovalerone 15% of isovaleraldehyde and also methyl alcohol.Similar results have been obtained with higher acids and other alkyl formates. The direct reduction of acids by means of formic acid will be described in a further communication. w. 0. w. Optically Active Dialkylacetic Acids. EMIL FISCHER JULZUS HOLZAPFEL and HANS VON GWINNER (Bey. 1912 45 247-257. Compare Fischer and Platau Abstr. 1909 i ,62t)).-~-isoButylhexoic acid has been resolved into optically active components by crystal- lisation of the brucine salt. The difference between the butyl and isobuty 1 radicles is apparently enough t o cause pronounced optical asymmetry. a-isoButylvaleric acid has also been resolved but definite results were not obtained with a-isopropylvaleric acid.Ethyl butylisobutylmalonate prepared by the interaction of n-butyl bromide on ethyl isobutylmaloriate and sodium has b. p. 137-140'1 10 mm. When hydrolysed by means of todium hydroxide butgl isobutylnzulonic acid is obtained in colourless crystals m. p. 136-138'. The neutral solution of the ammonium salt gives a colourless precipitate with silver nitrate and crystalline precipitates of the corresponding salts with barium and calcium chlorides. On heating a t 1 60° butylisobutylucetic [a-isobutylhexoic] acid is obtaiced as a colour- less oil b. p. 145-145.5' (corr.)/lO mu. The brucine salt forms small microscopic prisms. The first separations were hydrolysed by heating with sulphuric acid.The optically active d-a-isobutyl- hexoic acid had [a] +5*73'. Ethyl propylisobwtylmulonate was obtained as a n oil b. p. 126'1 9.5 mm.i. 158 ABSTRACTS OF CHEMICAL PAPERS. Propylisobutylmalonic acid crystallises in stunted prisms or plates m. p. 147-149" (corr. decomp.). Propylisobutylacetic [a-isobutylvccleric] acid is a colourless oil D20 0.8928 b. p. 122' (corr.)/8*5 mm. ; it forms a colourless silver salt crystallising from ammonia in microscopic slender needles. The calcium salt also consists of microscopic slender needles. The bmcine salt forms microscopic small prisms and yields d-a-isobutylvaleric acid as a colourless oil m. p. 100°/0.5 mm. D22 0.8576 CUE] + gaso. The monoamide of propylisopropylmalonic acid CO,H*CPraPrp* CO*NH obtained by heating cganoisopropylvaleric acid with concentrated sulphuric acid crystallises in colourless bunches of intergrown prisms m.p. 137' (corr. decomp.). When heated over the flame in a distillation flask a-iso~rop~lvaZ~~ccm~de is obtained a t about 250'. It crystallises in slender colourless needles m. p. 131-1 33' (corr.). By the action of sulphuric acid and sodium nitrite at SO" propyl- isopropylacetic [a-isopropylvaleric] acid is obtained b. p. 11 6" (wrr.)/ 12 mm. 112-113°/9 mm. D17 0,9076. A partial resolution was obtained by means of the quinidine salt the acid formed having [a]? + 0.7'7'. E. F. A. Coniposition of Linseed Oil and the Distribution of Oxygen in Dried Layere of the Oil. 11. E. I. ORLOFF (J. Buss. Phys. Chem. SOC. 1911 43 1509-1524. Compare Abstr. 1910 i SlO).- The author criticises Fokin's work (Abstr.1907 i 820) the results of his own experiments being in agreement with Genthe's theory (Zeitsch. angew. Chem. 1906 19 2087) except that he finds that when a layer of the oil 100-108 sq. em. in area weighs 0.1-0*15 gram 15-16% of oxygen is taken up although setting occurs when oniy 12% has been absorbed. Experiments in which a cobalt dryer was employed give for the rates at which oxygen is fixed results corresponding with the formula B + x where A re- dx/dt=k(A - z ) ( B + x ) or k = ____ presents the total amount of oxygen absorbed expressed as reduction of pressure x the atmospheric pressure and B a constant. After the oil has combined with 12% of its weight of oxygen a solid phase is formed and the further velocity of the absorbing process is expressed by dx/dt = k ( A -fx)(S +fx) where 3' the correction coefficient is less than unity and corresponds with the product of combination of the solid phase k f being a constant magnitude.In parallel with this chemical process proceeds a physical one of diffusion of the oxygen into the oil the amounts of oxygen in successive layers starting from the surface being in the proportions of n n2 n3 n' . . . np where n is less than 1 (0.5 0.6 etc.). The quantity of oxygen combined is related to the factor n according to the expression S/Q=n/(l -n) where Q is the quantity of combined oxygen corresponding with the iodine number and S is the amount of oxygen fouud i n each separate case. Assuming complete distribution A 1 t ( A +B)' 'adz* 7)ORGANIC CHEMISTRY.i. 159 of the oxygen by diffusion the value of n must be taken as two-thirds. T. H. P. Molecular Rearrangements in the Camphor Series. IX. Lauronolic Acid and Campholactone. WILLrAnr A. NOYRS and CHARLES E. BURKE (J. Amer. Chem. Soc. 1912 34 174-1S3).- Tiemarin (Abstr. 1901 i 6) found that lauronolic acid prepared from bromocamphoric anhydride has a rotatory power which differs con- siderably from t,hat of the acid obtained by the distillation of camphanic acid and suggested that the acid produced by the latter method con- sisted of a mixture of optical isomerides. This has now been proved to be the case. Lauronolic acid prepared from active bromocamphoric anhydride by Aschan's method (Abstr. 1895 i 154) has been obtained in the form of rosettes of long needles; it has m.p. 6*5-S0 b. p. 230-235' under the ordinary pressure vapour pressure 99-100 mm. at 184" D',"5 1.0109 Dt5 1.0133 D;') 1.0249 [a] + 1 8 7 - 7 O 12 1.47556 and the dissociation constnnt I. 1.36 x The calcium salt crystallises with 3II,O instead of only 2H,O as stated by Bredt (Abstr. 1911 i 417) and when heated with soda-lime yields laurolene. When hydrogen iodide is passed into a solution of lauronolic acid in light petroleum the hgdriodide is obtained in the form of yellow plates and is very unstable. On reducing this compound with zinc dust and alcohol dihydrolauronolic acid C,H,,*CO,H is produced which has DY'5 0.9008 [a]$'5 +1.74' vapour pressure 100 mm. at 178" and 749 mm. a t 215' and [n] 1.45786; the amide has m.p. By decomposing inactive bromocamphoric anhydride prepared from synthetical camphor inactive lauronolic and camphanic acids were obtained. Inactive lauronolic acid has m. p. 5-S.5" vapour pressure 100 rurn. a t 192" DY 1.0318 and [nID 1.47655; its calcium s a l t crystallises with 1 H,O. Campholactone preparcd in various ways from lauronolic acids of widely different rotatory powers has m. p. 50" and [a] - 21.7" and when warmed with barium hydroxide solution is converted into tho corresponding hydroxy-acid m. p. 143" and [a] + 16.0". 50-51". E. G. Molecular Rearrangements in the Camphor Series. VIII. Ganiphonolic Acid and Camphonololactone. WILLIAM A. NOYES E. E. GORSLINE and R. S. POTTER (J. Amer. Chem. Xoc. 1912 34 62-67).-Four hydroxy-acids and three lactones have been described which retain the tertiary carboxyl group of camphoric acid.The structural formulz assigned to these compounds have not been well established and the present work was therefore undertaken with the object of obtaining further evidence as t o their constitution. Camphononic acid prepared by a modification of Lapworth and Lenton's method (Trans. 1901 79 1287) has I ~ I . p. 289-2330" [a]:'' in benzene (2.4 grams in 100 c.c.) + 17-8°,L[a]2 in alcohol ( 3 grams in 100 c.c.) - 3.9". On reducing this acid with sodium and ainyli. 160 ABS'l'HACTY OF CHEMICAL PAPERY. alcohol cmyl camyhonolccte is obtained as a yellow viwons oil of b. p. 222-223O/40 mm. ; the calcium copper and silver salts were prepared. It is shown that the lactone obtained by Noyes and Taveau (Abstr.1906 i 397) by decomposing the nitroso-derivative CH2*CMe*Co of aminolauronic anhydride with sodium hydroxide is I $Me 1 identical with cis-camphonololactone (annexed formula) prepared by Bredt (Abstr. 1909 i 498) by the cHz*CH-o electrolytic reduction of camphononic acid. cis- cHz'CMe*Co,H I - 22*3O. The coriesponding hydroxy-acid cis- camphonolic acid (annexed formula) has m. p. UR,.&W(OH) 202-203' when rapidly heated [a] in alcohol (10 grams in 100 c.c.) +29*2O and on oxidation with chromic acid is converted into camphononic acid. Camphonololsctone has m. p. 165-167' a] in alcohol (5 grams in 100 c.c.) - 20.2' and [a (10 grams in 100 c.c.) E. G. The Melting Point of Oxalic Acid. EYVIND EODTKER (Chem. Zeil. 1912 36 105).-Purc crystallised oxalic acid does not appear to have a definite melting poiut ; a small crystal placed in a capillary tube had m.p. 99*5-101-5° whilst a layer in the capillary tube 1 mrn. in height had m. p. 100-102.5° when the temperature was raised very slowly and maintained a t 100' for about one minute. w. P. s. Conversion of Maleic into Funiaric Acid. SEBASTIAN M. TANATAR (J. Buss. Yhys. Chem. Soc. 1 If 11 43 1742-1 746).-It was discovered by Skraup (Abstr. 1891 1338) that the interaction of hydrogen sulphide and sulphur dioxide in aqueous solution in presence of maleic acid is accompanied by transformation of the latter acid into fumaric acid ; this ef€ect he termed Since the reaction liquid after filtration from the sulphur formed contains nothing capable of bringing about this transformation the author has investigated the action of sulphur on maleic acid.Milk of sulphur is without effect and the same is apparently the case with the sulphur separated by the action of hydrogen sulphide on ferric chloride in presence of maleic acid. With sodium thiosulphate and a mineral acid however which normally give precipitation of sulphur maleic acid prevents such precipitation and is simultaneously con- verted into fumaric acid ; a similar transforrustion is produced also without separation of sulphur by addition of the thiosulphate to a solution of maleic acid alone That these solutions contain no dissolved sulphur is shown by extraction with carbon disulphide and the con- clusion is drawn that it is the reaction of the thiosulphuric and maleic acids with formation of an unknown product that induces the isomeric change.This same change is brought about by treatment of maleic acid with ammonia or potassium polysulphide (liver of sulphur) although in the latter case i t may be due to the presence of thiosulphate. resonance." T. H. P.ORGAN1 C C €1 EM I WRY. i. 161 Relation between the Configuration and Rotation of t h e Lactones in t h e S u g a r and Saccharinic Acid Groups. EENEST ANDERSON (J. Amn2er. CImnz. SOC. 1912 34 51-54).-Hudson (Abstr. 1310 i 220) has pointed out that dextrorotatory sugw lactones have the ring on one side of the st'ructure whilst Izvorotatory lactones have it on the other. It is now shown that this relation is true not only for the lactones to which Hudson referred but for nearly all monobasic and some dibasic acid lactones in the sugitr and saccharinic acid groups.The configurations and specific rotations of eighteen such lactones are tabulated. The relation affords a new method for determining the I configuration of the lactones formed by certain dibasic acids. E. G. E thy1 Orthotrithioforrnate. BROE HOLMBERG (Bey. 19 12 45 364-365).--In reply to Houben and Schultze (this vol. i 5) it is claimed that the product obtained by the ant,hor (Abstr. 1907 i 474) was pure. D. F. T. Action of Potassium Hydroxide on Tetrolacetal. PAUL L. VIGUIER (Compt. Tend. 1912 154 2 17-220. Co-mpare Abstr. 1909 i 691 ; this vol. i 7).-When tetrolacetal (diethoxybutinene) is dropped on potassium hydroxide a t 1SO-200° a liquid distils and on fractionation yields a compound C,H,O b.p. 29-33"/16 mm. D19.5 0.826 mL9.B 1.462. CHiC*CH:CH*OEt since it forms an explosive silver derivative C,H70Ag and is hydrolysed by acids forming an unstable substance having the properties of the uldehyde CHiC*CH,.CHO. The latter changes spontaneously into tiiacetyl benzene acetoace taldehyde probably being produced first. Hydroxylamine yields 1-methylisooxazole. On treat- i n g the aldehyde with sernicarbazide hydrochloride a semicarbctxone C,H,ON,Cl is obtained ; this yields the corresponding aldehyde This probably has the constitution C,H,OCl on hydrolysis. w. 0. w. Tartardialdehyde. ALFRED WOHL and BRUNO MYLO (Bey. 1912 45 322-349).-From the result of their endeavours the authors conclude that the synthesis of tartnrdialdehyde by the symmetrical linking together of two molecules each containing two carbon atoms presents excessive difficulties and they have finally attained success by other means.The action on acetyl chloride of copper hydride gives ethyl acetate and ethylidene diacetate whilst the action of copper on the additive product of dibromoacetaldehyde and acetyl bromide yields bromovinyl acetate. Dibromoacetaldehyde also reacts slowly with magnesium methoxide the product *being a /3/3S(or SSp-)-trib~omo-y- keto-n-but32 alcohol b. p. 77-79°/14--16 mm. Glyoxal sodium bisulphite in acetic anhydride solution reacts with hydrogen chloride producing unstable s-tlichloroglycol diacetate b. p. 110-115°/14 mm. (compare Prud'homme Zeit. Chenz. 1870 380).i.162 ABSTRACTS OP CHEMICAL PAPERS. Ethyl diethoxyacetnte in ethereal solution with potassium gives as chief product a n un d istilla ble syrupy substance P-ii ydrox y -y-ket o- succimdialdehyde dietluJaceta1 CH(OEt),*CO*CH(Ol3)*CH(OEt) ; the substance was not obtainable in a pure state and the action of sodium gave still less satisfactory results. The action of sodium on the piperidide of diethoxyacetic acid (Wohl and Lange A bstr. 19OS i 943) yields monoethoxyacetopiperidide b. p. 72-74°/0-0S-0.1 1 mm. Diethoxyacetoh ydrazide obtained from the e thy1 ester mi t h h y tl razine in alcoholic solution forms capillary crystals m. p. 43-45' and has b. p. 110'/0.05 mm. ; it reacts with mercuric oxide or metaboric acid eliminating nitrogen and forming bis-diethoxyacetohydrcczide CH(OEt),*CO*NH*NH*CO*CH(OEt) which crystallises in needles m.p. 67-70'; the mercury copper and lead compounds are described. Iodine removes mercury from the mercnry compound with the formation of azo-a-ketodi-P-ethoxyetlmne CH(OEt),*CO*N :N*CO*CH(OEt) a viscous colourless oil b. p. 131-134'/0*07-0~08 mm. which on warming decomposes giving ethyl orthoformate instead of the desired tetraethoxydiacetyl CH(OEt),*CO-CO*CH( OEt),. Success was attained by starting with di-magnesium acetylene dibromide (from acetylene and magnesium ethyl bromide) which on treatment with ethyl orthoformate gives acetylenedialdehyde diethyl- acetal CH(OEt),.CiC*CH(OEt) D1H.5 0-956 (compare Jotsitch Chem. Zeit. 1907 31 979) ; by reduction with hydrogen in the presence of colloidal palladium this passes into mnleinuldekyde diethylucetul b.p. 112-112*5°/1 1 mm. DZ3 0.926 which is oxidisable by potassium permanganate (compare Wohl Abstr. 1898 i 556) into tartur- &aldehyde diethylacetal a viscous oil b. p. 157-160'/11 mm. Tho hydrolysis of this acetal is most satisfactorily accomplished by N/lO- sulphuric acid in the cold when a sweet solution of tartardiuldehpda is obtained ; this solution on slow evaporation deposits microscopic rieedles which having a bitter taste and being sparingly soluble in water probably represent a polymeric form ; they re-dissolve slowly in warm water giving a sweet solution which from i t s cryoscopic behaviour contains the substance in a unimoleculm condition ; this solution on evaporation gives a sweet amorphous residue.The diphenylhydraxone of tartardialdehyde forms yellow crystals m. p. 197.5" (corr. decomp.); no osazone was obtainable; the cli-semicurbaxone has m. p. 227.5' (corr. decomp.) ; the dioxime 153.5" (corr. decomp.). Oxidation of the tartardialdehyde by bromine water gives meso- tartaric acid ; for this reason the above ethylenic aldehyde is supposed to be t h a t corresponding with maleic acid. Dihydroxyacetone as an Intermediate Product of Alcoholic Fermentation. ARTHUR SLATOR (Bey. 1912 45 43-46).-1t is sometimes assumed t h a t dihydroxyacetone is an intermediate product of the alcoholic fermentation of dextrose (compare Buchner and Meisenheimer Abstr. 1910 ii 73'7). If this is the cilse dihydroxy- acetoue must be fermented by the yeast at least as quickly as D.F. 7'.ORGANIC CHEMISTRY. i. 163 dextrose. Experiments are quoted to show that during twenty minutes no dibydroxyacetone is fermented although a n equal weight of dextrose is entirely fermented by the same yeast during this time. The conclusion is drawn that dihydroxyacetone is not directly fermented and that it is therefore not an intermediate product of alcoholic fermentation. E. F. A. The Physico-chemical Bases of the Seliwanoff Lzevulose Reaction. HARRY XOENIGSFELD (Biochenz. Zeitsch. 19 12 38 310-320).-1t is shown that the Seliwanoff reaction for 13evulose is also yielded by dextrose when the latter is present in a concentration higher than 2”/ and also when the hydrochloric acid exceeds 12-12.5% i n strength. As the reaction appears to be due t o hydroxy- methylfurf uraldehycle formed from the laevulose and as under certain conditions lawulose can be formed from dextrose the author draws the conclusion that the latter sugar only gives a positive result in the Seliwanoff reaction when the conditions are such that it can b‘e con- verted in appreciable quantity into the former sugar.This hypotliesis is supported by the investigation of the action of acids and bases on dextrose which it is shown probably changes under certain conditions into fructose. Chemistry of the W o o d Dextrins. C. A. YLLNER (Zeitsch. nngew. Chern. 1912 25 103-107).-The dextrins obtained by Honig m d Schubert (Abstr. 1887 125) are mixtures of homologues from which the individual substances can be obtained only after repeated precipitation.The reducing power increases with the rotation of the dextrin; 1 gram of a dextrin with the rotation +25” corresponds with approximately 0.1 gram of cuprous oxide a rotation of +50° corresponding with about 0.2 gram of cuprous oxide. The velocity and extent of hydrolytic decomposition with acids w:is do termined. T. 8. P. Photolytic Decomposition of Smokelees Powders by Ultra- violet Light. Influence of Stabilisers. Damaged Powders. DANIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 191 2 154 201-203. Compare t h i s vol. ii 2 LO),-Exposure of nitroglycerol to the light from a quartz-mercury lamp results in decomposition with production of the following gases CO (24 vols.) CO (19.5 vols.) N (39 vols.) N,O (7 vols.) XO (9 vols.) with a considerable amount of nitrogen peroxide which however is not evolved from the gelatinised material treated with stabilisers.At a distance of 20 mm. from the lamp powders stabiliJed with amyl alcohol withstood decomposition better tshan those containing diphenylamine whereas at 50 mm. diphenylamine was the more effective stabiliser. Damaged Erench naval powders showed themselves less resistant to the rays S. B. S. than sound powders of the same compobition. w. 0. w. General Method for the Preparation of Aliphatic Amines by Catalytic Reduction of Alkyl Nitrites. GEOHGES GAUDION ( A mn. Chim. Phys. 191 2 [viii] 25 125-1 36).-The author has applied Sabatier and Senderens’ method (Abstr. 1905 i 333) of catalytici. 164 ABSTRACTS OF CHEMICAL PAPERS. reduction by means of finely divided nickel or copper in presence of hydrogen to a series of alkyl nitrites and finds that these are reduced giving t h e corresponding secondary amine with small amounts of the primary amine and very small quantities of the tertiary amine.Nickel generally acted at a lower temperature than copper ; thus in the case of isoamyl nitrite the former gave good results a t 220-230' and the latter at 350'. Several possible explanations of the reaction are discussed and it is considered that i t is best explained by assuming that the alkyl nitrites are first isomerised into the corresponding nitro-paraffins which are then reduced in the ordinary way. This explanation is the more probable in view of the fact that the reaction seems to take place in the same way as the catalytic reduction of the nitro-paraffins investigated by Sabatier and Senderens (Abstr.1902 i 701). T. A. H. Ammonium a n d Sulphonium Perchlorates. Relations between Solubility and Constitution KARL A. HOFMANN KURT HOBOLD and FRITZ Quoos (Annalen 1912 386 304-317. Compare Abstr. 1910 i 818; 1911 i 608).-Ammonium and sulphinium perchlorates are eminently suitable substances for the study of the relationship betwoen solubility and constitution because they do not form hydrates are nearly allied crystallographically and whilst not being hydrolysed in aqueous solution are electrolytically dissociated to the same order of magnitude ; several factors therefore which might possibly mask the relationship are eliminated from the field. The following perchlorates are described (the numbers in brackets denote the grams of water in the saturated solution at 15' containing one gram-molecule of the salt) NH,*CIO (635) ; NHMe,*ClO (800) ; NMe,*ClO (32,640) ; NMe,Et*ClO (1710) ; NMe,Pr.C1O4 doubly refracting rhombic plates or prisms m.p. 118' (1310) ; N31e3(C3H5)*C104 thin rectangular plates m. p. 90' (100) ; ClO,*NMe,*C,H almost rectangular plates m. p. 186' (5810) ; C10,*NMe3*C,H,I doubly refracting rhombic plates or prisms (10,300) ; NMe,Ph*C104 rhombic crystals m. p. 1 7 5 O (decornp.) (1315) ; CH2Z*NMe3*C104 rhombic or monoclinic plates m. p. 184' (decomp.) (9535) ; C10,*NMe3*CH2*CH(OH)=CH2*OH thin doubly refracting rhombic plates sinters at 86O (150) ; NEt,-ClO (6130) ; NMeEt3*C110 rhombic plates (915) ; NEt3Pr*C10 quadratic prisms m.p. 275" (3090) ; NMe,Et,*C10 (150) ; C2H,(NH,*C104) rhombic plates (200) ; U,H,(NMe,*ClO,) stout rhombic plates (28,700) ; C3H,(NMe3*C10,) doubly refracting leaflets (23,500) ; SMe,-ClO stout rhombic prisms or elongated plates m. p. above 267O (1280) ; SMe2Et*C10 elongated rhombic plates (840) ; SMe,Pr-ClO (1700) ; ClO,*SMe,*C,H (1650) ; C,H,(SMe,*ClO,) rhombic prisms m. p. 250' (2360) ; ClO,*SBIe,*CH CH elongated plates (1 368) ; C3H,(SMe,*C10,) (2480). The most striking result is the sparing solubility of the quaternary ammonium perchlorates in comparison with the great solubility of metbylmnmonium perchlorate ( 1 20) dimethylammonium perchlorate (70) diethylammonium perchlorate (1 15) and ethylnmmonium per- chlorate (70). Another striking fact is the enormous difference in theORGANIC CHEMISTRY.i. 165 solubilities of quaternary ammonium perchlorates containing like alkyl groups from those containing unlike alkyl groups ; for example NMe4-C104 (32,640) NMe,Et*ClO (1710). These two groups of per- chlorates also differ in their stability towards alkaline potassium permanganate those of the type NR,*C10 being stable whilst members of the other group are rapidly oxidised at the ordinary temperature. The molecular dilutions of glyceryltrimethylammonium perchlorate (150) and of choline perchlorate (70) show how enormously the solubility is increased by the introduction of hydroxyl groups ; when the hydroxyl groups are esterified however the solubility is very largely diminished as shown in the case of nitratocholine perchlorate (40,000). Deductions similar to the preceding can be drawn in the case of the sulphinium perchlorates.c. s. Decompoaition of Quaternary Ammonium Hydroxides. 11. JULIUS VON BRAUN (Annalen 19 12 386 273-303. Compare Abstr. 1911 i 610).-The decomposition by heat 01 diammonium hydroxides of the type OH*NMe,*[CH,],*NMe,*OH may result in the formation of di-olefines unsaturated tertiary amines or ditertiary diamines. Substances in which x is 3 5 7 and 10 have been examined. All four yield by decomposition unsaturated tertiary amines CH,:CH*[CH,],-,*NMe the amount of which increases as x increases ; thus hexamethyldecylenediammonium iodide I*NMe,*[CH,],,*NMe,I white leaflets m. p. 231° obtained from arc-di-iododecane (Abstr. 1910 i 25) and alcoholic trimethylamine at loo' is converted by the usual treatment into a syrupy mass of hexumethyldecylenediamrnolzium hydroxide by the distillation of which very little di-olefine (unex- amined) is formed the chief product being a mixture of 30% of dimethyldecenylamine CH,:CH*[CH,],*NMe b.p. 118-1 20°/17 mm. (platinichloride ; picrate m. p. 137" ; methiodide m. p. 137-140') and 50% of aK-tetrumethyldiaminodecune C,,H,,N b. p. 157-15So/ 17 mm. (platinichloride m. p. lS9" [decomp.]; pacrate rn. p. 139-140'). The distillation of trimethyldecenylammonium hydroxide gives a 75% yield of dimethyldecenylamine ; hence the latter can be obtained from hexa- methyldecylenediammonium hydroxide with comparative ease and in good yield. Bexameth y Zheptylenediammonium bromide Br*NMe,*[ CH&*NMe,*Br m.p. 245O prepared from ar)-dibromoheptane and alcoholic trimethyl- arnine a t looo forms a diammonium hydroxide the distillation of which yields about 15% of a heptadiene 28-29% of di~methylheptenyl- amine CH,:CH*[CH,],-NMe b. p. 166-1 69" or 60-65'/10 mm. (picrute m. p. 88' ; methiodide m. p. 120°) and 51% of ay-tetrarnethyl- diccminoheptane NMe,*[CH,],*NMe b. p. 225-230' (decomp.) or 101-102°/10 mm. (picrate m. p. 136"; dimethiodide m. p. 242'). Unlike the two preceding diammonium hydroxides hexnmethyl- amylenediammonium hydroxide prepared from the iodide (loc. cit.) begins to decompose during the evaporation of its aqueous solution. Its complete decomposition yields mainly trimethylamine water and piperylene very little tetramethyldiaminopentane b.p. 193-1 94' VOL. CII. i. ni 166 ABSTRACTS OF CHEMICAL PAPERS. (platinichlode m. p. 218' [decomp.]; picrate m. p. 149") and dimethyIpenterLylallnine (isolated as the naethioditle m. p. 200O) being produced. Similar results are obtained by the decomposition of hexa- methylbutylenediammonium hydroxide and hexamethylpropylene- diammonium hydroxide ; in the latter case the non-nitrogenous pro- duct is not allene but a mixture of viscous oxidation products from which an unsaturated substance C,HIoO (semicnrbaxone m. p. 192O) probably an isomeride CH3*CO*CH,*CMe:CH of meeityl oxide has been isolated. The experiments indicate that in the decomposition of diammonium hydroxides whilst the lower members of the series decompose simultaneously at both ends of the chain the higher members experience changes first a t one end of the chain only.For example OH*NMe,*[CH2],o*NMc~3*OH -+ Me*OH + OH*N11Ze,*[CH2],,-NMe2 and H,O + NMe + OH*NMe;[CH,],*CH:CH ; then OH*NMe,*[CH,],,*NMe -+ MeOH+NMe,*[CH,],,*NMe and H,O+NMe,+ CH,:CH*[CH,],*NMe whilst OH*NMe,*[CH,],*CH:CH -+ MeOH + NMe,*[CH,],*CH:CH and H20 + NMe + C,,H, It has been shown (Zoc. c d . ) that the presence of an ethylenic linking in an aliphatic group in a quaternary ammonium hydroxide facilitates the elimination of the group when the point of unsaturation is adjacent to the nitrogen atom. The decomposition of the hydroxides OH-NMe,*[CH,],*CH:CH shows that the loosening influence of the ethylenic linking weakens as its distance from the nitrogen atom increases ; trimethyldecenylammoni um hydroxide yields not more hydrocarbon than does the corresponding saturated quaternary ammonium hydroxide.c. s. The Asymmetric Cobalt Atom. V. ALFRED WERNER (Bey. 1912 45 121-1SO).-According t o the author's theory there are two possible salts of triethylenediaminecobalt which stand t o each other in the relation of object and mirror-image and are not super- posable. These may be represented thus Such compounds form the simplest possible case of molecular asymmetry being specially characterised by having all the co-ordination positions of the central atom occupied by structurally identical groups the asymmetry being caused by the special spatial arrangement of these groups. Such asymmetry the author denotes as molecuulas. asymmetry I1 (compare Abstr.1911 i 838) and he has been successful in resolving some of the salts into the optically active isomerides. Resolution by means of the camphorsulphonates a-bromo- camphorsulphonates etc. was unsuccessful since the salts woiild not crystallise. Triethylenediaminecobaltic tartrate w:ts obtained in theORGANIC CHEMISTRY. i. 167 crystalline condition however and proved to he a partial racemate which underwent slight resolution on fritctional crystallisation the extent of the resolution being ascertaiiied by taking advantage of the very strong rotation dispersion of these compounds. The lesser soluble crystals contained an excess of the Iavo-i~omeride the final mother liquors containing the excess of the dextro-isomeride ; the pure isomerides could then be isolated by making use of the fact that their bromides mere readily soluble in concentrated hydrobromic acid the rttcemic bromide being almost insoluble.'J'he yields of the active components were very poor by this wethod which was theii replaced by the following Co en3 c' I'i o does not form a partial racemate and by one recrystallisation can be separated into the sparingIy soluble d-ti iethylenediamiriecobaltic chloride-d- tartrate and the readily soluble Z-tIiethylenediaminecobaltic chloride- d-tartrate from which other salts can be obtained without difiiculty. The bromide tartrates behave similarly to the chloride tartrates. The specific rotations of the various salts are very large and the rotation dispersion is very marked as shown by the following table The chloride tartrate I 1 C f 4 6 [a],.[QI,. [MID. [q.. ............ { &45" { +552'50 &153'6" Chloride - 560 Bromide ............ { rkl65 + 195'5 ............ Nitrate {%I ( - 4 4 { 2;; - 187 1 +46 The active salts are very stable; their solutions cau be evaporated down with concentrated hydrochloric or hydrobromic acid without suffering any loss of activity. The active isomerides w e much more readily soluble than the racemates. The triethylenediaminecobaltic salts (Co en,)X are best prepared as follows 10 grams of cobalt chloride are dissolved in 150 grams of 10% ethylenediamine and oxidised by leading air through the solution. The brown solution so obtained is acidified with hydrochloric acid evaporated to crystallisation the crystals dissolved in water and ammonium nitrate added t o the solution whereby 1 6-dicliloro- diethylenediaminecobaltic nitrate is precipitated.After collecting this salt the filtrate is precipitated with sodium bromide giving pure triethylenediaminecobaltic bromide. C,H,O,) is obtained from the bromide by double decomposition with silver tartrate ; i t crystallises in spherical aggregates of light yellow needles. Tri- ethyZenedianiimcobuZtic chloride-turtrate Co en3 o is prepai ed by interaction of 1 molecule of the chloride with 1 molecule of silver tartrate the precipitate of silver chloride being extracted with boiling water until pure white in colour. The solutions thus obtained are concentrated and allowed to crystallise columnar and tabular crystals separating ; these are collected and the filtrate further concentrated.~~iethylenediami~aeco~c6l~ic tccrtrccte (Co I 1 9 r a 12 2i. I68 ABSTRACTS OF CHEMICAL PAPERS. A second crop of crystals often separates and then the concentrated solution sets t o a jelly-like mass. The crystals consist of d-triethylene- diumineco6aZtic chloride-tartrute [co en3]::~4~6,5H20 and are purified by one recrystalhation from water ; they have [a] + IOi" [MI +517.6' [.Ic + 3 5 O [MIc + 179.4O. The gel consists of tile corresponding Zaevo-salt mixed with srriall quail tities of the d-isomeride. d-T?wiethylenediuminecoba~t~c bromide-tartrate Co en3 C4H ,5 H,O is obtained similarly and forms R felted mass of light yellow silky needles which in contact with the solution slowly change to much darker stout plate-shaped crystals ; they have [a] + 9 8 O [MI + 555' [ale + 38" Lr\l] + 2 11 *7'.The corresponding laevo- isomeride forms a gel. d-~riethylenediu~,zinecobaItir bromide [Co en3]Br3,2H,0 is prepared from either the bromide-tartrate or the chloride-tartrate by trituration with warm concentrated hydrobromic acid. The soliition after filtering deposits large hexagonal plates which are probably an acid bromide ; on recrystallisation from water large columnar crystals of the bromide are obtained. The I-bromide [Co eo3]BrR,2H20 is similarly prepared from the gel of I-bromide-tartrate or 1-chloride- tartrate the sparingly soluble racemic bromide remaining undissolved. The d- and 1-chlorides [Co en,]CI3,H2O are obtained from the bromides by reaction with silver chloride; they crystallise in small golden- yellow needle-shaped crystals The d- and 1-nitrates [Co enJ(N03)3 are prepared from the bromide by treatment with the theoretical quantity of silver nitrate ; they form pyratuidal crystals 'which are readily soluble in water. L I l B r 4 6 T.S. P. Preparation of Hexamethylenetetramine Borocitrates. ATHENSTAEDT and REDEKEH (D.R.-P. 238962).-Alkali and magnesium borocitrates have been previously described. The hexametiiylene- tetrsmine derivatives have now been obtained by thoroughly mixing the required proportions of the ingredients in either concentrated aqueous or alcoholic solution. They form colourless crystalline powders and are readily soluble in water or alcohol. liex:ccmetl~ylenetetra~~~?~~ borocitrutes having the following composition a r e mentioned C,H,O7,3WBO,,2C,Hl2N decomp.182O ; CGH,0,,3HB0,,3C t-i 13N4 192' ; ~ C G H s 0 7 2 H B 0 2 3 C H 2 ~ ~ 185' ; 2C,El8O7,4HBO,,3U,H1,N 180" ; 2C,H,07,6 I€B0,,3C,H,,N4 178'. F. M. G . M. Compounds of Chromic Hydroxide with Amino-acids Derived frod Proteins. LOUIS HUGOUNENQ and ALBERT MOREL (Compt. rend. 1912 154 119-120).-Chromic hydroxide (1 mol.) dissolved in a boiling aqueous solution of glycine (6 mols.) gives a purple-red solution which deposits red crystals containing four mole- cules of the amino-acid and two hydroxyl groups to two atomsORGANIC CHEMISTRY. i. 169 of chromium. The excess of chromic hydroxide is removed by lixiviittion or treatment with acid. The filtrate from the red crystals 0 1 1 slow evaporation deposits brilliant vermilion acicular prisms of a compound containing six molecules of the amino-acid t o two atoms of chromium Both compounds are soluble in acids and are slowly decomposed byalkalis. They do not show the ordinary reactions of chromium salts but resemble more closely the chromoxalates.w. 0. w. Action of Amino-acids on Sugars ; Formation of Substances Resembling Melanins. LOUIS U. MAILLARD (Compt. s*end. 191 2 154 66-68. Compare this vol. i 13).-Continuing his experiments on the action of natural polyhydric alcohols on amino-acids the author finds that when glycine is heated on the water-bath with four times its weight of dextrose and the same amount of water i t rapidly loses carbon dioxide and forms dark brown cyclic condensation products the molecules of which contain a t least two dextrose residues to one nitrogen atom.They are said to be identical with the melanin pig- ments obtained in the hydrolysis of proteins. If this is so the comparatively low yield of amino-acids in such hydrolyses receives an explanation. The reaction is instantaneous between glycine and xylose or arabinose rapid in the case of galactose and mannose slow with lactose and maltose whilst several hours elapse before it occurs in the case of sucrose. Of the common amino-acids alanine is the most act iv w. 0. w. The Action of Moist S u l p h u r on Cholic Acid and Taurine. J. A. A. AUZIES (Rev. gen. chim. pure up$ 1911 14 278-280). -A study of the composition of the gall and bile of cattle and pigs from which the author corroborates the results of Langheld (AbLtr.19OS ii 211). Cholic acid OH*NMe,*CH,*CO,H is prepared by mixing calcium chloroacetate (1.92 parts) with trimethylnmine (1.18 parts) and heatiug the chloride of ccdciurn trimethylctmmoniumacetate so obtained with milk of lime at 120-150". Acetaldehyde is heated at 140' with chlorosulphonic acid CH,*CHO + SO,HCl= HCI + SO,€€*CH,*CHO ttie product converted into its calcium salt (CRO*CH,*SO,~,Ca which by treatment with ammonium hydroxide yields the aldehyde amiiiotii;t [NH,*CH(OII)*CH2-S0,]2Ca this loses water (2 mols.) on heating and 1s converted into the imine (NH :CH*CH,*SO,),Ca which after reduction to the corresponding amine and elimination of calcium with sulphuric acid furnishes the required taurine. Preparation of Brom oacylisocarbamide Ethers.FARBEN- FABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 240353).-When iso- carbamide ethers of the general formula NH,-C(0R):NH (R = alkyl or alkylaryl) are treated with bromodiethylacotyl halides they yield bromo-a-ethylbutyrylisocarbamide ethers which are of therapeutic value. Bromo-c~-etl~ylbutyrylisocarbamide mzethyl eLher colourless crystals m. p. 7 2 O was obtained by boiling brorno-a-ethyl butyryl bromide with Tnurine is prepared on an industrial scale as follows F. M. G.M.i. 170 ABSTRACTS OF CHEMICAL PAPERS methyl iiocarbamide hydrochloride (Abstr. 1900 i 340) in aqueous solution cooling and rendering alkaline when the product separated. F. M. G. M. Specific Rotatory Power of Glutamine. Ammonium Glutamate. ERNST SCHULZE and GEORQ TRIER (Bey.1912 45 257-262).-Supposed pure preparations of glutamine obtained from different plant preparations by precipitation with mercuric nitrate and continued crystallisation shorn [a] varying from + 5.4" to 8.9". By purification of the copper salt these preparations all yield glutamine of constant rotatory power [.ID + 6" to 7". The higher values are due to the presence of traces of glutamic acid which acting as an acid increases the rotatory power of glutamine. Glutamic acid forms a monobasic amm,onium salt [aID - 3*6O which begins t o lose ammonia when kept over concentrated sulphuric acid and readily loses ammonia when evaporated iu aqueous solution. Since glutamine when boiled in aqueous solution is to some extent hydrolysed to the ammonium salt the presence of glutamic acid is explained.E. F. A. Action of Ammonia on Ammonium Thiocyanate. WALTER P. BRADLEY and W. B. ALEXANDER (J. Amel.. Chem. Soc. 1912 34 15-24).-Comparatively few substances become deliquescent on exposure to dry ammonia and of these autmooium thiocyanate appears to possess the property in the highest degree the deliquesoence continuing up to a temperature of 88". The absorptive power f the salt was determined a t various temperatures between 0" and 100". At O" the product corltained 43.10% of ammonia; a t 25O 31.16%; at 50° 19.40%; a t 7 5 O 6-17% whilst a t 100' none was absorbed. F.-p. determinations were made of solutions of ammonium thiocyanate 111 ammonia the concentrations ranging from 0% to 100% of the latter. On plotting the results it is shown that there are certainly three and probably five compounds formed. The former are NH,CNS,NH LU.p. - 16" (metaytable) ; NH4CNS,3NH m. p. - 38' ; and NH,CN S 8N H m. p. about -87". The ot8her two compounds are N,H4CNS,6NH m. p. -76" and NH4CNS,7NH8 m. p. -84'. Indications were also obtained of the possible existence of the compound 2NH4CNS,13NH I I I . p. about -SO". - 9 6 O . E. G. The lowest eutectic point was in the vicinity of The Composition of Prussian Blue. P. WORINGER (Chem. Zeit. 1912 36 73).-Evidence for regarding Prussian blue as a ferro- cyanide hns been given by Hofrnann Heine and Hochtlen (Abstr. 1905 i 38). On the other hand when a ferric salt is precipitated with an excess of potassium ferrocyanide the filtrate contains considerable yunnti ties of potassium ferricyanide formed by the reactions FeCI + K,Fe(CN) = FeCl + K3Fe(UN) + KCl = KEeFe(CN) + 3KC1 and in the filtrate 3KFeFe(CN) = Fe,[Fe(CN),] + K,Fe(CN&.If aiximonium carbonate solution is added to a boiling suspension ofORGANIC CHEMISTRY i. 171 Prussian blue ammonium ferricyanide as well as ferrocyanide is found in the tiltrate and the iron remains as Pe,O,. This is considered to prove that Prussian blue is a ferricyanide. C. H. D. Organic Boro-Nitrogen Compounds ARDEN RICHARD JOHNSON (J. Physical. CJLetn. 19 12 16 1-28).-A series of compounds of boron tribromide with amines and nitriles was prepared in which boron as well as nitrogen is supposed to function as quinquevalent. Various additive compounds of boron trichloride tribromide and t,ri-iodide with ammonia are known in which the proportion of ammonia varies from 1.5 to 15 molecules per molecule of boron compound.Boron tribromide reacts with amines and nitriles with liberation of heat and additive compounds of the type (X)N:BBr are apparently formed in most cases. The nitriles and tertiary amines except trimethylamine give fairly stable crystalline products. Compounds of this type were also isolated from the primary isoamylamine and aniline. The compounds of the aliphatic secondary amines im- mediately lose hydrogen bromide amorphous products of the type R,N*BBr2 resulting. Similarly the product from ethylamine has the constitution NHEt- BBr With methylamine the reaction apparently goes a stage further and the product isolated has the formula B(NHMe),Br.Piperidine and diphenylamine give compounds of the type (YNH),,BBr3. The compounds were prepared by passing the dry gaseous amines into a carbon tetrachloride solution of boron tribromide or by adding the bromide Eolution from a burette to the anhydrous amine or nitrile dissolved in carbon tetrachloride. I n aome cases an oily insoluble product containing excess of amine was first formed and afterwards converted into a solid product by further addition of bromide. The substances (NHNe)2:BBr NBEt*B13r2,. NH,(C,H,,):BBr NH2Ph:BBr NMe,*BBr and NPr2*BBr2 are white amorphous solids sparingly soluble in carbon tetrachloride. The monoisoamylamine compound which may be handled in the air turns yellow in sunlight but does not dissociate very rapidly below 40'.When heated up quickly it appears to melt and decompose simultaneously. It burns furiously colouring the flame intensely green. Tbe isoamyl compound N(C,H,,),:BBr may be crystallised from carbon tetrachloride. It dissolves in water giving diisoamylamine hydrobromide and boric acid. The substance SC,H,,N BBr is formed from piperidine in a violent reaction which must be moderated by careful cooling. It has been obtained as a pale yellow precipitate which readily loses hydrogen bromide when exposed over sodium hydroxide in a desiccator being converted into the szcbstance (31,H,oN-BBr,(C,H,1N),. The latter is a stable solid giving greenish-yellow fluorescing solutions in organic solvents. The substance 3NHPh2,BBr is a white precipitate comparatively stable in air.. Trimethylamine reacts with boron tribromide with development of heat. White fumes were givea of€ and no solid compound could bei. 172 ABSTRACTS OF CHEMICAL PAPERS. isolated. The substance NEt,:BBr crystallises from carbon tetra- chloride in long slender prisms. The substance NMe,Ph:BBr forms a camphor-like crystalline hygroscopic mass. When exposed in a desiccator over sodium hydroxide the elements of methyl bromide are removed and the substance NMePhOBBr? remains. The latter is very rapidly decomposed by hot alkali with precipitation of boron nitride BK. The pyridine compound C,H,N:BBr is a snow-white amorphous mass fairly stable in the air but tending to dissociate with rising temperature; a t 120' i t turns brown and sinters.When placed in a desiccator over sodium hydroxide the elements of hydrogen bromide are removed and the substance C,H,N-BBr remains as a stable powder. It is suggested that boron is probably combined with the carbon as well as the nitrogen of the pyridine nucleus in this compound. The white substance C,H7N BBr formed from quinoliiie IS more stable than the pyridine compound and scarcely fumes in the air. The substances CNMeIBBr CNEt:BBr and CNPh:BBr are obtained from their carbon tetrachloride solutions as white crystals The methyl compound dissociates very rapidly a t 30° and the ethyl compound is slightly more stable. The substance CH2Ph*CN:BBr3 which is difficult to purify by crystallisation was obtained as a slightly yellow crystalline mass. Most of the above boron tribromide compounds decompose or sublime without melting.Some of the nitrile compounds may be heated to nearly 200' before decomposing. Of the amine products those of pyridine and quinoline are the most stable. The products of decomposition by heat probably contain boron nitride in most cases. The substances described are violently decomposed by water absolute alcohol acetaldehyde and acetic acid the products containing boric acid accompanied by hydrogen bromide ethyl bromide bromoacetaldehyde and acetyl bromide respectively. Acetone the esters and ether have a less violent action and crystalline products containing boron and carbon have been obtained. Hydrocarbons usually exert no solvent action on boron bromide compounds but with prolonged contact in sunlight the hydrocarbon assumes a red to brown tint.A slow decom- position also occurs in contact with chloroform and bromoform. Carbon tetrachloride and tetrabromide in which the substances are but slightly soluble have no chemical action on them. It melts with some decomposition. R. J. C. Preparation of Me thylcyclopentape. S. S. NAMETKIN (J. IZUSS. Phys. (?hem. Xoc. l911,43,1611-1613).-The preparation of methyl- cyclopentane by the action of fuming hydriodic acid a t 100-105° on cycZopentanylcarbinoI (compare Zelinsky Absbr. 1908 i 727) and reduction of the iodide thus obtained by means of zinc dust in aqueous alcoholic solution gives a product containing cyclohexane. Hence when heated with hydriodic acid the cyclopen tanylcarbinol undergoes partial isomerisation into a six-carbon atom ring compound.Similar cases of the ready isomerisatioh of substituted cyclic carbinols have been observed by Demjsnoff (Abstr. 1910 i 838) and by Kijner (Abstr. 1905 i 772; 1908 i 530 864; 1911 i 42). T. H. P.OKGANIC CHEMISTRY. i. 173 Polymerisation of Diethylene Hydrocarbons. Polymerisation of as-Dimethylallene. IV. SERGIUS V. LEBEDEFF (J. Nuss. Phys. Chem. Soc. 1911 43 1735-1739).-For a n unsymmetrical di- substituted allene six dimerides are possible three of each of the F-QZC types F-7:' and Two of the compounds of the former c-c:c C=C-C of these types have been obtained (Abstr. 1911 i 774) failure to isolate the third being due probably to its high velocity of polymeriss- tion. The author's results indicate that the velocity of polymerisation of hydrocarbons with conjugated systems of double linkings :C:C*C:C increases with diminution of the loading of the extreme carbon atoms and with increase of that of the intermediate ones.Hence of the three dimerides of as-dirnethylallene of the first type 1 2-diiso- propenylcyclobutane should be the most stable 1 1 2 2-tetramethyl- 3 4-dimethylenec~clobu tane should occupy an intermediate position in this respect (Zoc. cit.) and the third 3 3-dimethyl-Tmethylene- 1 -isopropenylcycZobutane sbould readily polymerise. By the choice of suitable conditions the remaining dimeride (the second) has now been obtained. . . 1 1 2 2-Tetramethyl-3 4-dimethyZenecyclobutane has b. p. 140-141°/760 mm. 66-67'755 mm. DSo 0.7927 r$ 1.46063 ~i 1.45701 n:? 1,46988 nz 1.47807 and yields tetramethylsuccinic acid when treated with ozone. The physical properties of these three dimerides some of whicb were given wrongly in the previous paper are as follows Optical exalta- B.p. DIO. tion. 1 2-Dis~~pro~cr1ylc~cZobutsne ............ ... ...... ... ... 179-181" 0'8422 2'34 1 l-Dimethyl-2-metliylene-3-isopropcnylcycZobutane 149-150 0.7982 2.09 1 1 2 2-Tetrainethyl-3 4-dimethylenecyclobutane 140-141 0 7927 1-81 As regards the non-formation of dimerides of the second of the two types given above it is pointed out that the relations of unsaturated compounds to reactions of combination indicate clearly that the tensions of the affinities in the molecule are distributed unequally. For the complex :C:C:C they are directed the most strongly towards the middle carbon atom so that combination of the two molecules takes place first a t this place there being possible the two annexed 2 3 1 arrangements.CH,:C:CMe CH,=C:CAle With the former of these arrange- ments further saturation of the free CH,:b:CMe CMe,:C:CH affinities gives the two dimerides 1 1 2 2-tetramethyl-3 4-dimethylenecycZobutane whilst with the latter owing t o its symmetrical character only one dimeride namely 1 1 -dimethyl-2-methylene-3 -isopropenylcycZobutane is obtained. This scheme hence excludes the possibility of formation of dimerides of the second type. T. H. P. and 1 2 3 3 1 2 - diisopropenylcyclobutane andi. 174 ABSTRACTS OF CHEMICAL PAPERS. Chemical Action of Light. XXII. Autoxidations. I. GIACOMO TJ.CIAMICIAN and PAUL SILBER (Bey. 1912,45 38-43 ; Atti R. Accccd. Liizcei 191 1 [v] 20 ii 673-677).-Aromatic hydrocarbons on prolonged exposure to the action of light in presence of water in an atmosphere of oxygen in sealed vessels are partly oxidised to the corresponding carboxylic acids ; small quantities of the corresponding aldehydes and of formic acid are also formed. Thus toluene yields benzoic acid and benzaldehyde ; p-xylene gives p-toluic acid m. p. 181" and a little terephthalic acid as well as traces of the aldehyde ; m-xylene forms m-toluic acid m. p. 11 lo and isophthalic acid ; o-xylene forms 0-toluic acid m. p. 107-108". p-Cymene yields some aldehyde p-cuminic acid m. p. 119" p-propenylbenzoic acid m. p. 165" and a-hydroxy-p-cuminic acid m.p. 156". I n the dark the hydrocarbons are unchanged. p- and 0- Nitrotoluene also phenanthrene are practically unaltered after prolonged exposure to light. E. F. A. [Orientation in the Benzene Nucleus.] JULIUS OBERMILLER (h'er. 1912 45 165-167. Cornpare Abstr. 1911 i 960).-The author upholds his claim of priority over Holleman (this vol. i 20) and maintains that there is no essential difference between their views concerning substitution in the benzene nucleus. F. B. Benzene Hexachlorides and their Decomposition into Trichlorobenzenes. T. VAN DER LINDEN (Bey. 19 12,45 23 1-247). -a- and P-Benzene hexachlorides prepared by the action of chlorine on benzene in snnlight form a eutectic solidifying at 155.5". This p i n t was mistaken for the melting point by Matthew (Trans.1891 59 166). I n addition to the a- and p-isomerides two new benzene hexachlorides are formed in the reaction all four compounds are stereoisomerides. The y-isomczride crystallises in needles and lozenge- shaped forms m. p. 112- 1 13" ; the 6-isomeride forms slender lustrous twin platelets m. p. 129-132". 0n:decomposition of a- benzene hexachloride with alkali a mixture of 1 2 4- 1 2 3- and 1 3 5-trichlorobenzenes is obtained. The temperature at which decomposition is effected has no influence on the relative proportions of these or is this proportion altered on replacing potassium hydroxide by sodium hydroxide or substituting methyl alcohol for ethyl alcohol. The proportion is however altered by the use of pyridine or quinoline more of the 1 2 4- and less of the 1 2 3- isomeride being obtained the amount of the 1 3 5-trichlorobenzene remaining constant. @-Benzene hexachloride when decomposed by potassium hydroxide in ethyl alcohol yields the same three trichlorobenzenes as the a-isomeride but in different proportions which are very similar to those obtained on decomposing the a-isomeride with pyridine.Pyridine however has hardly any action on the /I-compound. y-Benzene hexachloride yields the three trichlorobenzenes in slightly different proportions than either of the a- or P-isomerides. It was not found possible to eliminate the chlorine in stages neitherORGAKIC CHEMISTRY. i. 175 could hydrogen chloride be split off by means of aluminirim or ferric chlorides. The fact that a considerable proportion of 1 2 3-trichlorobenzene is formed indicates that the elimination of hydrogen chloride is not entirely between two neighbouring carbon atoms.E. F. A. Preparation of 7-Chloropropylbenzene and its Homologues. EMANUEL MERCK ( D. R. -P. ~ 3 9 0 7 6 ) . - y - C h Z o r o ~ ~ r o ~ ~ Z ~ ~ ~ ~ e ~ e C:,H,.CH,*CH,*C H,Cl a colourless oil with penetrating odour b. p. 279-220" or llOo/21 mm. is obtained in 78% yield from y-chloropropylanilino by diazotisation and subsequent reduction with stannous chloride in alkaline solution. F. M. G. M. 2-Chloro-3 5-dinitrotoluene. WALTHER BORSCHE and ANNA FIEDLER (Bey. 191 1 45 270-273).-2-Chloro-3 5-dinitrotoluene is formed in only small quantity by nitrating o-chlorotoluene and does not constitute the main product of the reaction as stated by Nietzki and Rehe (Abstr.1893 i 15). It crystallises from alcohol in stout yellow rhombs m. p. 63-64'; Nietzki and Rehe give 45'. It is best prepared by heating 2-chloro-3-nitrotoluene or 2-chloro-5- nitrotoluene with a mixture of equal parts of sulphuric and fuming nitric acids for two hours on the water-bath. The above-mentioned mononitro-compounds are conveniently pre- pared by nitrating aceto-o-toluidide and hydrolysing the product with hydrochloric acid ; the resulting mixture of 3-nitro- and 5-nitro-0- toluidine is separated by steam distillation and the amino-group replaced by chlorine according to Ullmann's method. 4-Chloro-3 5-dinitrotoluene has m. p. 116-11'i0 and not 48' as given by Horiig (Abstr. 1887 1034). ' F. B. Conversion of the Bromonitrobenzenes into the Corre- sponding Dichlorobenzenes by Phosphorus Pentachloride.JULIUS SCHMIDT and HANS WAGNER (AnnuZen 1912,387 164-165)- When heated with phosphorus pentnchloride in a sealed tube at 180' for six hours 0- m- and p-bromonitrobenzenes are converted more or less smoothly into 0- rn- and p-dichlorcbenzenes. c. s. Action of Nitric Acid on cycZoPentane and Methylcyclopen- tane. S. 8. NAMETKIN (J. Buss. Phys. Chem. Xoc. 191 1 43 1603-1611. Compare Abstr. 1910 i 830).- Nitrocyclopentune C5H,*N02 obt,ained by the interaction of aluminium nitrate and cyclopentane iu a sealed tube is a colourless liquid b. p. 90-9lo/40mm. DY 1.0776 r, 1-4518 with the characteristic odour of secondary nitro-compounds. On oxidation with nitric acid it yields glutaric acid which is also formed when cyclopentane itself is oxidised.Nitration of methylcyclopentane by means of nitric acid yields 1 -nitro-1-methylcyclopentane and 2-nitro-1 -methylcycEopentane b. p. 98-99'/40 mm. Di2 1.0381 rng 1.4488 (compare Markownikoff Abstr. 1899 i 799). Thus in the secondary nitro-product of methylcyclopentane thei. 176 ABSTRACTS OF CHEMICAL PAPERS. nitro-group occupies the a-position whilst in that of methylcydo- liexane i t occupies the P-position. The above two nitro-compounds formed by the nitration of methylcydopentane are accompanied by succinic and a-methylglutaric acids; probable schemes are given for the formation of these two acids. T. H. P. The Preparation of ~-2-Dinitrotoluene its Honiologues and Derivatives. SOCIETE CHIMIQUE DES USINES DU R H ~ N E (L).R.-P.239'353).-w-2-Di,~itrotoZueize NO;C,II;CH,.NO or NO C6H4 C H NO (OH) m. p. 67' is readily prepared in 70% yield by heating o-nitrotolueno (2 parts) a t 1 10-220° during eight hours with the gradual addition of 70% nitric acid (1 part) o-nitrobenzaldehyde and o-nitrobeuzoic wid being simultaneously produced as by-products. The followiug compounds are desribed ~-4-dirnitrotoZuene m. p. 9 1" ; 4-Ch~OrO-o-2- di&trotoZue?z,e In. p. 112' ; 4-bro?no-w-2-tlinitrotoZuel..Le m. p. 113.5' ; Ci-chZoro-w-2-clinitrotolu~ne m. p. 82' ; whilst o-nitro-m-xylem yields a mixture of w-6-dinitro-m-xyZene m. p. 86*5" and o-4-clinitro-m-xyle?~e u1. p. 64". F. M. G.M. Preparation of Chloroalkylarylsulphonic Acids and of Chloroalkylarylcarboxylic Acids.BADISCHE ANILIN- & SODA- PABHIK (D.R.-P. 23931 l).-o-Chlorotoluene-p-suZphonic acid is readily prepared by slowly dropping water (18 parts) into w-chlorotoluene-p- sulphonyl chloride (225 parts) dissolved in 80 parts of hot alcohol. The sodium salt SO,Na*C,H,*CH,CI is sparingly soluble in water. w-Dichlorotoluene-m-suZph.0 rr y? chlo?*ide a crys tal line powder insoluble in water and prepared by the action of phosphorus pentachloride on benzaldehyde-?it-sulphonic acid is converted by the foregoing treatment into w-dichlorotoluenc-m-sulphonic acid ; the sodium salt is moderately soluble in water. w-ChZovo-p-toluoyl chEoride a colourless oil b. p. 150-155O (pre- pared by chlorinating a hot solution of p-toluoyl chloride) when dissolved and maintained a t 0-5" in 08% sulphuric acid until the evolution of hydrogen chloride ceases furnishes w-chloro-p-toluic acid m.p. 190-192" (decornp.) and insoluble in water. F. 1sI. G. M. Preparation of Aromatic Sulphonyl Ammonium Corn- Dounda. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 239i63).- When sodium o-chlorotoluene-p-sulphonate is he&ted with dimethyl- aniline at TO" it yields the compound C,H4<YH2>NMoPh a bO3 colourless powder. Ethyl w-2-dichZorotoluene-p-sulp7to~~ate a colourless oil prepared by hydrolysing the corresponding sulphonyl chloride with sodium ethoxide when similarly treated furnishes the compound S0,Et*CGH,Cl-CH2-NC1Me,Ph in colourless hygroscopic crystals readily soluble in water and alcohol. F. M. G. M.ORGANIC CHEMlS‘rHY. i.177 System of Noiiienclature for Bridged Rings.” VICTOR GRIGNARD (Bull. SOC. c h 2 . 1912 [iv] 11 184-129).-The author proposes to avoid the inconveniences of von Baeyer’s system of nomenclature for such structures by (1) selecting for the nucleus of the name t h a t of the fundamental ring which is immediately apparent traversed by one or more bridges; (2) numbering the atoms in the bridges after those of the fundamental ring so that the bridges appear t o be merely particular substituents attached a t two points arid identified in the name by their ‘ 6 characteristic.” This character- istic consists of the numbers of all the atoms which appear in the ‘‘ bridge,” and the highest number in it indicates the total number of carbon atoms in the structure. The number of constituent rings apart from the fundamental ring is always twice the number of bridges and is indicated by prefixes bicyclo tetracyclo etc.Where the bridge contains a n ethylenic linking these prefixes become bicycleno and tetracycleno respectively and the number of the atom at which the double linking begins is accented in the “character- istic.” The following examples of the application of the system may be given 1 I 1 T. A. H. Compounds of A n t i m o n y Trichloride and Tribromide with Polynuclear Benzene Hydrocarbons. KoRIs N. MENSCRUTKIN (J. 12uss. Phys. Chem. Soc. 191 1 43 1805-18~0).- 1 Iiphenyl and diphenylmethano form with antimony trihalitles mole- ciilitr compounds containing 2 mols. of antimony salt to 1 mol. of hydrocarbon 2SbC13,C,H,Ph m.p. 71” ; 2SbBr,,C6H,Ph 60.5’ ; 2Sbl,,O,H,Ph 161’ ; 2SbCl,,CH,Ph m. p. 100’ ; 2SbBr,,CH2Ph m. p. YO”. Xach concentration-temperature diagram exhibits two eut,ectic points as follows M. p. Hydro- System. carbon. SbCIs-C,H,Ph 70.5” S b Br,-CtjH ,Ph S b ‘2 I,- C H 1 ’11 7 0 -5 S1) 12 - C H ,l’h S I ) Br,-CH,I’h 26 70.5 2 6 1st eutectic point. +7 Tempera- ture. n. 50” 2’2 47 1-75 68 89.4 22-5 15’6 22.5 14.6 - 2nd eiitectic point. 7- Tempera- ture. 12.. 57” 0.18 60.5 0.52 67 82 0.18 160 0.2 0-6 M. p SbX,. 7 3” 94 166 73 94 With antimony trichloride and . tri-iodide diphenyl gives stable compounds which melt without decomposing whilst with antimony tribrornide it yields a compound with a melting point in the region of unstable equilibrium.i. 1'78 ABSTRACTS OF CHEMICAL PAPERS.Triphenylmethane forms no molecular cornpound with antimony tri- bromide but with the trichloride i t gives the compound SbCI,,CHPh melting a t 49.5' in the region of unstable equilibrium. The diagram consists of three branches the first eutectic point corresponding with SbC1,,0*93CHPh3 lying at 49O and the second with SbC13,0*37CHPh at 35'. The diminished capacity t o form compounds with antimony tri- halides otlserved in the case of triphenylmethane may be related t o the fact that this hydrocai-lion differs considerably in its chemical properties from diphenylmethane ; thus i t forms molecular com- pounds with benzene and other hydrocarbons and yields metallic derivatives etc. Colorations are often observed on fusing these polynuclear hydro- carbons with antimony trihalides (compare -Watson Smith Abstr.18'79 831). T. H. P. Halogen Derivatives of Fluorene and Bisdiphenylene- ethylene. JULIUS SCHMIDT and HANS WAGNER (Annalen 191 2 387 147-1 64).-The method of converting 9 9-dichlorofluorene into bisdiphenylene-ethylene by heating with copper powder in benzene (Abstr. 1910 i 550) has been applied t o other halogenated fluorene derivatives ; thus 9 9-dichZoro-2-bromoftzcorene F,H,Br >CCI In. p. ( 7 3 4 - 178") colourless needles obtained from 2-bromofluorenone and phos- phorus pentachloride at 160-lSOo is converted into 2 2'-dibromo- C;,H,Br >C:C<fE3Br m. p. 312O red crystals bisdiphenylene- ethy Zene or by sublimation yellowish-green needles. This substance is con- verted into 2 ; 2'-dibromobisdip12enyZ~ne-etlzccneJ C6H4- 6 4 ?6H3Br>CH*CH<<H $? H Br m.p. 272') colourless needles by heating its ethereal solution with platinum black for eight hours in R current of hydrogen aud reacts additively with chlorine in cliloroform and with bromine in carbon disulphide in sunlight to form respectively 9 Y'-dichEoro-2 2'-dibromo- xn. p. 268O colour- $! H Br bisdiphen yZene-ethane ?6H3Br>CC1 cCl< less crystals and 2 2' 9 9'-tetrabroinobasdzphenylene-ethne m. p. 258'; the latter in benzene reacts with silver acetate to form the c6H4- 6 4 c6H4- C 6 H 4 ?6H3Br m. p. 285'. diacetate 3->C(OAc)*C(OAc)<C 9 9-DicAZoro-2 'I-dibromoJuorene H Br >CCl m. p. 260") colour- c6H4 ?,".,".r C,K,Br less needles obtained from 2 7-dibiomofluorenone and phosphorus pentachloride a t 210-2'20° is converted by copper into 2 :2' :7 :7'-tetra- 364' red AromobisdiphenyZene-ethylem 76H3Br>C:C< C,H3Br' p.crystals from which the following substances have been prepared 9 B'-dichZoro-2 2' 7 :'i'-tetrubrornobisd~~}~e~a~lerLe-~t?~ane m. p. 298-299' H Br C6H,BrORGANIC CHEMISTRY. i. 179 colourless needles; 2 2' 7 5' 9 9'-hexccbromobisdip?henylene-ethane m. p. 310° colourless crystals ; 2 2' 7 7'-tetrab~omobisdiphe.lzylelze- ethane m. p. 284' colonrless leaflets. The disappearance of colour coincidently with that of the ethylenic linking is noteworthy. When heated in a sealed tube a t 180' for six hours fluorenone and phosphorus pentachloride yield 9 9'-dichZorobisdiphenyZene-etha.ne m. p. 235-236' 2 7 9 Y-tetraclAZoroJuorene m.p. 215' and a little 2 7-dichZoroJEuorenone (?) m. p. 187-189'. 2 7-Dichlorofluorenone m. p. lS5-1S6O (which appears to be identical with Goldschmiedt and Schranzhofer's P-dichlorofluorenone) is obtained best by heating 2 7-dinitrofluorenone with phosphorus pentnchlorids in a sealed tube a t 17O-1SO0 and boiling the resulting 2 7 8 9-tetrachlorofluorene with water ; it forms an oxime decomp. 243' phenylhydraxone decomp. 186-187' and semicurbaxone decomp. 345' and is converted by copper into 2 2' 7 7'-tetracl~Zorobisdiphenytene-ethylene a red substance m. p. above 380'. c. s. The Preparation and Reactions of Bis-a-hydrindone-(2 2-)- spiran. HERMANN LEUCHS and DAN RADULESCU (Ber. 1912 45 189-201).-Dibenzylmalonic acid the preparation of which is fully described is converted by means of phosphorus pentachloride in to dibenxylmaZony2 chloride b.p. 216-21So/17 mm. 232-235"/32 mm. m. p. 68-69'. When dissolved in ether and treated with ammonia and aniline respectively this yields the corresponding amide (m. p. 198-199") and anilide (m. p. 196-197'). Boiling alcohol converts i t into the ester. During distillation of the chloride under diminished pressure as also when it is heated at 250-270' for some time hydrogen chloride is evolved and small quantities of bis-a-hydrindone- ( 2 2-)spiran formed. The latter is best prepared by distilling the chlosids under diminished pressure in the presence of 2% of alumininni chloride. It has b. p. 255-257'/12 mm. (corr.) m. p. 174'. Phenyl- hydrazine converts i t into bis-a-hydrindone-( 2 2-)-spiranbispl~en?/I- hydrazone colourless prisms m.p. 200-201° (decomp.). When treated with hydroxylamine a substance C17€11302N is formed (m. p. 214-215") which possibly has the formula c G H < E ~ ~ > c < ~ ~ D c G H ~ * Under the action of sodium hydroxide bis-a-hydrindone-( 2 2-)-spiran readily yields the sodium salt of a strong monobasic acid which is stable towards excess of alkali. The free acid has m. p. 140-142' and when heated a t 220° evolves water vapour with the reforma- tion of spiran. The composition of the acid is probably expressed by the for mula C,H,<2$&'HC(C6H4. It can be resolved into optically active forms by crystallisation of the brucine salt from acetone. Attempts were made to prepare the methyl ester of the acid by the action of methyl iodide on the silver salt. When distilled under diminished pressure it decomposed with the regeneration of spiran.Bis-a-hydrindone-(2 2-)-spiran when treated with alcoholic ammonia The ester could not be obtained in the crystalline state.i. 180 ABSTRACTS OF CHEMICAL PAPERS. forms two compounds C17H,,0N m. p. 246-248' (decomp.) and CIpH,,O2N. The latter when rapidly heated melts a t 124-128O (decomp,) and is readily transformed into the former by heating it above its m. p. or by treating i t with concentrated hydrochloric acid. These substances are probably not the nitrile and amide described acid since * neithei evolves ammonia when potassium hydroxide. The following formulae are proposed for them c 6 H 4 < ~ ~ ~ > c < ~ ~ ~ > c 6 H 4 and of the above- treated with provisional I y Anhydrobig-a-hydrindonespiran obtained in small quantity by the distillation of dibenzylmalonyl chloride under ordinary pressure in the presence of 4% of aluminium chloride crystallises from glacial acetic acid in light red needles m.p. 256-257'. H. W. Reactivity of Side-chains in Nuclear Nitrated Hornologues of Benzene. WALTHER BORSCHE (Annulen 19 12 386 35 1-3~9.- One of the halogen atoms is readily substituted the other only with difficulty when 1 3-dichloro-4 6-dinitrobenzene is warmed in ether with an excess of ethyl sodioacetoacetate. On the other hand both methyl groups react readily when 4 6-dinitro-m-xylene and benzaldehyde (2 mols.) are heated at 190' with a little piperidine ; the main product is 4 6-dinitro-1 3-distyrylbenzene C,H,(NO,),(CH:UHPh) m.p. 186' yellow needles very little 4 6-dinitro-3-methylstilbene C,H,Me(NO,),*CH:CHPh m. p. 145* being formed. Trinitromesitylene dinitromesitylene trinitro-$-cumene and 2 4-dinitroethylbenzene do not react with benzaldehyde. 2 4 6-Trinitrotoluene yields trinitrostilbene (Ullmann and Gschwind Abstr. 1908 i 622). 2 4 6-Trinitro-m-xylene benzaldehyde and a little piperidine when heated in boiling amyl alcoholic solution yield 2 4 6-ts.initro- 1 3-cZistyylbenzene C22H1506NS m. p. 147-148' yellow needles. Corresponding substances C,,H1?O,N3 m. p. 155' and C2,Hl3OI0N5 m. p. 268' (decomp.) are obtained with anisaldehyde and p-nitro- benzaldehyde respectively.These condensations proceed most smoothly in the toluene series less readily in the xylene series and badly or not at all in the mesitylene series. The author is of opinion that in these nitrated methylbenzenes the distribution of the residual affinity of the benzene nucleus is such that when only one methyl group is present the influence of the residual affinity is concentrated on the carbon atom of this methyl group its hydrogen atoms therefore becoming more mobile; as however the symmetry of the whole molecule is increased by the introduction of two and three methyl groups the influence of the residual affinity is distributed between the methyl groups with the result that their hydrogen atoms become less and less mobile. In the case of tbe chloronitrobenzenes the elimination of the halogen atom is due according to the author not to any weakening of the union between it and the carbon atom but rather t o a striving of the molecule t o assume an ortho- or para- quiuonoid structure ; the reagent s then held additively the final product being obtained by the elimination of a halide ; thus :ORGANIC CHEMISTRY.i. 181 Ullmann and Gschwind (Zoc. c k ) have shown that the reactivity of the methyl groiip in 2 4-diuitrotoluene still persists when one of the nitro-groups is replaced by a carboxy lie sulphonic or cyanogen group. The author finds however that in 6-nitro-4-cyano-m-xylene only one methyl group reacts with benzaldehyde and a little piperidine at 190-20Oo giving a very poor yield of 6-nitro-4-cyano-3-methyZ- stilbene (?) NO,*C,H,Me(CN)*CH :CHPh M.p. 183-184O yellow needles. 2 4-Dicyanotoluene does not react with benzsldehyde. 4 6-Dinitro-1 3-distyrylbenzene forms a tetrabromide C,H,(NO,),(CHRr*C HPhEr) m. p. 207-20bO (decomp.) and by reduction with stannous chloride and acetic and hydrochloric acids yields 4 6-diamino- 1 3-distyryZbenzer~e m. p. 204O yellow crystals with green fluor- escence. The base forms fluorescent solutions yields a dibenxoyl derivative which is unchanged at 2 7 5 O and react3 with benz- aldehyde in boiling alcohol to form the dibenxylidene derivative C,H,(N:CHPh),(CH:CHPh) in. p. 238-239' deep yellow non- fluorescent needles. A methyl-alcoholic solution of the base is reduced by hydrogen in the presence of a little colloidal pitlladium yielding 4 6-diamino- 1 3-di-P-phenyZethy2benxen~ C,H,( NH,),(CH,*CH,Ph) (diacet9Z derivative m.p. 224'; dibenzoyl derivative m. p. 273'). 4-Cyano-m-xylene and nitric acid D 1.52 a t 0' yield a mixture of sparingly soluble (in alcohol) yellowish prisms m. p. 107-108° (probably 6-nitro-4-cyano-m-xytene) and easily soluble white needles m. p. 120-1 2 1' (probably 4-cyano-2-nitro-m-rylene). By diazotisa- tion and treatment with cuprous cyanide 4-cyano-o-toluidine yields Non-Existence of $-Diphenyleneketone [ $-Fluorone]. A New Red Hydrocarbon. RUDOLF PUMMERER (Ber. 1912 45 294-298).-The red modification of fluorone obtained by Kerp (Abstr. 1896 i 238 ; compare also Stobbe ibid. 1911 i 651) by the distillation of calcium diphenoxide is shown to be the ordinary yellow variety of fluorone contaminated with traces of the red substance first observed by Fittig and Ostermayer (this Journ.1873 892) and shown by them to be produced simultaneously in the This red impurity is insoluble in alcohol /\-fN and solvents of low b. p. but dissolves to a slight II I I extent in solutions of fluorone from which i t may be \/\/\/ removed by shaking in the cold with animal charcoal. I II It may be isolated by repeatedly triturating the /\/\/\ '' red fluorone" with cold alcohol and crystsllis- 'I 1-11 I ing the residue from benzene. It forms slender \/ \/ lancet-shaped crystals m. p. 306O yields strongly 2 4-dicyanotoZuene m. p. 144-145' white needles. c. s. distillation. VOL. CII. 1. 0i. 182 ABSTRACTS OF CHEMICAL PAPERS. yellow fluorescent solutions and has the composition C26H14.On account of its bright red colour the hydrocarbon is termed by the author rubicene. Its constitution has not yet been definitely established but argu- ments are advanced in favour of the formula given on the preceding page. With bromine in chloroform solution it forms a bromo-substitution product ; the picrate crystallises in very slender brownish-red prisms. Kerp's "red fluorone" contains in addition to rubicene a white substance which remains behind on dissolving the ketone in concen- trated sulphuric acid. F. B. Isomeric SchiFs Bases. BRONISLAW PAWLEWSKI (Chem. Zentr. 1912 i 2 9 ; from Chem. Polski 1911 11 121-122).-0f the five substances obtained by the author by condensing benzoin with benzylamine one m. p. 88-90' is the trans-modification of benxylidene- benxylamine CHPh:N*CH,Ph and is stereoisomeric therefore with the liquid benzylidenebenzylamine b.p. 200-202'/10-20 mm. The Homo-chromoiaomerism of the Phenylmethylpicr- amides. ARTHUR HANTZSCH (Bey. 1912 45 360-363)- Polemical ; a reply to Biilmann (Abstr. 1911 i 963). F R ~ D ~ R I C REVERDIN and ARMAND DE Luc (Bey. 1912 45 349-354).-A continuation of earlier work (Abstr. 1909 i 377 913 ; 1910 i 470) in which a study has been made of the effect of the subetitution of the nitrobenzoyl group into the amino-group of p-anisidine on the behaviour of the base towards nitration. m-Nitro benxenesulphon yl-p-anisidide NO,*C,H,~SO,*NK~C,H,~O~~e obtained by the action of the acid chloride on the base forms white needles m. p.135'; the acetyl derivative forms needles m. p. 1 8 1-1 82'. o-Nitrotoluene-p-sulphonyl-p-anisidide obtained similarly forms needle crystals m. p. 81'; acetyl derivative m. p. 161'. The nitration of the above nitrobenzenesulphonyl-p-anisidide with nitric acid D 1.38 without cooling (max. temperature 36') gives as chief product an orange-yellow dinitro-derivative m. p. 1 70° which can be hydrolysed to the corresponding free base 2 5-dinitro-p-anisidine. I f the temperature is allowed to rise to 62" a mixture of the previous dinitro-compound with the isomeric 3 5-dinitro-compound m. p. 165-166' is obtained; this forms white needles and hydrolyses to 3 5-dinitro-4-aminoanisole. If the mixture during nitration is heated over a free flame there is obtained the nitrobenxemesulphonyl deriv- ative of 2 3 6-trinitro-4-aminoanisole which forms small prismatic crystals ni.p. 189-190'. When nitrated as an emulsion in acetic acid at 70' with nitric acid D 1.38 the main product is the above 3 5-dinitro-derivative. With nitric acid D 1.52 between 0' and 5' the product consists of a mixture of the 2 5-dinitro- and the 2 3 6-trinitro-derivatives; at higher temperatures decomposition occurs ; if the nitration with acid of this strength is perFormed at 5-10' in an emulsion in acetic acid described by Mason and Winder (Trans. 1894 SS 191). c. s. D. F. T. Nitration of the Acyl Derivatives of p-Anisidine.ORGANIC CHEMISTRY. i. 183 a mononitro-derivative is obtained (yellow needles m. p. 127O) which on hydrolyais gives 3-nitro-4-aminoanisole. With nitric acid D 1.38 the above-mentioned nitrotoluenesulphonyl- p-anisidide at 36' yields a mononitro-derivative (prismatic crystals m.p..13Y),the constitution of which is shown by its hydrolysis to 3-nitro- p-anisidine. At higher tern p erat ures the r~itrotolueneaulphonyl derivatives of 3 5-dinitro- and 2 3 6-trinitro-p-anisidine are obtained (m. p. 125-140' and 184-185O respectively); the former of these is also the product of nitrating a solution in acetic acid. With nitric acid D 1.52 at 5-10' the product contains the nitro- toluenesulphonyl derivatives of 2 3-dinitro-p-anisidine and 2 5- dinitro-p-anisidine (m. .p. of acyl derivatives 180' and 154' respectively); on nitrating in acetic acid in the cold the above- mentioned nitrotoluenesulphonyl derivatives of 3-nitro-p-anisidine and 2 5-dinitro-panisidine are obtained the latter preponderating.D. F. T. Decomposition of Mixed Phenyl Oxides in Presence of Nickel and Hydrogen. ALPHONSE MAILHE and M. MURAT (Bull. Soc. chim. 1912 [iv] 11 122-123).-1t is shown that all phenyl alkyl oxides when passed over heated nickel in a current of hydrogen are decomposed in accordance with the equations (1) C,H,*O*R + H = C,H,*OH + RH and (2) C,H,*O*K. + H2 = C,H + R*OH the alcohol and the paraffinic hydrocarbon formed being destroyed by the further action of the nickel. Anisole is most readily attacked and yields 52% of the possible weight of phenol whilst phenyl isoamyl oxide yields ouly 22%. Diphenyl oxide is attacked with great difficulty and gives only 6% of the possible weight of phenol.Veratrole at 205O yields 16% of the possible weight oE guaiacol and the latter on further treatment at 205' yields a mixture of phenol and catechol. T A. H. [Preparation of p- Aminophenyl Methyl Mercaptole.] AKTIEN- GESELLSCHAFT FUR ANILIN-FABRIKATION (D.R.-P. 239310).-p-Bmino- phanyl methyl mercaptole a colourless oil comparing favourably with phenacetin in therapeutical action is obtained by reducing p-nitro- phenyl methyl mercaptole (Blanksma Abstr. 1902 i 281); the salts are colourless and crystalline and the acatyl derivative forms colourless needles m. p. 127-128'. F. M. G. M. Preparation of 4-Chloro-a-naphthol. AKTIEN-GESELLSCHAFT FGR ANILIN-FABHIKATION (D.R.-P. 240038).-It is found that 4-chloro- a-naphthol can be prepared by treating a-naphthol arylsulphonyl ethers with chlorinating agents.a-Naphthyl p-toluenesulphonate colourless needles m. p. 83-84' prepared by the action of p-toluenesulphonyl chloride on sodium a-naphthoxide in alcoholic solution was dissolved in carbon tetrachloride and treated with chlorine when a satisfactory yield of 4-chloro-a-naphthol (m. p. 116') was obtained. F. M. G. M. 0 2i. 184 ABSTRACTS OF CHEMICAL PAPERS. The Red Coloration Produced in the Ferric Chloride Reaction with Catecbol in Alkaline Solution. I. RUDOLF FRIEDRICH WEINLAND and KARL BINDER (Bey. 1912 45 148-154). -The green coloration of an aqueous catechol solution produced by ferric chloride is changed to deep red on the addition of sodium potassium ammonium barium calcium and magnesium hydroxides.The red coloration is due to the formation of salts of an acid analogous to the ferricyanides or ferrioxttlates. The potassium salt K3[Fe”’(C6H40,),],2H20 is obtained as a lustrous crystalline brownish-black to dark brouze-red powder consisting of microscopic triangular priBms by the addition of ferric acetate to a solution of catechol in strong aqueous potassium hydroxide. It readily dissolves in water to deep red solutions which are decolorised by excess of acid with the liberation of catechol. When heated with sodium sulphide or potassium cyanide in aqueous solution the potassium salt is decomposed yielding ferrous sulphide and potassium ferro- cyanide respectively although in the presence of potassium hydroxide the aqueous solutions may be heated with the substances without undergoing change.The tendency to form salts of the above acid is so pronounced that freshly precipitated ferric hydroxide in the presence of aqueous alkalis or ammonia dissolves on the addition of catechol forming the corresponding alkali or ammonium salt. The ammonium salt ( NH4)3[Fe”’( C6H402)J,H20 prepared in a similar manner to the sodium salt is a brownish-black powder consisting of microscopic fliLt violet-red needles. Tho sodium salt Nas[ Fe’;’(C6H4OJ3] 1 OH,O forms microscopic red hexagonal columns capped with truncated pyramids. The lead salt is precipitated quantitatively on the addition of lead acetate to an aqueous solution of a n alkali salt. The morphine and strychnine salts are crystalline; the quinine and brucine salts are amorphous.Similar complex salts stable towards alkalis are obtained from catechol and aluminium cupric nickel cobalt and manganous salts and also from pyrogallol salicylic gallic or protocatechuic acids and ferric salts in alkaline solution. H,[ ~’”’’(CsH4@2)31 F. B. Derivatives of 4-Amino-orcinol (2-Amino-3 5-dihydroxy- toluene). FERDINAND HENHICH G. TAUBERT and H. BIRKNER (Ber. 1912 45 303-314. Compare Abstr. 1903 i 413).-2-Amino- orcinol has now been isolated in the free condition by the addition of sodium hydroxide t o a cold aqueous solution of the hydro- chloride in quantity just insufficient for complete decomposition. It crystallises from ethyl acetate in lustrous silvery-white leaflets decomposing a t 188-1 go’ with previous darkening at 160-180’.Its hydrochloride is oxidised by chromic acid in aqueous solution to 4-chloro-3-hydroxytolupuinone C O < ~ ~ ~ ~ ~ ~ ~ > C O which forms intensely yellow crystals m. p. 181-182’ volatile in ether vapour dissolves in alkalis yielding intensely red solutions and is reduced byORGANIC CHEMISTRY. i. 185 sulphur dioxide in aqueous solution to 4-chloro-2 3 5-trihydroxytoluene C,H70,CI colourless needles m. p. 137.5'. Acidification of the solutions of the quinone in aqueous ammonia or sodium carbonate results in formation of a substance having the same composition as the original quinone. This substance separates from benzene or chloro- form in yellow crystals darkening a t 220' dissolves in water less readily than the original quinone and is not volatile in ether vapour; but whether these differences are to be referred t o isomerism or polymerism has not yet been determined.That the auinone has the above constitution and not that of the isomeric been established by the synthesis of the latter compound from 2-amino-orcinol hydrochloride. This is converted by amyl nitrite in alcoholic solution into orcinoZ-2-diazoniunz chlo~ide a yellowish- white powder which forms with cuprous chloride a red crystal- line additive compound C,H2Me(OH),*N2CI,Cu2CI2. When heated under diminished pressure the additive compound melts a t SO-go' and decomposes a t a higher temperature into 2-chZoro-orcinol C,H,O,Cl m. p. 138-139O with previous sintering a t 115". The last-named compound reacts with amyl nitrite and potassium hydroxide in alcoholic solution to form the potassium sa.lt of 2-chloro- 6-nitroso-orcinol from which the free nitroso-compound is obtained by acidification with dilute sulphuric acid.2-ChZoro-6-nitroso-orcinol C7H,0,NCI exists in two modifications a stable yellow crystalline form melting a t 159-1 60' with previous darkening and a brown modification which passes into the yellow variety when heated. 2-ChZoro-6-amino-orcinoZ hydrochloride is obtained in slender white needles by reducing the preceding nitroso-compound with stannous chloride and hydrochloric acid. It is oxidised by chromic acid in aqueous solution to 6-chZo~o-3-hydrozytoZuene ruby-red crystals m. p. 165-166' (decomp.). F. B. Constitution of Diisoeugenol. ERNESTO PUXEDDU (Atti R. Accnd. Lincei 1912 [v] 21 i 42-46.Compare Abstr. 1909 i 225).-The paper deals with the action of light on isoeugenol and on its methyl ethyl and propyl ethers as well as the action of light on eugenol and its ethers. The author has also examined the action of nitrous acid on isoeugenol ethyl ether and on diisoeugenol diethyl ether. When a solution of 100 grams of isoeugenol in 200 C.C. of alcohol is treated with 25 C.C. of hydrochloric acid and exposed to light in a sealed tube crystals of diisoeugenol are quickly deposited and if the precipitate is collected after t w o days the yield amounts to 60%. If the filtered solution is again exposed to light a further quantity of the polymeride can be obtained. The mother liquors show a splendid blue fluorescence. Under the same conditions sulphuric acid also acts feebly as a polymerising agent.isoEugeno1 methyl ether isoeugenol ethyl ether and isoeugenol propyl ether yield the analogous polymerides when treated in the same way. isoEugenoZ propyl ether C,,HI,O,,i. 186 ABSTRACTS OF CHEMICAL PAPERS. prepared from isoeugenol with sodium propoxide and propyl iodide crystallises in long prismatic needles m. p. 54O. Diisoeugenol dipropyl ether (G,3H,,0,!2 forms prismatic needles m. p. 94". Eugenol and Its methyl and ethyl ethers under the same conditions are not acted on by light. When isoeugenol ethyl ether is treated with glacial acetic acid and potassium nitrite a substance C,,H,,O,N is obtained which crystallises in yellow tabular prisms m. p. 8 5 O . It is assigned the formula of the peroxide C,H,(OMe)(OEt)*F- -No0 CMe:N*(J' analogous t o that from isoeugenol methyl ether (compare Malagnini Abstr.1895 i 35). Diisoeugenol diethyl ether does not react with nitrous acid and therefore probably does not contain an unsaturated side-chain. R. V. 8. Action of Phorone on Catechol and Pyrogallol. MARIO GHTGLTENO ( A t t i R. Accad. Sci. Torino 1912 4'7 16-22).-Fabinyi and Szdki (compare Abstr. 1905 i 591 888) obtained products by heating acetone with catechol and with pyrogallol in a sealed tube at 145". I n the present paper i t is shown that the formulae ascribed t o these substances are incorrect. Under tbe conditions of experiment the acetone is condensed to phorone which reacts with the phenols giving substances of the following constitutions respectively and C(CH:CMe,),[C,H,( OH),],.This explains the existence of the tetrabromo- and dibromo-derivatives. I n confirmation of this view the authors have prepared the same substances using phorone instead of acetone. It is not necessary to heat the mixture a t 145'; the same products are obtained when phorone and the phenol are heated together in a sealed tube a t looo o r even in an open flask with condenser. I n t h e case of the product from pyrogallol the somewhat discordant analyses of Fabinpi and Szdki are explained by the fact that the substance contains 1 mol. H,O which i t loses completely only at 130-140° and which i t re-absorbs very readily on exposure to air. R. V. S. C(CH:CMe,)*[C,H,(OH),] Action of Formic Acid on Triarylcarbinols. ALFRED GUYOT and A. KOVACHE (Compt.rend. 1912,154 121-122).-Triarylcarbiools are readily reduced when treated with twenty times their weight of crystallisable formic acid giving the corresponding hydrocarbons with formation of water and evolution of carbon dioxide. The reaction may be made use of for accurately determining the number of hydroxyl groups in such carbinols by weighing the carbon dioxide evolved from less than a gram of the substance. Quantitative results were obtained with triphenylcarbinol phenyldi-p-tolylcarbinol o-benzoyltriphenyl- carbinol and 9 10-diphenylanthranol whilst 9-phenylanthrmol and 9 10-dihydroxy-3 10 10-triphenyldihydroanthraceoe gave less than the calculated amount of carbon dioxide although the yield of hydrocarbon was theoretical. w. 0. w.ORGANIC CHEMISTRY.i. 187 The Walden Inversion and Substitution Processes. EMIL FISCHER (Annalem 1912 386 374-386. Compare Abstr. 1911 i 418).-An amplification of the author’s view that the phenomena met with in the addition of halogens or halogen hydracids to stereoisomeric unsaturated compounds are probably of a similar type to the Walden inversion Reactions such as t h a t whereby both inactive dibromo- succinic acids result by the addition of bromine to maleic or to fumaric acid have been regarded by Werner and by van’t Hoff as exceptional and due to a specific action of the halogen. Examples are given however to show that similar results may be obtained by the addition of groups or atoms other than halogens. It is true that the oxidation of cinnamamide by potassium permanganate yields only one phenyl- gZyceYam,ide OH*CHPh*CH(OH)*CO*NH2 m.p. 161-162’ (corr.) (which yields the phenylglyceric acid having m. p. 1 41° by hydrolysis) and the oxidation of cinnamoylglycine gives only one phenylglyceryl- glycine OH*CHPh*CH(OH)*CO*NH*CH,*CO,H m. p. 144-145’ (corr,). However Baeyer has shown that Al-tetrahydrophthalic acid yields two stereoisomeric hexahydrophthalic acids by reduction whilst Fittig has obtained two dimethylsuccinic acids by the reduction of dimethyl- fumaric acid. c. s. Spectrochemical Differentiation between Hydroaromatic Compounds with Endocyclic and with Semicyclic Double Linkings. KARL AUWERS and PHILIPP ELLINGER (Annalen 19 12 38’7 200-239).-Unsaturated hydroaromatic hydrocarbons contain- ing semicyclic double linkings exhibit a moderate exaltation of the specific refraction and a marked exaltation of the specific dispersion. Unsaturated hydroaromatic hydrocarbons containing endocyclic double linkings are optically normal These statements are based not only on the spectrometric examination of the many alkylidenecyclo- paraffins which have been prepared by Wallach but also on a direct comparison of the alkylidenecyclohexanes (methylene- ethylidene- and isopropylidene-cyclohexanes) with the isomeric alkyl-A1-cyclo- hexenes (methyl- ethyl- and isopropyl-cyclohexenes) ; the latter are optically normal whilst the former exhibit an exaltation of 0.28-0.47 of SD and an exaltation of 6-10% of 2 - 8,.The spectrochemical method of differentiating between the two classes of isomerides has been utilised t o show t h a t Sitbatier and Mailhe’s alkylidenecyclohexane derivatives are really unsaturated endocyclic compounds and that Zelinsky and Gutt’s 3-methyl-1 - ethylidenecyclohexane must be on account of its optical normality 3-m e thy1 - 1 -ethyl- Al-cyclohexene. Al-cycZoHexenylacetic acid and its esters and their homologues containing a methyl group in position a 2 3 or 4 are optically normal.cycEoHexylideneacetic acid and its homologues containing a methyl group in position 2 3 or 4 have too high m. p.’s to be suitable for spectrometric examiuation but their methyl and ethyl esters show a marked exaltation 0.79-1.05 of the specific refraction BD and still more pronounced exaltation 31-40% of the specific dispersion S,-8,. These are due not only to the semicyr:lic b u t also to the conjugated double linking.Esters of the acids contain-i. 188 ABSTRACTS OF CHEMICAL PAPERS. ing a methyl group in the a-position contain a disturbed conjugation and therefore show smaller exaltations but even in these cases the exaltations are so pronounced that there can be no uncertainty in distinguishing such esters from those of a-substituted cyclohexenyl- acetic acids. The authors regard the spectrometric method as far safer than any chemical process for the determination of the constitution of such easily changeable substances as cyclohexenyl- and the cydohexylidene- acetic acids. The following new compounds are described; they have been obtained by Wallach's methods as a rule. 1 -isoPro~yZcyclohexccnol C9H,*0 b.p. 176.4-176-7' Dy'5 009142 nu 1.46064 n 1.46419 and ny 1.47387 at 15.5' ; eth$ A1-cyclohexenykctcelate C,H,*CH2*C0,Et b. p. 100'/12 mm. Di62 0,9829 n 1.46422 n 1.46906 ny 1-48017 at 16.2' ; methyl a-1-Aydroxycyclohexylpropionccte OH* C,H,,*CHMe*CO,Me b. p. 132'/18 mm. DY 1.0537 ; methyl a-A'-cyclohexenylpropionate C6H,*CHMe*C02Me b. p. 108-1 08*5'/18 mm. D:'" 0-9864 n 1.46373 n 1.46648 my 1.47885 at 18.3'; methyl 2-nzethylcyclo- Izexylidenecuetute C,H,Me:CH*CO,Me (prepared from methyl iodide and the silver salt of the acid m. p. GS') b. p. 119*9"/15 mm. D:'"'" 0.9'767 n 1.47681 n 1.48072 ny 1.49802 at 14.2'; the corre- sponding ethyl ester has b. p. 128-2'/13 mm. D:"'* 0.9587 n 1.47524 n 1.47906 and ny 1,49639 a t 14 8' ; methyl 3-metl~ylcyclo?~exylidm~- acetate C,HgMe:CH*CO,Me b.p. 117'/13 mm. Di55 0.9752 7~~1.47534 n 1.47926 ny 1.49668 a t 15.5'; the ethyl ester has b. p. 131.4'/ 18 mm. DY 0.9571 n 1.47347 n 1.47730 ny 1.49464 at 15'. c. s. Correlation of I o n i s a t i o n and S t r u c t u r e . 11. Negatively Substituted Benzoic Acids. C. G. YEHICK (-7. Amer. Chem. SOC. 1912 34 74-82).-1t mas shown in an earlier paper (Abstr. 1911 ii 713) t h a t the free energy of ionisation for negatively substituted monobasic fatty acids in aqueous solution at 25'is the sum of the mparate effects of each atom in the molecule. Hence it was demon- strated that the position of a negative atom or group in an acid can be determined if its a-" place factor" and the ionisation constant of the substituted acid a r e known. In the present pager i t isshown that the additive relationship in the free energy of ionisation is also true in the case of aromatic acids and t h a t i t is therefore possible to determine the structure of substituted benzoic acids containing negative groups or atoms if the ortho- meta- and para-'' place factors " are known for each negative radicle.The '' place factors " have been determined for benzoic acid for the acetoxy- carboxy- chloro- hydroxy- and nitro-radicles for the ortho- mettt- and para-positions ; for the aldehydo- benzoyl- bromo- carb- methoxy- carbet,hoxy- iodo- and methoxy-radicles for the ort ho-position ; and for the cyano- fluoro- and iodo-radicles for the meta-position. From these numbers the ionisation constants for the substituted benzoic acids were calculated and agreed closely with the experimental values in nearly all cases,3RGANIC CHEMISTRY.i. 189 There is no simple relation between the '' place factors" for the same radicle substituted in the ortho- meta- and para-positions in benzoic acid. Ionisation mill not differentiate between 2 3- and 2 5-di-substituted benzoic acids in which the substituting radicles in the 3- and 5-positions are the same and those in the 2-positions are also the same. The fact that the 3- and 5-positions are equivalent with respect to the 1-position has been proved in terms of the free energy of ionisation. E. G. Barium Hippurate. EYVIND B~DTKER (Chem. Zed. 191 2 38 105).-Analyses of this salt prepared by neutralising hippuric acid with barium hydroxide crystallising it from water aud drying the crystals between blotting paper show that it contains 5H20.The statement that it. contains only 1H20 may be due to the salt having been dried over sulphuric acid before analysis although the strontium salt. when similarly dried does not lose water. Attempts to prepare Preparation of Cinnamic Esters of Polyatomic Alcohols. Abstr. 191 1 i 858).-P-ChZoroethyZ cinnnnante CHPh:CH.CO,*C,H,Cl a colourless solid m. p. 31' b. p. 188-191'!20 mm. is prepared by the interaction of chloroethyl alcohol and cinnamic acid in the presence of concentrated sulphuric acid; when heated a t 140' with sodium acetate and dilute acetic acid it furnishes glycol cinnarnats b. p. 170-175°/15 mm. ferric hippurate were not successful. w. P. s. FARBENFABRIKEN VORM.FRIEDR. BAYER & CO. (D.R.-P. 239650. Compare y-ChZoro-P-hydroxypropyl cinnamnte CHPh:CH*C02*CH2*CH(OH)*CH2CI a yellowish viscid liquid b. p. 210-218'/20 mm. prepared from monochlorobydrin and cinnamic acid by similar treatment yields glycerol cinnamate. Other weak acids and their salts can replace acetic acid in this reaction. Sodium Phenyl Carbonate as I n t e r m e d i a t e Product of Kolbe's Synthesis for Salicylic Acid. CARL B. SLUITEB (Ber. 1912 45 59-62).-1t has been asserted (de Bruyn and Tymstra Abstr. 1905 i 209; Tymstra Abstr. 1905 i 439) that under the conditions of Kolbe's process sodium phenyl carbonate cannot be an intermediate step on account of its dissociation into carbon dioxide and sodium phenoxide; in their opinion the carbon dioxide molecule inserts itself directly between the carbon and hydrogen atoms in the ortho-position of the sodium phenoxide giving the phenolic sodium derivative of salicylic acid 1*272 Dloo 1.1032) and examines carefully t h e reaction products obtained by heating to 160' with an equimolecular quantity of dry sodium hydroxide (compare Hentschel Abstr.1883 588) in a current of nitrogen. The evolution of carbon dioxide ends after two to three minutes and the residue contains sodium phenoxide sodium carbonate and sodium salicylate with some unchanged diphenyl carbonate. Two reactions are therefore believed to occur concurrently F. M. G. M. The author takes diphenyl carbonate (m. p. 78*2-'78*4" (1) PhO*CO*OPh + 2NaOH = 2PhOH + Na2C0 ;i. 190 ABSTRACTS OF CHEMICAL PAPERS (2) PhO*CO*OPh + NaOH = Ph*OH + PhO*CO*ONa; the sodium phenyl carbonate then partly dissociates into carbon dioxide and sodium phenoxide and partly is rearranged into sodium salicylate.The alternative explanation given above for the formation of the last substance cannot hold in this case as the pressure of carbon dioxide would be quite insufficient for reaction with the sodium phenoxide. It appears therefore that under the conditions of Kolbe's synthesis sodium phenyl carbonate can undergo rearrangement I into sodium salicylat e. D. F. T. Two Phthaloximes and Some of Their Derivatives. WILLIAM R. ORNDORFF and DAVID S. PRATT (Amer. Chem. J. 1912,47,89-125). -It has been shown by R. Meyer (Abstr. 1905 i 440; 1909 i 652) that quinolphthalein yields three oximes of which two are coloured whilst the other is colourless.The coloured oximes were regarded as cis and irans-stereoisomerides and the group CNOH was considered to be the chromophore. In order to ascertain whether this group behaves as a chromophore when present in a five- membered ring a study has been made of phthalylhydroxylamine first described by Lassar-Cohn (Abstr. 1881 585) which the authors prefer to term phthaloxime. The compound was prepared by Lach's method (Abstr. 1883,1104) which consists of heating a mixture of phthalic anhydride hydroxyl- amine hydrochloride sodium carbonate and water for an hour a t 60'. As the reaction product cooled colourless crystals of phthaloxime separated in quantity equivalent to a 70% yield. When the mother liauor was heated a t 100' for one and a-half hours and then left to 1 cool lemon-yellow crystals of an isomeric phthaloxime appeared. These oximes C,H,@$Z?>O both melt a t 220-226' and are slowly decomposed when heated at 110'.Both forms dissolve in alkali hydroxides with the production of red solut'ions which gradually become coiourless owing to the formation of salts of the hydroxamic acid. If the colourless oxime is heated with a solvent containing a hydroxyl group it is partly converted into the yellow isomeride and if boiled for an hour with glacial acetic acid i t is quantitatively transformed into the yellow form. The yellow oxime can be quanti- tatively changed into the colourless variety by boiling it with acetic anhydride the same colourless acetate m.p. 183-185' being obtained in this case as when the colourless isomeride itself is acetylated. When the colourless acetate is treated with a solution of ammonia and afterwards acidified the white oxime is precipitated. A yellow acetate also of m. p. 183-185' can be obtained from the yellow oxime by the action of acetic anhydride at the ordinary temperature. Both oximes yield red ammonium sodium sodium hydrogen potassium hydrogen and silver salts from which the original oxime is regenerated in each case on treatment with acids. When the silver salts are treated with ethyl iodide that of the colourloss oxime yieldsORGANIC CHEMISTRY. i. 191 a colourless ethy2 ether and t h a t of the yellow oxime a lemon-yellow ethyl ether both melting at 95-100'. Each oxime has been submitted t o a crystallographic examination.The colourless oxime forms monoclinic needles elongated in the direction of the b-axis and usually flattened parallel to a pair of faces in the ortho-zone ; the crystals have n 1,522 in a direction parallel t o the elongation. The optical properties of the yellow oxime closely resemble those of the colourless form except in respect of colour. The colour of the yellow variety is due mostly if not entirely to fluorescence. A crystallographic study has also been made of the salts aketates and ethyl ethers. The constitution of these oximes is discussed and evidence is adduced to show that in all probability they are not structural isomerides but stereoisomerides of the formuh ,-co- ,-co- O-R-C,H and O-s-C',H,. E.G. H0.N N*OH RUDOLF PUMMERER and GUSTAV DORFM~LLER (Bey. 191 2 45 292-294).-The transformation of isophthalanil into phthalanil (?o'o>C:NPh -+ C,H4< >NPh takes place slowly at the ordinary temperature as indicated by the rise in m. p. of a specimen of the former compound from 116' to 150' after being kept for six months and also by the isolation of phthalanil from the product. When shaken with concentrated aqueoris sodium carbonate at the ordinary temperature isophthalanil undergoes complete trans- formation in the course of five hours. With dilute sodium carbonate i t is converted after several days mainly into phthalanilic acid only traces of phthalanil being produced ; phthalanil undergoes no change when subjected to the same treatment. The transformation has also been effected by boiling solutions of isophthalanil in pyridine quinoline and nitrobenzene ; with water and light petroleum no change occurs. isophthalanil reacts with benzene in the presence of aluminium chloride yielding o-benzoylbenzanilide.F. B. Simple Fatty Arnines containing Sulphur. WILHELM SCEINEIDER (Annulen 191 2 386 332-350).-The possibility that derivatives of aminosulphones other than cheirolin (met hyl-y-thio- carbimidopropylsulphone) (Abstr. 191 0 i 658) may occur in nature has led the author to prepare aliphatic aminosulphones and the corre- sponding thiocarbimides aliphatic aminosulphides and amino- sulphoxides. [With MAX MULLER and WILHELM BEcK.]-P-Pht~alimidoethyl methyl sulpliide CGEI,<~~>N*CH2*CH2*SMe m. p. 89' prepared from sodium methyl mercaptide and P-bromoethylphthalimide yields by hydrolysis methyl P-arninoethyl suZphide NH,*CH,*CH,*SMe b.p. 146-148O a colourless liquid having the odour of piperidine and strongly basic properties (hydrocldoride m. p. about 120' ; picrate m. p. >119' ; picrolonute decornp. 187' ; oxalate m. p. 197' ; beneoyl isophthalanil. co C,H,- COi. 192 ABSTRACTS OF CHEMICAL PAPERS. derivative m. p. 57'). By treatment with alkali and an excess of methyl iodide it yields not a n NS-dimethiodide as does methyl- y-aminopropyl sulphide (Zoc. cit.) but the methiodide of methyl P-dimethylaminoethyl sulphide SMe-CH,.CH,*N Me,I decomp. 220-5' colourless leaflets which is decomposed by warm alkalis with evolution of trimethylamine. P- PhthalimidodiethyZ sulphide C,H4<CO>N* co CH,* CH,*SEt m.p. 39' yields by hydrolysis fi-aminodiethyl sulphide C,HIINS b. p. 163' (hydrochloride m. p 147'; hydyogen oxalate m. p. 145.5'; picrate m. p. 148' ; pic.r*olonate dlxomp. 184" ; benzoyl derivative b. p. 221-222'/40 mm. [decomp.]). The rnethiodide of /3-dimethyl- nminodiethyl sulphide decomposes a t 21 6.5'. By oxidising its hydrochloride with hydrogen peroxide and treating the product with alcoholic sodium ethoxide methyl P-aminoethyl sulphide yields methyl P-arnircoeth?yl sulphoxide CH,*SO*CH,*CH,*NH which cannot be distilled but is volatile with steam. It forms an oxalate m. p. 165' picrate m. p. 158" and picrolonnts decomp. 205' and is decomposed when treated with methyl iodide. P-Aminodiethyl sulphoxide prepared in a similar manner forms an ozalccte m.p. 176' picrate m. p. 138O picroloiaate decomp. 190° and when heated with the calculated quantities of methyl-alcoholic methyl iodide and sodium carbonate is converted into the methiodide of P dimethylaminodiethyl sulphoxide m. p. 168". Methyl y-arninopropyl suZphoxide CH,-YO*[CH,],*NH forms an oxulate m. p. 197' picrate m. p. 143' and picrolonate decomp. 2 1 O'. Methyl-P-aminoethylsui'phone obtained in the form of the hydro- chloride UH,*SO,*CH,*CH,*NH,,HCl m. p. 169' by oxidising the hydrochloride of the sulphide by potassium permanganate forms a picrate m. p. 167' picrolonate decomp. 325',.platinichloride decomp. 227' and benzoyl derivative m. p. 134' yields the methiodide of methy1.P-dimethylaminoethylsulphone m.p. 220° with methyl- alcoholic methyl iodide a t 120° and is converted into di-P-methyl- suZphonethyZthiocGcrbamide SC(NH.CH,*CH,-SO,Me) m. p. 1 41' by carbon disulphide and into methyl-fi-thiocarbimidoeth ylsulphone S0,Me.C H,*CH,*NCS m. p. 46-47' by Hofmann's method with carbon disulphide. P-Amirtodiethylsulphone prepared as the hydrochloride m. p. 101-102' in a similar manner forms a picrate m. p. 163" picrolonate decomp. 2 1 O' pptinichloride decomp. 227" aurichloride m. p. 197" benxoyl derivative m. p. 86' and thiocarbamide m. p. 141'; the thiocarbimide could not be isolated. [With W ILHELM L~HMANK. ] - Fhthcdimidodimeth y 2 sulphide C,H,<gz>N .CH,*SMe m. p. 114' is obtained from bromomethylphthalimide and sodium methyl mercaptide in alcoholic solution.It is oxidised by hot aqueous potassium permanganate t o the sulphone C,,,H,O,NS rn. p. 203'. Both the eulphido and the sulphone decompose completely when hydrolysed. c. s.ORGANIC CHEMISTRY. i. 193 Chemical Action of Light on Vanillin and its Ethers. ERNESTO PUXEDDU (Atti R. Accad. Lincei 1911 [v] 20 ii 717-723). -When vanillin in solution in alcohol benzeue or other solvents is exposed t o light dehydrovanillin is obtained in smill quantity and no other product can be detected except a viscous oil. Vanillin methyl and ethyl ethers behave differently when exposed t o light in benzene solution the corresponding methyl and ethyl ethers of vanillic acid being formed respectively. R e a c t i v i t y of the Carbonyl Group. HERMANN STAUDINGER (AnnaZen 1912 387 254-255).-A note explaining more fully the pictorial representation of the unsaturation of an atom by the length of the dotted line representing its residual affinity (compare R.V. S. Staudinger and Kon Abstr. 1911 i 876). c. s. Behaviour of A n t i m o n y Trichloride and Tribromide towards certain Oxygenated Organic Compounds. BORIS N. MENSCHUTKIN (J. Russ; Phys. Chem. Xoc. 1911 43 17%-1804).- The concentration-temperature diagrams given by acetophenone or benzophenone wit,h antimony trichloride or t r i bromide are all nearly identical each system being characterised by the formation of one molecular compound which contains 1 mol. of t h e ketone t o 1 mol. of antimony salt and melts unchanged. Each diagram consists of four branches corresponding with (1) the lowering of the m.p. of the ketone by addition of antimony salt (2) the solubility in the ketone of the molecular compound (3) the lowering of the m. p. of this compound by the addition of SbX and (4) the lowering of the m. p. of SbX on addition to it of the molecular compound. Each diagram exhibits two eutectic points. The melting points of the various compounds are SbCl,,COMePh 60.5' ; SbBr,,COMePh 37.5' ; SbCl,,COPh 76' ; SbBr,,COPh 48.5". The eutectic temperatures and the corresponding numbers of ketone mols. ( n ) per mol. of antimony salt are as follows 1st eutectic point. M. p. M. p. System. Ketone. Temperature. n. Temperature. n. SbX,. 2nd eutectic point. SbC1,-COMePh ...... 19.5" 1" 4.05 32" 0.36 73" SbBr3-COMePh ...... 19.5 1.5 3.17 31 0.6 94 SbC13-COPh ........ 48 35 4.63 39 0-26 73 Sb Br,-CO Ph . . . . . . . . 4 8 29 2.82 40 0.5 94 Benzoic acid (m. p. 120') forms a molecular compound with neither antimony trichloride nor tribromide the concentration-temperature diagram consisting in each case of two branches meeting at the following eutectic points SbC1,,0-52Ph-C02H 46' ; SbBr3,O-42Ph*CO,H 79". The system SbC1,-CH,*CO,H gives a molecular compound which forms only with dificulty. The first branch of the curve terminates at the eutectic point - go corresponding with the composition SbCI3,3.13CH,*CO,H. Then begins the curve of solubility of the molecular compound in acetic acid but this is observable only on seeding with the molecular compound; unless this is done branch 1 is prolonged below the eutectic point and probably meets branch 4 ini.194 ABSTRACTS OF CHEMICAL PAPERS. another eutectic point. Branch 1 shows no arrest corresponding with the eutectic point CH;CO,H-SbCl,,C H,*CO,H as the compound is not formed on cooling the solution. Branch 3 cuts branch 4 (lowering of m. p. of SbC1 on addition of CH,*CO,H) at the eutectic point about 19' corresponding approximately with SbC13,0-94CH3*C02H ; branch 3 can be followed below this eutectic point but then represents an unstable condition. The system SbBr,-CH,*CO,H forms no molecular compound the curve consisting of two branches meeting a t the eutectic point 4O which corresponds with SbBr,,4-34CH,*CO2H. Benzoyl chloride forms no molecular compound with antimony chloride or bromide each curve showing a single eutectic point SbC13,1.95Ph*COC1 - 33' and SbBr3,5.45Ph-C0C1 - 6'. T.H. P. The Reduction of Poly-unsaturated Ketones with Crossed Double Linkings by Paal's Method WALTHER BORSCHE (Ber. 19 12 45 46-53).-The author has already successfully applied Paal's reduction method to the preparation of saturated ketones from such unsaturated ketones as cinnamylideneacetone (Abstr. 191 2 i SSO) and now extends the investigation to ketones in which each of the two carbon atoms adjacent to the carbonyl group has a double linking. The results indicate that where there is only one double bond on each side of the carbonyl group the reduction proceeds smoothly but that in other cases there is considerable formation of resinous substances as by-products. The reduction of distyryl ketone yields di-/I-phenylethyl ketone b.p. 224'/18 mm. ; the oxime melts a t 95-96' (compare Diinschmann and von Pechmann Abstr. 1891 674) ; a small quantity of a substmce C34H3402 m. p. 126' was also obtained. Di-p-methoxystyryl ketone is reduced to a€-di-p-methoxyphenylpentan-y-one which crystallises in needles m. p. 52". Di-o-hydroxystyryl ketone gives aedi-o-hydroxyphenylpentan-y-one a viscid m a s which when heated loses water with the formation of tetra- hydrodibenxospiropyvan (compare Decker and Felser Abstr. 1908 i 906) which crystallises in needles m. p. l l O o b. p. 217"/16 mm. 1 3-Dibenzylidenecyclopentan-2-one gives 1 3-dibenzyZcyclopentan-2- one as an oil b. p. 232-233' which slowly crystallises in needles m. p. 47'. I n a similar manner 1 3-dibenzylidenecyclohexan-2-one and 1 3-dibenzylidenecycloheptan-2-one give the corresponding 1 3- dibenzylcgclohexan-2-one m.p. 11 4' and 1 3-dibenxyZcycloheptan-2-one b. p. 261-262'/28 mm. Yhenyl cinnamylidenemethyl ketone produces phenyl 6-phenylbutyl- ketone b. p. 225-226'; the oxime forms prismatic crystals m. p. 81-82' and by the Beckmann rearrangement changes into the aniEide of 6-phenyZvaZeric acid m. p. 84-90'. Styryl cinnamylidenemethyl ketone gives av-diphenylheptan-y-one b. p. 239'114 mm. ; the semicarbaxone is an oil whilst the hydrazone phenylcarbamate CH,Ph*CH,*C( N*NH*CO*NHPh) [CHJ,*CH,Ph has m. p. 122-123'. Dicinnamylideneacetone gives ai-diphenylnonan-€-one (6-phenylbutyl ketone) an oil b. p. 258-260'/13 mm. which solidifies in a freezingORGANIC CHEMISTRY. i.195 mixture ; the oxime and semicarbaxone are liquids whilst the hydrazone phenylcarbamate forms silky needles m. p. 129-130'. 2 6-Di-ciunamylidenecyclohexanone gives 2 6-di-w-phenylpvopy Z- cyclohexanone as a viscous oil b. p. 276-278'. D. F. T. Synthesis of Butin. A. GOSCHKE and JOSEF TAMBOR (Ber. 1912 45 186-188. Compare Abstr. 1912 1 30).-The authors have succeeded in transforming synthetic butein into butin (compare Perkin and Hummel Trans. 1904 85 1459) thus completing the synthesis of both these natural products. Butin triacetate has m. p. 123'. By the action of 3 4-dimethoxybenzaldehyde on resacetophenone and resacetophenone dimethyl ether respectively they have prepared the 3' $-dimethyl ether of butein (m. p. 203') and butein tetramethyl ether (m. p.89'). 2' 4' 2-Trihydrox~chc~Zkone prepared by condensation of salicyl- aldehyde with resacetophenone crystallises in orange needles + 1 H,O and has m. p. 185'. Its transformation into 3 2'-dihydroxyflavanone appears to be difficult. H. W. Preparation of Benzanthrone and its Derivatives. ROLAND SCHOLL (D.R.-P. 239761).-When aromatic mono- or poly-ketones containing a free peri-position with regard to the carbonyl group are heated at about 140-150' with either aluminium chloride or bromide or ferric chloride condensation occurs yielding benzan throne or py ran throne derivatives. The following compounds have been prepared Beneanthrone from phenyl a-naphthyl ketone. Naphthabenxanthrone f rom 1 1'-dinaph- thy1 ketone which can be prepared by the interaction of naphthoic acid with naphthalene in the presence of aluminium chloride.Uibenzoylpyvene (I) m. p. 155" and tribenxoylpyrene m. p. 235-237' are prepared by the action of benzoyl chloride on pyrene in the presence of aluminium chloride and separated by fractional crystallisa- tion from acetic acid; when the former is heated a t 160' with aluminium chloride it yields pyranthrone (Abstr. 1910 i 271). 2%-a-naphthoylpyrene m. p. 2 18-2 1 go prepared from pyrene and a-naphthoyl chloride furnishes naphthapyranthrow. Dibenzoyl-1 l'-dinaphthyl obtained from 1 1'-dinaphthyl and benzog 1 chloride furnishes uiokanthren (11) a violet powder whilsti. 196 ABSTRACl'S OF CHEMICAL PAPERS nap~~thylanthraqzcinony~ ketone (from anthraquinone-2-carbonyl chloride and naphthalene) gives phthaloylbenxanthrone and m-tolyl-1-naphthyl ketone yields methylbe~zxantl~rons brownish-yellow needles m.p. 164-1 65". F. 31. G. M. Ketones Derived from isoMyristicin. EVERARDO SCANDOLA (Atti R. Accud. Lincei 1912 [v] 21 i 47-54).-The author has prepared the a- and P-keto-derivatives of isomyristicin and has attempted to obtain the dimeric form of isomyristicin. The a-ketone is prepared by heating together for some hours the dibromo-derivative of isomyristicin (Thorns Abstr. 1904 i 47) and sodium methoxide removing the excess of methyl alcohol and distilling the residue with steam. After fractionation in a vacuum of the oil which passes over the pure a-keto-derivative of isomyristicin C,,H120 is preferably obtained by way of the semicarbazide or oxime.It crystallises in small silky needles m. p. 93". It yields a crystalline bisulphite compound which does not melt below 330". The oxime C,,H1,O,N crystallises in very small prisms m. p. 124". The semicarbaxone C12H,,04N has m. p. 180". The ketone does not give an hydroxamic acid with Piloty's acid. The /3-ketone of isomyristicin was prepared by Hoering's method (Abstr. 1905 i 902) When the dibromo-derivative of isomyristicin is heated with water and acetone in the presence of calcium carbonate (marble) for two hours the acetone solution separated and heated for a further two hours and then distilled P-bromo-a-~~yclroxydi17Lydroiso- myristicin C,,H,,O,Br is obtained. It is a very dense yellowish- brown oil with a pungent odour and it cannot be crystallised or distilled in a vacuum.On treatment of this substance with alcoholic potassium hydroxide a glycol OH*CHR*CHMe*OH should be produced from which the oxide Ar*CH*CHMe and finally its isomeride the P-ketone Ar*CH,*COMe could be obtained. Actually the raw product of the reaction does not combine with bisulphite and it gives analytical figures intermediate between those required by the glycol ClIH140 and the oxide Cl1Hl2O4 but when it is distilled i n a vacuum most of it passes over at 230-240°/30 mm. ; the distillate readily crystallises and has m. p. 44-45'. After recrystallisation it forms long silky needles m. p. 54-55",-and gives on analysis numbers corresponding with the formula C,,H1,04. This substance gives a bisulphite compound and is evidently the @ketone.The isomerisation of the oxide is best effected by heating the substance in glacial acetic acid with a few*drops of concentrated sulphuric acid and purifying the product by way of the bisulphite compound. The semicarbuaone C,,H?,O,N has m. p. 143-144". The ozime C,,Hl,04N crystal- lises in tufts of prisms m. p 111-112". The &ketone was also prepared by reduction of P-nitroisomyristicin and hydrolysis of the oxime produced. Numerous attempts were made by various methods to polymerise isomyristicin. I n only one case was any new product obtained. When isomyristicin is heated for five to ten minutes in glacial acetic acid solution with a trace of concentrated sulphuric acid a substance '0'ORGANIC CHEMISTRY. i. 197 is obtained which crystallises in small prisms m.p. 232-233* and may be the dimeric form of isomyristicin. The yield is less than 2%. R. V. S. Constitution of Chrysophanic Acid. EUGBNE LPGER (Compt. rend. 19 12 154,281-283. Compare Robinson and Simonsen Trans. 1909 95 1085 ; Oesterle Abstr. 1911 i 887).-In order to deter- mine the position of the methyl group in chrysophanic acid the tetra- nitro-derivative was oxidised with nitric acid (D 1.5). 2 4 6-Trinitro- 3-hydroxybenzoic acid was isolated from the products but chrysammic acid could not be detected. It follows that the nitro- and hydroxy- groups in tetranitrochrysophanic acid occupy the same positions as they do in tetranitroaloe-emodin and therefore that the methyl group in chrysophanic acid can only occupy the position assigned to it by Fischer Falco and Gross (A.bstr.1911 i 309). Chrysophanic acid is therefore 1 8-dihydroxy-3-metbylanthraquinone. This conclusion is confirmed by fusing the acid with potassium hydroxide when 5-hyclroxy- isophthalic acid is formed together with a much smaller amount of 4-hydroxyisophthalic acid and other substances. w. 0. w. Preparation of Anthraquinone Derivatives Containing Sulphur. EARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 239$62).-When d iazot.ised arninoanthraquinones are treated with thio- carbaruides intermediate compounds are formed which evolve ammonia on treatment with potassium hydroxide and furnish the corresponding mercap tan. Carbain yZtf&iola?zthrapuiizone C,,H,O,*S* CO-NH orange yellow crystals was prepared from a-aminoaithraquinone a,nd thio- carbamide whilst with phenylthiocarbarnide a similar compound was produced.F. M. G. M. [Preparation of Benzoylaminoan thraquinone Derivatives.] FAXBWERKE ,VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 240079).- The preparation of benzoylaminoan tbraquinones and their condensa- tion products has previously been described ; it is now found that more valuable colouring matters are produced by employing nitrobenzoyl chlorides subsequently reducing the nitro-group and combining with another molecule of benzoyl chloride before condensing to form the dye. BenxoyZ-p-anzinobenzoy?- 1 -annzinoant?waquinone yellow crystals m. p. 3 1 5 O is prepared by benzoylating p-aminobenzoyl- 1 -aminoanthra- quinon e in nitro benzene solution ; benxo yl-p-aminobenxoyl-2 -amino- anthraquinone has similar properties.The tinctorial properties of the following final condensation products are tabulated in the original ; p-aminobenzoyl-1-aminoanthraquinone with succinic acid m. p. above 300' with anthraquinonecarbonyl chloride m. p. 280° and with 2-anthraquinonylcarbamyl chloride m. p. above 300'. p-Aminobenzoyl-2-aminoanthraquinone with 2-anthraquinonylcarb- amyl chloride. na-Aminobenzoyl-1-aminoanthraquinone with 2-anthraquinonylcarb- amyl chloride m. p. 285'. VOL. CII i. 23i. 198 ABSTRACTS OF CEEMICAL PAPERS. 3 5-Diaminobenzoyl-1-aminoanthraquinone with 2-anthraquinonyl- Benxoy Zaminoanthraquinonecarboxy - 1 -aminoantlwaquinone has m. p. carbamyl chloride (2 mols.) m. p. 235'. above 300'. F. M. G. 31. Preparation of o-Aminodianthraquinonylamine Types of Compounds.FARBENFABRIKEN VORM. FRIEDR BAYER & Co. (D.R. -P. 240276).-The poduct (annexed formula) dark blue needles was prepared by boiling together l-amino- /\/CO\/\ 4-hydroxyanthraquinone (10 parts) I I 1 1 naphthalene (1 00 parts) anhydrous \ / \ c o / \ p sodium acetate (5 parts) copper NH I powder (0.2 part) and slowly adding /\/"\/\ 2 - bromo - 1 - aminoanthraquinore (5 I I ' parts); when the latter component is '\/""\/ replaced by 2-bromo-1-methylamino- anthraquinone a similar compound is obtained likewise from a-amino-4-hydroxyanthraqninone with 1 3-di- bromo-2-aminoanthraquinone and from a-aminoanthraquinone with 2- bromo-1-aminoanthraquinone. OH F. M. G. M. A Supposed Compound of Camphor and Naphthalene. JOUNIAUX (Bull.SOC. chim. 1912 [iv]. 11 129-132).-When naphthalene containing increasing quantities of camphor is melted and allowed to cool the temperature at which solidification begins falls steadily from 80' to 32-59 a t which point the mixture contains 58 mols. of camphor to 42 mols. of naphthalene ; a similar fall reaching the same point at the same composition occurs when increasing quantities of naphthalene are added to camphor. For every mixture the finishing point of solidification is 32.5'. I n view of these facts Girard's surmosed comnound of these two substances L L * ~ ~ l ~ ~ l ~ ~ ~ l * ~ m. p. 32.6O (J. Pharm. Chim. 1891 [v] 24 lOS) appears to have been a eutectic mixture. T. A. H. Constitution of isoFenchocamphoric Acid and of Some Compounds of the Fenchone Series.OSSIAN ASCHAN [with w. SJOSTROM and A. PETERSON] (Annulen 1912 387 1-85).-The fractions obtained from a very large quantity of pinolene b. p. below 150' (Abstr. 1907 i 630) have been separately oxidised by 8% potassium permanganate at 60-80' whereby carbonic oxalic and dl-camphoric acids are produced. From these facts and from the molecular refractions of the various fractions the author deduces that pinolene contains at least three hydrocarbons (i) r-bornylene b. p. 148-149O m. p. 40-42O which yields &Z-camphoric acid by oxida- tion; (ii) a-pinolene b. p. 144-146" a dicyclic terpene and (iii) p-pinolene (cyclofenchene) C10H16 a tricyclic terpene which probably contains a trimethylene ring on account of its stability towards potassium permanganate.P-Pinolene (cyclofenchene) obtained from the pinolene fractions b. p. 24@-142° and 142-144" by oxidation as above has b. p.ORGANIC CEEMISTRP. i. 199 141&-143.5° Dfo 0.8588 [.ID + 0-28' and n2,0 1.44769 ; its molecular refraction therefore exceeds by aboiit 0.6 the value calculated for a tricyclic terpene a fact which furnishes additional evidence for the presence of a trimethylene ring. By further prolonged oxidation with potassium permanganate P-pinolene yields a very small quantity of isophthalic acid. This may be due to the presence of a little a-pinolene ; its formation however shows that the pinolene hydrocarbons can be converted into benzene derivatives of the meta-series P-Piuolene in dry ether at - 15' forms an unstable crystalline hydrochloride a-Pinolene hydrochloride m.p. 38O has been previously described as pinolene hydrochloride (Eoc. cit.). a-Pinolene probably has the annexed formula; the halogen atom in its hydro- CRI,*CH-CH chloride is attached to the CMe group. I P-Pinolene is unchanged by eight hours' boiling I yMe2 1 with 2076 sulphuric acid but when heated for four CH,*C=-CMe hours with 96% alcohol and 96% sulphuric acid yields a dicyclic ether C,,,Hl7*OEt b. p. 1 97-200° DSo 0.8904 nz 1.45217. Fractions b. p. 144.5-146' and 146-148' respectively of un- oxidised pinolene purified P-pinolene and also isopinene have been separately treated at 60-7'0" with glacial acetic and 50~; sulphuric acids by Bertram and Walbaum's method and the resulting acetates have been hydrolysed. I n each case the main product is dE-isofenchyl alcohol (m.p. 43-44') identified as the phenylurethane m. p. 95-96'. I n the case of the fraction b. p. 146-148' a little isoborneol is obtained (produced probably from the r-bornylene) whilst from the purified P-pinolece a mixture of dl-isofenchyl and db-fenchyl alcohols is formed. By oxidation with potassium permanganate therefore the mixture yields dl-isofenchone and dl-fenchone in addition to the chief product dl-isofenchocsmphoric acid (Wallach Abstr. 1908 i 809). These facts prove that db-isofenchyl alcohol is the chief product of the hydratisation of the mixture of fenchenes (consisting mainly of isopinene) obtained from a- and P-pinolenes. A diagrammatic representation of the transformations is given. A description is given of the preparation in quantity and the purification of dl-isofenchocarnphoric acid.It is best obtained from the pinolene fraction b. p. 140-150" which is converted into iso- fenchyl alcohol as above; the alcohol is then oxidised by alkaline 5% potassium permanganate without warming. The constitution CH,< CH(Co2H)-~Me2 is ascribed to isofencho- CMe(C0,H) CH camphoric acid on the following grounds. The saturated dibasic acid readily forms an anhydride m. p. 94-95'' by distillation or by treatment with acetyl chloride ; the acid therefore has the cis-con- figuration From the anhydride the anilic mid C0,H*C,H,4;CO*NHPh rn p. 191-192' ethyl ester C,H,,(CO,Et) b. p. 267-268' Di0 1.0054 n 1.44626 methyl hydrogen ester M. p. 72-74' and ethyZ hydrogen ester b. p.289-292' (decomp.) are prepared. The distillation of the C,,-,H,,,HCl m. p. 27*5-29' P 2i 200 ABSTRACTS OF CHEMICAL PAPERS. calcium salt C10H1404Ca does not produce a cyclic ketone indicating that the acid is a substituted succinic or glutaric acid. When heated with acetic and hydrochloric acids at 180' for ten hours dl-cis-isofenchocamphoric acid is transformed into the less soluble trans-isomeride m. p. 169-1705' ; hence one of the carboxyl groups is attached directly to a ring carbon atom. When dl-cis-isofencho- camphoric acid is treated with phosphorus pentachloride and tlhe product is brominated as in the case of camphenic acid (Abstr. 1910 i 709) two stereoisomeric a-bromoisofertchocamp~oric acids C H Br(C02H)2 m. p. 208-210' and 1 6 0 s 1 f 2 ° respectively are obtained.(The author's explanation of the production of the two stereoisomerides is given below.) The former acid which is the main product yields an anhydride m. p. Y 7 O and an ethyl ester b. p. 155-156'/5 mm. Dii 1.2425 and by reduction with zinc and acetic acid regenerates &-cis-isofenchocamphoric acid. The introduction of only one bromine atom even when an excess of the halogen is employed indicates that there is only one hydrogen atom in the a-position to a carboxyl group whilst the formation of the two stereoisomerides is regarded as evidence that the carbon atom to which this hydrogen atom is attached forms part of the alicyclic ring. Other facts in harmony with the preceding constitution of isofenchocamphoric acid are the following. When heated with aqueous sodium carbonate or barium hydroxide the a-bromo-acid m.p. 208-2 1 Oo yields isofeencholauronolic acid co2H*C~~e<CH2.CMe,' m. p. 44-45' a-JLydroxyieofencJLocam- phoric acid C,H,,(OH)(CO,H) m. p. 185-1 86' (decornp.) and dehy~roisofenchocamphoric acid CsHI2( CO,H) m. p. 189-1 90' ; methods for the separation of these throe acids are described. The same three acids are produced by the action of aqueous barium hydroxide on the a-bromo-acid m. p. 160-162O. When heated above its m. p. or warmed with 50% sulphuric acid a-hydroxyisnfencho- camphoric acid is converted into the lactonic acid is0 fenchocamphanic CH=C]H acid C7H1,<C(C0 co-- HI>O m. p. 177' which is also produced by \ d I heating the a-bromo-acid m. p. 208-210° with quinoline at 160' (best method) and is re-converted into a-hydroxyisofenchocamphoric acid by boiling 10% potassium hydroxide.a- Hy droxyisofenchocamphoric acid is oxidised by lead dioxide and acetic acid to isofenchocanzplhononic acid m. p. 68-70' which forms a eemicar~~zo~e,*Cl~H1703N~ m. p. 221'. Finally the fusion of a-hydroxyisofenchocamphoric acid with potassium hydroxide at the lowest possible temperature yields formic acid and an acid C,H1,O m. p. 192-193O which is regarded as identical with Michailenko and Jaworski's aayy-tetramethylglutaric acid m. p. 185-189" on account of its stability towards bromine and the forma- tion of an anhydride m. p. 88O and p-toluidino-acid CO,H.C,H,;CO*NH*~,H m. p. 160-161'.ORGANIC CHEMISTRY. i. 201 alcohols by fission of the trimethyl- Although this explanation is equally applicable t o transformations of the maleic-furnsric acid type the author prefers in such cases Wislicenus' explanation because the additive capacity of an ethylenic linking sogreatly exceeds that of the carbony1 group in a carboxyl Constitution of Camphene.KARL AUWERS (Annalen 19 12 group. c. 8. 38'7 240-253).-See this vol. ii 214. The Constituents of Ethereal Oils (Derivatives of Natural Cedrene). FRIEDRICH W. SEMMLER and FELIX RISSE (Ber. 1912 45 355-360. Compare Semmler and Hoffmann Abstr. 1907 i 946).-Natural cedrene has been oxidised on a larger scale than previously by the action of ozone The main neutral products are a ketone C,,H2,0 or C,,H,,O b. p. 120- 1 30°/1 3 mm. (semicarbazone m. p. 218') and the ketonic aldehyde CI5HP1O2 (Zoc.c i t . ) ; the chief constituent of the acidic portion of the oxidation product is cedrene- ketonic acid (Zoc. cit.) b. p. 205-215°/10 mm. (methyl ester b. p. 165-170°/10 mm. D20 1.0509 nD 1.4882 aD - 32.4" at 20'). The ketonic acid is probably a methyl-ketonic acid as it is oxidisable by sodium hypobromite to the dibasic acid cedrenedicccrboxylic acid m. p. 182.5'; the methyl ester (Zoc. cit.) has b. p. 179-183'/13 mm. D20 1.07'78 n 1.48084 aD - 31.6'. C . J. ENRLAAR (Chern. Weekblad 1912,9 68-72. Compare Abstr. 1909 i 690)-A descrip- tion of a method for the preparation of labile hydrocarbons of the D. F. T. Synthesis of an Aliphatic Terpene.i. 202 ABSTRACTS OF CHEMICAL PAPERS olefine series from tertiary alcohols of the formation of a n aliphatic terpene by the dehydration of linalool and of the behaviour of this product on hydrogenation and ozonisation.When linalool is brought into contact with active copper at 130-140' in a rapid current of carbon dioxide the formation of a cyclic hydrocarbon is in large measure obviated the main product being an aliphatic hydrocarbon. The copper was obtained in a very active condition by reducing copper oxide with hydrogen the oxide being prepared by gentle ignition of copper nitrate. The excess of hydrogen was expelled by carbon dioxide a t 170'. The hydrocarbon was separat4ed from the unchanged linalool by repeated vacuum distil- lation filially over sodium. Acraldehyde geraniol and citral were by-products. The same hydrocarbon was obtained by heating linalool with phenyl- carbimide 2CO:NPh + CloH,,O = CO(NHPh) + C,,H + CO,.The yield is best with a slight excess of linalool and a temperature of 150-170° a non-volatile brown oil being obtained as by-product. When the carbimide was in excesg the proportion of this oil was increased by 50%. The hydrocarbon had D15 0*811. The substance was not obtained quite pure but the following physical constants are given D15 0.802 ng 1,470 b. p. 62'/14 mm. hence it is probably myrcene. Reduction with nickel and hydrogen a t 130' and fractionation of the product yielded a decane b. p. 159-160'/760 mm. (uncorr.) D15 0.739 identical with P[-dimethyloctane obtained from ocimene (Abstr. 1908 i 664). Reduction with sodium and alcohol yiolded a hydrocarbon with the odour and b.p. (165-167') of dihydromyrcene. This substance probably has the formula CIOHIS because bromination by Baeyer and Villiger's method yielded a crystalline bromide m. p. 88O which produced no depression in the m. p. of dihydro-ocimene tetra- bromide (compare Rec. trav. chim. 1907 26 167 and 2'7 448). Ozonisation of the terpene by the method previously described (ibid. 1908 27 422) precipitated an explosive oxonide inflamed by concentrated sulyhuric acid and decomposed by water with formation of acetone probably succinic acid and other products not identified. The impure hydrogenation product yielded an oxonide with similar properties. The liquid obtained by the action of water gave the pyrrole reaction distinctly and probably contained acetone peroxide. It is a liquid D15 0.804.A. J. W. Reduction of Sabinene. OTTO WALLACH (Chem. Zentr. 19 1 1 ii 1802 ; from Nachr. K. Ges. Wiss. Gottingen 191O7544).-In the presence of metallic catalysts sabinene takes up 2 atoms of hydrogen with the - - >CH having b. p. CH*CHMe CH2<t?pr-C H. formation of dihydrosabinene 1 156-157' D20 0.8120 Vt'$' - 2'2'. w. P. s. Leaf-Oil of the Washington Cedar (Thujs plicata). ROBERT E. ROSE and CARL LIVINGSTON (J. Amer. Chern. SOL 1912 34 201-202).-As only a superficial examination of the oil obtained from the leaves of Thuja plicata (Brandel Pharm. Rev. 26 248) has hithertoORGANIC CHEMISTRY. i. 203 been made [compare however Elasdale Abstr. 1907 i 6301 a detailed study has now been carried out. On distillation with steam the leaves and twigs yielded about 1% of light yellow oil which had a cedar-like odour Dm 0.913 n? 1.4552 [a] - 4.77O ; acid number 0.518 ; ester number 2-25 ; saponification number 2.8 and acetylation number 8.8.The product was free from phenols soluble in all proportions in 70% alcohol and about 55% of it boiled at 100-110°/40 mm. The oil contains tanacetone S0-55% pinene 3-5% tanacetyl acetate 1-2% and tnnacetyl alcohol 1-3%. E. G The Chemical Degradation of Chitin. Huao BRACH (Biochem. Zeitsch. 1912,38,468-491).-A description is given of the preparation of the material from Nephrops norvegicus. The analyses showed that the substance had a composition corresponding with the formula C32H54021N4. The estimation of the acetyl groups by a modification of Wenzel's method which is described by the author showed that for each nitrogen in the atom there exists an acetyl group.The results indicate that the simplest formula for chitin is one made up of a complex of four acetylglucosamine groups. Lenk's chitosan appears to be formed from chitin by the scission of half the acetyl groups. By the action of nitrous acid the whole of the nitrogen in the molecule can be eliminated a fact which the author shows does not contradict the assumption of the presence of acetylamino-groups. S. B. S. Constitution of Rhein. OTTO A. OESTERLE (Chem. Zentr. 1912 i 142-143 ; from Schweiz. Woch. Chem. Pharm. 1911 49 661-665). -Contrary to the view of the author and Riat (Abstr. 1909 i 946) that aloe-emodin and its most nearly related derivatives are derived from 1 8-dihydroxyanthraquinone (chrysazin) Robinson and Simonsen (Trans.1909 95 1085) regard 1 6-dihydroxyanthra- quinone (isozhrysazin) as the parent substance of rhein. The author therefore has converted rhein through rhein chloride yellow needles and the amide dark red needles into an aminodihydroxy- anthraquinone C,,H,O,N m. p. 255' or 25S0 red needles from which by elimination of the amino-group impure 1 8-dihpdroxyanthra- quinone m. p. 182-183° instead of 191-192' (acetate m. p. 232'). has been obtained. c. s. Phylloxanthin. LEON MARCHLEWSKI (Ber. 191 2 45 24-25).- The phylloxanthin described by Schunck (Abstr. 1885 1241) is shown to be identical with allochlorophyllan (Marchlewski and Marszatek Abstr. 191 1 i 735). Phylloxanthin yields 30.02% of phytol instead of 31.8%.On prolonged exposure to concentrated hydrochloric acid phylloxanthin is converted into basic products including a substance soluble in 20% hydrochloric acid. A more recent preparation of phylloxanthin gave a solid substance instead of phytol on hydrolysis. E. F. A. Tannin. VIII. MAXIMILIAN NIERENSTEIN (Annalen 19 12 386 318-332. Compare Abstr. 1910 i 265).-Purpurotannin thei. 204 ABSTRACTS OF CHEMICAL PAPERS. amorphous red oxidation product of penta-acetyl-leucotannin (Abstr. 1909 i 402) has the composition C,,H,O forms a puinoline salt C,,H,0,,2C,NH7 dark red needles and dissolves unchanged in boiling 2N-potassium hydroxide. It forms a tetra-acetate m. p. 324-3.27" (decornp.) tetrabenxoate m. p. 279-281' C0,H C0,H (decornp.) and tetramethyl ether C1,H,O,(O~~e),,H,O ene not naphthalene as stated (Zoc.cit.) by m. p. 242-244" (decomp.) and yields diphenyl- HO 0 OH distillation with zinc dust. It is shown to be 1 2 7 ; 8 - tetrahydroxydiphenyleneoxide - 4 5 - dicnrboxylic acid (annexed formula). When heated with piperidine (but not with quinoliue) a t 180° i t yields 1 2 7 8-tetrtchyh.oxy- diphenylene oxide CI2HSO5 red needles m. p. 334-338" (decornp.) (tetra-acetate m. p 247-251") whilst by reduction with hydriodic acid and phosphorus at 180" it is converted into diphenylene oxide. A course of formation of purpurotannin from leucotannin is suggested. The cause of its colour will be discussed later ; apparently i t is connected with the presence of hydroxyl groups in the peri- position to the oxygen of the furan ring.c. s. u Luteo-acid " (A Correction). MAXIMILIAN NIERENSTEIN (Ber. 1912 46 365).-l'he analytical results for the composition of " luteo- acid" (pentahydroxydiphenylmethylolidecarboxylic acid) (Abstr. 1908 i 897 ; 1909 i 174 ; 1910 i 265 389) were low in the percentage of carbon ; as the more carefully dried substance gives results agreeing well with the formula C,,H,O i t is proEable that the earlier discrepancies were due to occluded solvent,. D. F. T. Decomposition of Alkylidenehydrazines. Conversion of Furfuraldehyde into 2-Methylfuran. NICOLAI RI. KJJNER (J. Buss. Phys. Chem. SOC. 1911 43 1563-1565).-When heated in presence of a small quantity of potassium hydroxide fui furylidene- hjdrazino decomposes giving nitrogen ar;d 2-methylfuran a colourless liquid b.p. 64"/757 mm. D;'' 09159 n 1.4344. The constants given for this compound by Atterberg (Abstr. 1880 663) and by Harries (Abstr. 1898 i 232) are inaccurate doubtless on account of impure products being examined. T. H. P. Coumerandione the Oxygen Analogue of Isatin. KARL FRIES and W. PFAFFENDORF (Bey. 1912 45 154-162. Compare Abstr. 1910 i 186; also Stoermer ibid. 1909 i 174 and following aEstract,).-Coumaran-l 2-dioae C,H,<$>CO is readily prepared by heating a solution of o-hydroxpphenylglyoxylic acid in light petroleum with phosphoric oxide or by distilling the acid under diminished pressure. I t crystallises in large yellow prismatic plates m. p. l34" b. p. 142'/17 mm. and dissolves in concentrated sulphuric acid yielding a yellowish-red solution which gradually becomes colourless owing to the loss of carbon monoxide arid conversion of the diketone into salicylic acid.ORGANIC CHEMISTRY.i. 205 With o-phenylenediamine it yields 2-hydroxy-3-hydroxyphenyl- quinoxaline (Marchlewski and Sosnoweki Abstr. 1901 i 415). On exposure to air it takes up water with the formation of o-hydroxy- phenylglyoxylic acid or its hydrate m. p. 43'. When heated at 220' under ordinary pressure it loses carbon monoxide yielding a ruby-red glassy mass which sinters at 150° forms a transparent viscid liquid at 200° and finally becomes mobile at 240'. The latter substance is hydrolysed by alkalis i n alcoholic solution to salicylic acid and gives a colloidal solution in chloroform. It probably consists of a polymeric salicylide which however is different from the polymerides described previously.Ethyl o-hydroxyphenylglyoxylnte ClpH1004 prepared by boiling coumarandione in alcoholic solution IS a yellow 011y liqnid which solidifies in a freezing mixture m. p. 15'. It readily loses alcohol yielding the original ketone. Cowmcwan - 1 2 - dione-2-phenyZhyd~ccxone O<!bEf>C:N*NHPh obtained from its components in glacial acetic acid solution crystallises in lustrous yellow plates m. p. 185' and is hydrolysed by alkalis in alcoholic solution to the phenylhydrazone of o-hydroxyphenylglyoxylic acid C,,H,,O,N,. This crystallises in light yellow needles m. p. 148' (decornp.) and is also obtained by heating o-hydroxyphenyl- glyoxylic acid with phenylhydrazine in aqueous solution.It readily loses water yielding coumarandione-2-phenylhydrazone. The a i d of o-hydroxyphenylglyoxylic acid C,,H,,O,N prepared by heating coumnrandione with aniline in benzene or alcoholic solution crystallises in pale yellow plates m. p. 102" and shows no tendency to form a lactone ; the acetyl derivative has rn. p. 138'. The p-dimethyZaminonni2 OH*C,H,:C( :N*C,H,*NAfe,)*CO,H crys- tallises in dark red needles of a metallic lustre rn. p. 153'; the rnono- sodium salt and monohydrochloride crystallising in yellow prisms are mentioned. On treatment with phenylhydrazine the p-dimethyl- aniline residue is eliminated Kith the formation of the phenylhydr- azone of o-hydroxyphenylglyoxylic acid. With o-phenylenediamine i t yields 2 -by d roxy- 3-h ydrox y pheny lquin oxaline.When hydrolysed with aqueous alcoholic sodium hydroxide and the resulting solution neutralised with acetic acid coumaran-1 2-dione-l- p-dimethylarninoanil (Fries and Hasselbach Abstr. 1911 i 151) is converted into o - hydroxyphenylylyoxylo - p - dimeth ylaminoanilide OH*C6H4*CO*CO*NH-C/,H,*NMe which however could not be obtained in a pure condition and was therefore characterised by means of its benxoy2 derivat'ive C,,H,,O,N stout red prisms m. p. 138'. With excess of bromine in glacial acetic acid solution coumaran- dione yields 3 5-dibromo-2-hydroxyphenylglyoxylic acid which has m. p. 148' (decomp.) (compare Abstr. 1910 i 332) and forms a hydrate C,H,0,Br2,H20 crystallising in slender pale yellow needles m. p. 110'. l-Bromo-2-cournaranone C,H,O,Br prismatic needles m.p. 8 7 O and 1 :l-dibromo-2-coumar~none C,H,02 Br pale yellow needles m. p. 1 4 2 O are obtained by brominating 2-coumarmone in carbon tetra-i. 206 ABSTRACTS OF CHEMICAL PAPERS chloride solution. When warmed with sulphuric acid the dibromo- compound is converted into coumarandione and finally into salicylic acid. On treatment with o-phenylenediamine it yields coumaro- phenazine. 1 l-l)ichZoro-2-coumaranone prepared by chlorinating 2-coumaranone in glacial acetic acid solution forms white prismatic needles m. p. 70'. Coumarandione the Analogue of Isatin in the Coumarone Series. A Correction. RICHARD STOERMER (Ber. 1912 45 162-1 63. Compare preceding abstract).-The compound described previously (Abstr. 1909 i 174) as the hydrate of coumarandione is now found t o be the acetyl derivative of 1-oximino-2-coumaranone F.B. c,H,<_COCI>C:N*OA~. It is shown that the substance is formed by the action of acetic acid on aci-nitrocoumaranone and not by the oxidation of '' leuco- oxindigo," as previously supposed. With respect to the mechanism of the reaction the author imagines that an intermediate compound of the composition c,H,<-\~>cH*No(oH)~oA~ is first produced by the combination of acetic acid and aci-nitro- coumaranone and that t h i s is subsequently reduced by the nitrous acid formed by the spantnneous decomposition of the aci-nitro- compound loss of 1 mol. of water taking place simultaneously. F. B. Constitution of the Desaurins. C. KELBER and A. SCHWARZ (Ber. 1912 45 137-147).-By the interaction of carbon disulphide potassium hydroxide and ketones of the type R*CO*CH,*R Meyer (Abstr.1888 484; 1890 1144 ; 1892 340 1127) obtained a number of desaurins t o which he ascribed the constitution R-CO~CR:C<~>C:CR*CO~R (R a aryl). This forniula has now been confirmed by the synthesis of similarly constituted desaurins (11) by the removal of hydrogen sulphide from 2 mols. of the aryl PP-dithiolvinyl ketones of the formula I (I) R*CO*CH:C(SH) = (11) R*CO*CH:C<E>C:CH*COR + H2S. S A number of desaurins of the type R*CO*CMe:C<S>C CMe-COR have also been prepared by heating aryl ethyl ketones R*COEt with carbon disulphide and finely-powdered potassium hydroxide. The compound COPh*CH:C:S,:C:CH*COPh is obtained in small yield by heating phenyl PP-ditbiolvinyl ketone (Kelber Abstr.1910 i 390) at 100'. It is also produced together with carbon oxysulphide benzophenone and benzoyl sulphide by rapidly heating the dibenzoyl derivative of the ketone (Zoc. cit.) either alone a t 210° or in solvents of high b. p. such as ethyl benzoate or acetophenone. It crystal- lises from ethylene dibromide in yellow rectangular prisms m.. p. 212-214O (decornp.) and dissolves in strong sulphuric acid yielding orange-red solutions having an intense green fluorescence.ORGANIC CHEMISTRY. i. 207 The lead salt of phenyl PP-dithiolvinyl ketone C,H,OS,Pb is a heavy reddish-brown powder ; the mei*curic salt Cl,H,,OI,S,Hg is soluble in organic solvents and crystallises from toluene in orange needles which have m. p. 185-190' (decomp.) with previous darken- ing at 130-140'.When heated in solvents of high b. p. both the lead and mercuric salts are decomposed with the formation of metallic sulphide and the above-mentioned desaurin. The monothiourethane COPh*C,H,S,*CO=NHPh obtained from phenyl PP-dithiolvinyl ketone and phenylthiocarbimide in benzene solution crystallises in slender needles m. p. 94' (decomp.) and when carefully heated gives a small yield of the corresponding desaurin. The compound (C,H,S*CO*CH:U),S may be prepared from a-thienyl PP-dithiolvinyl ketone (Abstr. 191 I i 740) by methods similar to those employed in the case of the preceding desaurin. It crystallises in moss-like aggregates of slender yellow needles which decompose at 260' with previous*darkening and yields with sulphuric acid deep red solutions having a green fluorescence.The mercuric salt of a-thienyl PP-dithiolvinyl ketone C,H,OS,Hg is obtained from mercuric chloride and the. ketone in alcoholic solution. The thiourethane C,H,S*CO*C,H,S,*CO*NHPh prepared from the ketone and phenylthiocarbimide decomposes at 80'. The desaurin from p-tolyl PP-dithiolvinyl ketone (Zoc. cit.) crystallises in yellow rectangular prisms. The cornpouud COPh*CMe:C:S,:C:CMe*COPh prepared by heating phenyl ethyl ketone with carbon disulphide and potassium hydroxide crystallises in lustrous golden-yellow leaflets m. p. 225'; the compound (C6H,Me*CO*CMe:C),S from p-(?)tolyl ethyl ketone in strongly refractive yellow needles m. p. 263-265O. (C,H,S*CO*CMe:C),S from a-thienyl ethyl ketone forms yellow needles m.p. 258-260'; the cornpound (CloH,*CO*CMe:C),S from 8-naphthyl ethyl ketone crystallises in yellow leaflets which have m. p. 264' and decompose at 268-269'. F. B. The compound The Simplest Thiopyronine. FRIEDRICH KEHRMANN and L. LOWY (Bey. 1912 45 290-292).-The chloride of the simplest thiopyronine 3 6-diaminothioxanthinium chlovide (annexed formula) is obtained in small yield by the addition of a glacial acetic acid solution of di-p-acetyl- /\/\/\ aminodiphenylmethane to a solution of I I INH flowers of sulphur in fuming sulphuric acid HH'\/N/\/ at a temperature not exceeding lo' and subsequent hydrolysis of the resulting 3 6- diacetylaminothioxanthinium szclphate (not isolated). It crystallises from alcohol in metallic green needles or prisms which yield scarlet-red solutions having a greenish-yellow fluorescence.The carbonate acetate iodide diclwomate and also the nitrate cryetallieing in scarlet- red needles are described ; the platinichloride (C,,H,,N,SCl),P tCl was analysed. Elimination of one of the amino-groups from the preceding chloride CH S*Cli. 208 ABSTRACTS OF CHEMICAL PAPERS. by successive treatment with nitrous acid (1 mol.) and alcohol results in the formation of apothiopyronine (3-uminothioxccnthinizcm) chloride NH *U H < >C,H which was converted into a red crystalline nitrute and pZatinichZoride (C,,H,,NSCl),PtCl,. [Preparation of Ketonaphthathiophen.] KALLE & Co. (D. R. - P. 23 9 0 9 3) .- Derivatives of o-carboxy n apht hyl thiolacetic acids yield valuable dyes and the following series of compounds have been prepared a-Naphtbylamine-2-sulphonic acid is converted by diazotisa- tion and subsequent treatment with copper sulphate and potassium cyanide into sodium l-cyanonuphtl~alene-2-suZphonate leaflets which furnishes an acid chloride long needles or prisms m.p. 143’; this when reduced with zinc dust in sulphuric acid solution and treated with chloroacetic acid yields a mixture of 1-cyunonupl~thuZene-2-thioZacetic acid and 1 -carboxynaphthaZene-2-thioZacetic acid which can be separated by fractional crystallisation from water when the acid is obtained in long coloi~rless ‘7’S-\CH*C02H needles m. p. 93’ and (when anhydrous) Ketonaphth thiophencurbox y Zic acid (an- nexed formula) colourless aggregates is obtained by the fusion of the foregoing mixture with sodium hydroxide and is converted by treatment with mineral acids into naphthoxydhiophen glistening grey crystals m.p. 118-1 19’. KALLE & Co. (D.R.-P. 2 3991 ti).-When indoxyl oxythionaphthens or compounds of the same type (2 mols.) are condensed with a dialdehyde or diketone (1 rnol.) substances are obtained having the general formula CH 2 6 3 SCl F. B. 12 7-128”. F. M. G. M. [Preparation of Indigoid Compounds.] c6 H,<go>C CR’ R*CR” C<g!>C,H4 where R is a hydrocarbon ; R’ R,” hydrogen or hydrocarbon residues ; X and Y alike or different atoms or groups such as sulphur oxygen or the imino-group. The yellow crystalline compound c,H~<~~>c CH C,R,. CH C<-~~>C,H 4 was prepared from ketothionaphthen (2 mols.) and terephthalnldehyde (1 mol.) whilst the analogous compound obtained from the bisulphite derivative of glyoxal (1 mol.) forms brownish-yellow needles.The ketothionaphthens can be rsplaced by indoxyls in these reactions. F. M. G. M. [Preparation of ‘‘ Dihalogendimethylthioindigos.”] KALLE & Co. (D.R.-P. 239094).-The symmetrical ‘‘ dihalogendimethylthio- indigos ” of the annexed general formula (where R is a halogen atom and R’ a R / \ A /\/‘R methyl group or vice versa) are of 1 1 ’:’ I 1 technical value and in this connexion \/\/ ‘\/\( the following compounds have been S S R’ prepared.ORGANIC CHEMISTRY. i. 209 5-Cl~loro-3-anbino-o-tolzcic acid needles (prepared by the reduction of the corresponding chloronitrotoluic acid) when diazotised xantho- genated and treated tvit,h chloroacetic acid yields 5-cldoropheizyl-3- methyl -2-carboxyplie~zyIthio2cccetic ucid colourless needles which on fusion with sodium hydroxide furnishes 6-chZoro-3-h~d~oxy-4-methyl-( 1 )-thio- naphthen-o-carboxylic acid and subsequently on treatment with mineral acid 6-chloro-3-hydroxy-4-methyZ-( 1)-thionaphthen glistening colourless needles.The reaction is stated to be applicable to other halogenated nitro- toluic acids. F. M. G. M. [Preparation of " Naphthioindigo."] KALLE & CO. (D.R.-P. 2401 18).-" Naphthioindigo " (formula I) is prepared as follows S S 2-amino-3-naphthoic acid is diazotised and converted successively into 2-thion~pl~thol-3-carboxyEic mid a yellow powder m. p. 275-276' and 3-carboxynaphthyl-2-tl~iolacetic acid (11) a colourless crystalline powder m. p.203'; this wheu treated with alkali or acetic anhydride yields 3-keto-(l)-thioanthren and by subsequent oxidation with potassium ferricyanide the foregoing '' naphthioindigo." F. M. G. M. Bromo-derivatives of the Alkaloids of Peganum harmala and their Basic Uerivatives. V. HASENFRATZ (Compt. rend 19 12 154 225-217. Compare Fischer Abstr. 1889 730; lS9S i 160). -On treating harmaline harmine npoharmine and methylupoharmine with bromine in acetic acid the hydrobromides of the corresponding monobromo-derivatives are ob tained. BromoZmrrlrmZi.ne Cl3HI20N2Br crystallises in colourless slender needles in. p. 195' ; the ?hydro- cldoride and pbihichloride are yellow. I n the case of har'mine two isomeric compounds are formed and may be separated by heating the hydrobromides at 50° bvomohurmine hydrobrocmicle alone fusing a t this temperature.Bromoha~mine C,,H,,ON,Br occurs in orthorhombic prisms m. p. 275'; the salts crystallise from alcohol but form jellies with water. isoBromoharrnine crystallises in long needles m. p. 203' and its salts crystallise from water ; the pkati?ddoride is orange-red. Bvornoapoharminc C8H1N2B1. crystallises in long needles m. p. 229O and bromoniethylapoharnzine C9H9N2Br in needles IU. p. 196'. On brominating harmine in presence of sulphuric acid arid sus- pending the product Pischer's supposed tetrabromide in hot dilute alcohol slender needles of dibronzoharmine sizonohydi.obrornide are obtained ; when treated with ammonia this gives dibromohurmine C!,H,,ON,Br m.p. 209'. Fischer's compound appears to be the ciahydrobromide of this base. w. 0. w. Preparation of a Compound of Codeine with Diethyl- barbituric Acid. KNOLL & Co. (D.R.-P. 239313).-Codeinei. 210 ABSTRACTS OF CHEMICAL PAPERS. diethylbarbiturate . prisms m. p. 8 5 O is readily prepared by mixing molecular proportions of codeine and diethylbarbituric acid (veronal) in aqueous or alcoholic solution or by intimately mixing codeine hydrochloride with sodium diethylbarbiturate in the absence of solvents. F. M. G. M. Degradation of Sparteine. Formation of a Hydrocarbon Sparteilene. CHARLES MOUREU and AMAND VALEUR (Comnpt. rend. 1912,154 161-163. Compare Abstr. 1908 i 43 44 563).-When methylhemisparteine is treated with methyl iodide the product has the composition C,,H,,N,Me,I but appears to consist of a mixture of a t least two isomerides.On treatment with silver oxide it gives a quaternary ammonium base which on heating in a vacuum yields inactive dimethyZhemispayteiZene C15H21NMe2 b. p. 201-202°/27.5 mm. This substance forms a methiodide and a quaternary hydroxide ; the latter decomposes at 75' in a vacuum giving trimethylamine and sparteilene C,,H,,. The new hydrocarbon is a colourless odourless optically inactive liquid b. p. 157-159'/1S mm. showing a molecular refraction corresponding with the existence of six ethylenic linkings. Its production with trimethylamine taken in conjunction with the formation of methylsparteilene and trimethylamine from dimethyl- sparteine is sufficient to establish the symmetrical character of the sparteine molecule.Oxidation of sparteilene by means of potassium permanganate Ieads to the formation of an acid C,,H,,O m. p. 300-305° on the Maquenne block. w. 0. w. Strychnos Alkaloids. XIV. Derivatives and Decomposition Products of Brucinolon e. Decomposition of Dihydrobrucinonio Acid into isoBrucinolone and Glycollic Acid. HERMANN LEUCHS and J. F. RREWSTER (Ber. 1912 45 201-221. Compare Abstr. 1908 1,563 ; 1909,1,253 954).-For the preparation of brucinolone brucine dissolved in acetone was oxidised by potassium permanganate whereby brucinonic and dihydrobrucinonic acids were obtained The two acids are difficult to separate completely. Brucinolic acid was obtained by reduction of brucinonic acid (containing some dihgdro- brucinvnic acid).This latteracid appears to be formed even when the most carefully purified keto-acid is reduced and the authors have come to the conclusion that it is stereoisomeric with brucinolic acid since they were also able t o show that the two acids are similarly affected by sodium hydroxide. Since dihydrobrucinonic acid is formed by the direct oxidation of brucine it follows that the latter must contain a secondary alcoholic group. For the conversion of brucinolic acid into brucinolone the authors recommend the use of normal sodium hydroxide ( l a mols. instead of 14 mols. previously employed). The m. p. of brucinolone is now given as about 270° and [a] -34.79 The latter value is somewhat dependent on concentration and source of light used. By means of ice-cold nitric acid (D lea) brucinolone was converted into ~zik~obisapomethyZdeh~drobrzccinoZorne which forms orange-coloured leaflets.Bisapomethylbrucinolone (bisdemethylbrucinolone of Abstr. 1909,ORGANIC CHEMISTRY. i. 211 i 954) was converted into the triacetate by treatment with acetic anhydride and sodium acetate. It crystallises in colourless leaflets m. p. 260-261'. I n brucinolone hydrate I. (in which the ZN-GO- of brucinolone is supposed to have been transformed into =NH H0,C-) the presence of the imino-group bas been proved by the regeneration of brucinolone by the action of heat on the hydrate I. and by the formation of a derivutiue when treated with phenylcarbimide. The latter is a non- crystallisable amorphous white powder m. p. 192' (decomp.) after previous softening. The presence of the carboxyl group is shown by thezisolation of the hydrochlorides of the methyl ester m.p. 189-190' (decomp.) and of the ethyl ester m. p. 181' (decornp.). The isolation of a by-product CzlH,,O6N during the action of sodium hydroxide on brucinolic acid has been previously described (Abstr. 1909 i 954). This substance when heated with 5~V-hydro- chloric acid yields a hydrochloride which is completely melted at 255' after previous gas evolution. The free base obtained from this which has been named brucinolone hydrate II. separates from water with vary- ing amounts of water of crystallisation. It has m. p. 240' (decomp.) after softening at 190'. It differs from the hydrate I. in possessing less tendency t o lose water. When the by-product C21H2406N2 is heated with sodium hydroxide brucinolone is formed.I n order to gain further insight into t h e oxidation products of brucine brucinolone acetate (m. p. 253-254') was prepared by heating brucinolone with acetic anhydride and sodium acetate. This was oxidised in acetone solution by potassium permanganate. I n this manner an acid C2,H,,0,N21 was isolated which gave a brownish-red coloration with alcoholic ferric chloride and thus appears to be a keto- acid. When heated i t softens at 120° melts at about 160' (decomp.) then solidifies becoming yellow at 240° and melting again at about 275". When heated during ten minutes at 160-18U0 i t evolves carbon dioxide and leaves a neutral substance C20H2407N2 which has m. p. about 281'. During the oxidation? a neutralproduct C,,H,,O,N (m.p. about 312') is also formed. By the action of normal sodium hydroxide (18 mols.) on dihydro- brucinonic acid glycollic acid was obtained together with isobmcinolone. The latter forms yellow crystals my p. 308' (decomp.) and has [a32 + 26.9' in glacial acetic acid solution. H. W. Action of Acetic Anhydride on Some Benzylideneanthr- anilic Acids. JOHN B. EKELEY and PAUL M. DEAN (J. Amer. Chem. Xoc. 1912 34 161-164).-The products of the condensation of anthranilic acid with aromatic aldehydes (compare Wolf Abstr. 191 1 i 735) react with acetic anhydride to form a series of oxazines which are crystalline very stable and usually colourless. Benzylideneanthranilic acid m. p. l2fi0 yields 1 -keto-d-acetyZ-3-phen& 'O-? NAc*CHPh' m.p. lOS' which when dihydro-2 ; 4-benxoxaxine C6H,< heated with hydrochloric acid is decomposed into benzaldehyde and acetylanthranilic acid. m-Nitrobenzylideneanthranilic acid m. p. 202O and p-nitrobenzylideneanthranilic acid m. p. 164' yield 1-hto-i. 212 ABSTRACTS OF CHEMICAL PAPERS. 4-acetyl-3-m- and -p-nitvophenyldihydr0-2 4-benzoxccxines m. p. 192' and 199' respectively. When p-hydroxybenzylideneanthranilic acid m. p. 207O is heated with acetic anhydride l-keto-4-acetyl-3-p-acetoxypT~enyl- dihydro-2 4-benxoxcbzine m. p. l48' is produced. Salicylidene- anthranilic acid m. p. 195' similarly gives l-keto-4-acetyl-3-o-acetoxy- phenyldihydro-2 4-benzoxaxine m. p. I. 62'. Vanillylideneanthranilic acid m. p. 170° crystallises in lemon-yellow needles and when heated with acetic anhydride yields l-keto-4-acetyl-3-p-7ydroxy-m-methoxy- phenyldi?hydro-2 4-benxoxuxine m.p. 184O which forms pale straw- coloured needles. E. G. Thiazines. RICHARD MOHLAU HEINRICH BEYSCHLAG and H. KOHRES (Ber. 1912 45 131-137. Compare Abstr. 1910 i 337)- The authors have repeated the work of Kehrmann and Steinberg (Abstr. 1911 i 1034) and agree with them that the dinitrophen- thiazine obtained by the interaction of picryl chloride and o-amino- thiophenol has the constitution originally ascribed to i t by Kehrmann and Schild (Abrjtr. 1900 i 61). The synthesis of the isomeric 2 4-dinitrophenthiazine is also described. Di-o-aminodiphenyl disulphide is best prepared by reducing di-o-nitro- diphenyl disulphide (Blanksma Abstr. 1901 i 460) with hydrazine hydrate in alcoholic solution The dzbenxoyl derivative (NHBz*C6H4),S2 crystallises in pale yellow needles m.p. 141° and is reduced by aqueous sodium sulphide to o-benzoylaminophenyl mercuptan which reacts with picryl chloride in the presence of sodium acetate yielding trinitrophenyl o-benxoylamino- phenyl sdphide NHBz*C6H,*S*C,H,(N0,),. The latter compound crystallises in yellow prisms m. p. 169O and when boiled with sodium hydroxide in aqueous alcoholic solution is converted into 2 4-diyzitro- phenthiuxine (annexed formula) which crys tall ises in almost black lustrous prisms m p. 218O /\/\/\NO (appearing reddish-brown by transmitted light) I 1 1 1 dissolves in alcoholic sodium hydroxide yielding \/\/\/ bluish-violet solutions and on reduction with stannous chloride and hydrochloric acid is converted into 2 4-diamino~her~thi~xine stannichloride NH This forms brownish-yellow needles and is oxidised by ferric chloride in alcoholic solution in the presence of hydrochloric acid to 2 4-di- - _ aminophenazthionium chloride c6 H,<:>C,H,( NH,),.The ferri- chlovide C,2H,,N,SC1,Fe,H,0 forms greenish-black microscopic crys- tals which lose their water of crystallisation at 110'; the p l a t h i - chlo~ide chromate caybonate and the thiazonium base itself are briefly mentioned. Kehrmann and Steinberg's 1 3-dinitrophenthiazine has m. p. 187'. F. B. Decomposition of Alkylidenehydrazines. NICOLAI &I. EIJNER (J. Buss. Phys. Chem. Soc. 1911 43 1554-1562).-The autlhor hasORGANIC CHEMISTRY. i.213 been able to pass from carone through carylidenehydrazine t o carane (compare Abstr. 191 1 i lOZS) the hydrocarbon thus obtained being structurally identical with that prepared from pulegone but exhibiting a laevo- instead of a dextro-rotation. the action of hydrazine hydrate on caroie is a &ous liquid b. p. 131°/20 mm. Di0 0.9683 n 1.5082 [a] + 375.7-378.8O (absolute alcohol). Its thioureide NHPh*CS*NH* N:CloH16 forms hexagonal plates m. p. 100-101'. Hydrolysis of carylidenehydrazine by either boiling dilute sulphuric acid or hydrochloric acid at the ordinary temperature yields a product showing all the physical properties of carvenone with the exception of a slight laevo-rotation apparently due to admixture of a small quantity of an intermediate compound in the hydrolysis.I-Camme C10H18 has b. p. 169-169*5'/761 mm. Dto 0.8411 n 1*4,569 [a] -47.06' is very stable towards permanganate and combines with generation of heat with halogen hydrslcids and bromine. The bromo-derivative CloHl,Br obtained by the action of hydrobromic acid has Dto 1.1774 nD 1.4910 [a] - 6-40' and yields A8(g)-m-merithene and a"@)-m-menthene in the same way as d-carane (ZOC. cit.). 2'. H. P. Refutation of Bulow's Views Concerning Pgrazoline- carboxylic Acids. EDUARD BUCHNER (Ber. 1912 45 117-lZl).- Many arguments are advanced to disprove Bulow's view (this vol. i 134) that a niixed azine CHX:N*N:CX-CH,X not a pgrazoline cx-?Hx is produced by the action of ethyl diazo- NH*CHX' derivative N< acetate on an unsaturated ester of the type CHXICHX (X = C0,Et).c. s. Derivatives and Decomposition Products of Methyl Methoxy- benzoylacetates. ANDRB WAHL and C. SILBERZWEIG (Bull. Soc. Chim. 1912 [iv] 11 61-69).-The methoxybenzoylacetates are convertible into ap-diketonic esters and as these may react with various reagents giving compounds identical with those obtainable from the initial P-ketonic esters the following compounds have been prepared and characterised so that they may be readily identified. Methy I a-oximino-o-methoxp benxoylacetate OMe*C',H,-CO-C(NOH)* CO,Me m. p. 146-147" produced by the action of nitrous P-ketonic ester in acetic acid crystallises from ether. ester reacts with phenylhydrazine to form Tahara's - - - N=~*C,H,-OMe methoxyphenyl-5-pyrazolone PhN< CO*CH 9 acid on the The original 1 -phenyl-3-0- p.133-1 34O yellow needles and with p-nitrophenylhydiazine t o form 1 -p-mitro- phenyZ-3-o-methoxyphenyZ-5-pyraxoZone m. p. 2 17-2 1 BO brown needles. OMe*C,H,-CO*C(:N*NHPh)*CO,Me Methy I a-phenylhydraxornoazo-o-methoxgbenzo ylacetate VOL. CII. i. 4i. 214 ABSTRACTS OF CHEMICAL PAPERS. m. p. 138-139' obtained by the action of benzenediazonium chloride on the ester in the cold forms yellow crystals from alcohol and reacts with phen ylhydrazine t o form 4-phen ylh ydruxono- 1 -phenyl-3-o-methoxy- phenyl-5-pyraxolone m. p. I39' orange crystals and with p-nitrophenyl- hydrazine to form 4-phenylhydrazono-I-p-nitro;~henyl-3-o-methoxyphe~yZ- 5-pyrazolone m. p. 200' red crystals from pyridine. Methyl p-nitropl~enylhydruxono-o.metl~oxybenxoylucetute m.p. 1 TO" obtained by the action of the sodium derivative of p-nitrophenylnitroso- amine on the P-ketonic ester forms yellow crystals and reacts with phenylhydrazine to give 4-p-nitrophenylhydrazono-l-phenyl-3-o-methoxy- phenyl-5-pyrazolone m. p. 267' red crystals. Methyl oximino-rn-wthoxybcnxoylacetute m. p. 115-1 16" forms colourless needles from ether and light petroleum and on treatment with phen yl h y drazine gives 4-o~imino- 1 -phenyl-3 -m-rnethoxyphen yl-5- pyruzolone m. p. 1 5 7 O which forms red crystals from acetic acid. Methyl phenylhydruzono-m-methoxybenzoykccetute m. p. 72-73" forms yellow crystals; the free acid m. p. 118-120° forms yellow needles. Methyl p-nitrophenylhydrazono-m-methoxybenzoylacetate m. p. 155-156" crystallises in yellow needles.1-Phenyl-3-m-methoxy- phenyl-5-pyraxolone m. p. 124O forms pale yellow crystals. 4-Phenyl- hydrazono-1 -pheny1-3-m-rr~ethoxyp?~enyl-5-pyrazo20ne7 m. p. 137' and the corresponding 4-p-nitrophenylhydruzone m. p. 235" both form red crystals. Methyl oxirninoanisoylacetate m. p. 1544 forms colourless crystals from boiling methyl alcohol. Methyl phenylhydraxonounisoylucetate m. p. 121-1 22" forms orange crystals ; thefree acid m. p. 149-150° is yellow. The ucetyl deriv- ative of the ester has m. p. 116' crystallises in colourless needles and on reduction furnishes some acetanilide whence it is believed to have the constitution OMe*C6H,*CO*C( :N*NPhAc)*CO,Me (compare Auwers Abstr. 1909 i 222). Methyl p-nitrophenylhyd~uzonoanisoylucetate m. p. 175' forms yellow crystals; the free acid m.p. 236-238' is also yellow but dissolves in alkalis with an intense red colour. l-PhenyZ-3-p-rnethoxyphenyl-5-pyraxolone has m. p. 137-138' ; the 4-0xirnino-derivative~ m. p. 244" forms red crystals. p-Nitrop?Aenyl- 3 ~p-methoxyphenyZ-5-pyraxolone m. p. 204-205' is brown. 4-Phenyl- hydruzono-l -phenyl-3-p-methoxyphenyl-5-pyraxolone m. p. 177" is red ; the corresponding p-nitrophenylhydrazone 111. p. 2 13-2 14' separates from acetic acid in violet crystals and the isomeric 4-phenylhydraxono- 1-p-nitrophenyL3-pmethoxyphenyl-5-p~ruzolone m. p. 239O is red. The methoxybenzoylacetic esters are hydrolysed by boiling with 20% sulphuric acid into the corresponding 0- m- and p-methoxyaceto- phenones. The semicarbazone of m-methoxyacetophenone has m. p.195-197" (compare Klages Abstr. 1904 i 45) and that of the p-compound melts at 197'. T. A. H. Quinazolines. XXVIII. 4-Quinazolone-2-phthalones and Certain of their Derivatives. MARSTON T. BOGIERT and MICHAEL HEIDELBEHGER (J. Amer. Chem. Xoc. 1912 34 183-201).-An account is given of certain phthalones obtained by the action ofORGANIC CHEMISTRY. i. 215 phthalic anhydride on 2-methpl-4-quinazolone (2-methyl-4-hydroxy- quinazoline) and its derivatives. These compounds like the quino- phthalones behave as yellow dyes but are inferior to the latter in tinctorial power. Q-Qui~xolo~ae-2-phthcclone 14- hydroxyquinaxoline -2-phtha Zone 2-in- dandionyl-4-quinaxolone or p- (4'-quinanolon yl-2')-diketohydrindene] ~6H4*N>C*CH<co>06Hg m. p. 318' (corr.) obtained by heating a CO-NH CO mixture of 2-methyl-4-quinazolone and phthalic anhydride to about 200° forms pale yellow prismatic needles or hexagonal plates and when heated above 200' sublimes in woolly masses of minute needles.In one experiment in which a large excess of phthalic anhydride was used on extracting the reaction product with hot water 2-methyl- 4-quinazolone phthalnte was obtained which crystallises in pale yellow fluorescent needles with 1H20; the anhydrous salt has m. p. 171' (corr.). The di-sodium salt of the phthalone is orange-red whilst the mono-sodium and silver salts are pale yellow. On reducing the pht hnlone with zinc dust and sodium hydroxide 4-quincczoZone-2- N=Y-QH*YH CO NH CO-CAR,' is obtained which forms olive- hydrindone C6H4< yellow microscopic crystals subli&es above 160° and melts at about 328' (decomp.).When the phthalone is heated with anilite in Dresence of zinc chloride the anil. m. p. 284-285O (uncorr.) is produced which crystallises in brilliant scarlet needles ; its sodium salt and compound with zinc chloride are described. From the product of this reaction a small quantity of another anil m. p. 258' was obtained which forms red crystals and appears to be acondenaation product of 1 mol. of aniline with 2 mols. of the phthalone. 4-Quina~olone-2-phthalonemonophenyZhydrazone m. p. about 225' (uncorr.) was obtained as an orangsbrown micro- crystalline powder. 4-Quinaxolone-2-phthalone-6-sulphonic acid m. p. about 355-360' (uncorr.) crystallises in minute plates or needles ; its mono- and di-sodium and barium salts are described.Solutions of the di-sodium salt dye wool or silk light yellow shades. By the action of bromine on the sulphonic acid there were formed a di- and a penta- bromo-2-methyl- 4 - quinazolone a bromo - 2 - methyl - 4 - quinazolone- sulphonic acid phthalic acid and sulphuric acid. Dibromo-%methyl- 4-quinmolone m. p. about 293' (decomp.) forms masses of delicate colourless needles. Pentabromo-2-methyZ-4-quinazoZone m. p. about 243.5' (decomp.) crystallises in colourless prismatic needles. Bromo- 2-methyl-4-puinaxoZones~~hoic acid m. p. 285-286.5' (uncorr.) forms a grey amorphous solid containing lH20; its barium salt crystallises with 4&H20. Attempts to prepare 4-quinazolone-2-phthalines by heating the ammonium salt of the phthalone with alcoholic ammonia in sealed tubes did not meet with success.Bis-(4-q?~i~,axoEone-2)-P-pht~aZ~ne C,H,ON,.CH:C<~~~>C:CH.CBH,ON obtained by heating a 6 4i. 216 ABSTRACTS OF CHEMICAL PAPERS. mixture of phthalimide and 2-methyl-4-quinazolone is an orange-brown substanre which darkens gradually when heated ; its solution in dilute acetic acid acts as a powerful yellow dye. 4-QuinazoZone- %P-phthuZine C,H,0PLT2*CH:U<NH>C,H co- m.p. about 349' (decomp.) is also produced in t h i s reaction and forms orange-brown microscopic pi Lms. 2-Methyl-4-quinazolone reacts with succinic anhydride with production of a tarry mass from which a small quantity of tt substance m. p. 274-277" (decomp.) was isolated in the form of thin colourless lustroiis plates.6-Nztro-4-quinaxolone-2-phthc~lone obtained by heating 6-nitro- 2-methyl-4-quinazolone with phthalic anhydride a t about 210" forms minute yellow crystals and does not melt below 355'. 7-Acet~lamino-4.quislccxolone-2-p?~thalone resultiog from the action of phthalic auhydride on 7-acetylamino-2-methyl-4-quinazolone crystallises in bright yellow lustrous plates and does not melt below 356". N=$?Me 2-iCiet?~yl-3-et?~yl-4-quinaxolone C,H,<CO. NEt m. p. 67' (corr.) obtained by heating acetylanthranil with excess of an aqueous solution of ethglamine in presence of a little potassium hydroxide forms colourless slender needles ; its ptatinichloride decomposes at about 229". I n one experiment in which potassium hydroxide was not added anthrunilethylumide NHEt*CO*C,H,*NHAc m.p. 139.5-140.5' (corr.) was isolated in the form of transparent prismatic plates. 3-Ei%yZ-4-puinaxolone-2-p?~thaZone m. p. 19 8.5O (corr.) obtained from 2-methyl-3-ethyl-4-quinazolone and phthalic anhydride forms bright yellow lustrous prismatic needles with a slight green fluorescence. E. G. Formation of Pyrimidines by Use of Nitromalonaldehyde. WILLIAM J. HALE and HARVEY C. BRILL (J. Amer. Chem. Xoc. 1912 34 82-94).-Hill and Torrey (Abstr. 1899 i 788) have shown that nitromalonaldehyde reacts readily with primary amines. This work has now been extended to other amino-compounds. When carbamide is allowed to react with the sodium derivative of nitromalonaldehyde in presence of a few drops of piperidine the mono- ureide and 6-nitro-2-hydroxypyrimidine are produced.Nitromalonaldehyde mono-ureide NH,*CO*N:CH*CH(N02)*CH0 m. p. 154" (corr.) forms pale yellow crystals; its sodium salt crystallises with 3H,O. The a d NH,*CO*N:CH*CH(NO,)*CH:NPh m. p. 211" (corr.) crystallises in lustrous red needles. The oxirne NH,*CO*N:CH*CH(N02)*CH:NOH m. p. 174-175' (corr.) forms yellow leaflets. 5-Nitro-2-h~droxypyrimidilnir O H * C < ~ ~ ~ ~ > C * N O m. p. 203.5" (corr,) crystallises in small yellow plates ; the sodium potassium,ORGANIC CHEMISTRY. i. 217 barium and silver salts are described. The methyl ether m. p. 168-169' (corr.) forms colourless plates. 5-Nitr0-2-phenyZpyrirr~idine CPh<E ~ ~ ~ > C * N O m . p. 2 19" (corr.) obtained by the interaction of benzamidine hydrochloride and sodium nitromalonaldehyde crystallises in white plates.5-Nitvo-2-aclninopyrimidine7 N B * C < ~ ~ ~ ~ > C * N O m. p. 236' (corr.) prepared by the action of guanidine carbonate on sodium nitromalonaldehyde forms colourless slender needles and whea heated with solution of alkali hydroxide is converted into &nitro- 2-hydroxypyrimidine ; the acstyl derivative N H A ~ - C < ~ ~ ~ X - N O N*CH\ m. p. 172.5' (corr.) crystallises in long colourless needles. When a small quantity of potassium hydroxide is added to a mixture of 5-nitro-2-aminopyrimidine and carbon disulphide at 60° 5 5'-di- nitro- 2 2' - dip yrinzicEyk?~ioca~bamide CS[ N H C<z ;g>C*NO,] m. p. 230-231' (corr.) is produced which forms a mass of glistening leaflets. NitromaZonaldeiyde phenyluraide CHO*CH(NO,) * CH :N *CO*NHPh m.p. 1'76-177' (corr.) was obtained by the condensation of nitro- malooaldehyde with phenylcarbamide. The corresponding benzyl- ureide m. p. 150-151' (corr.) and methylureide were also prepared E. G. Chlorides of Amino-acids. CARL MANNICH and R. KUPHAL (Ber. 1912 45 314-322).-By the internal condensation of benzyl- sminoacetyl chloride and of similar amino-acid chlorides in the presence of aluminium chloride the authors hoped to prepare derivatives of isoquinoline CH',Ph*NH*CH,*COCl -+ C,,H,< It was found however that the chlorides readily lost hydrogen chloride even in the absence of aluminium chloride with the formation of d i ketopiperazines. Ethyl banzylarninoacetate prepared by the interaction of ethyl chloroacetate and benzylamine is a colourless liquid of aromatic odour b.p. 153-154'/13 mm. and is readily hydroiysed by hydrochloric acid to benzylaminoacetic acid (Mason and Winder Trans. 1894 67 187). It is accompanied by a substance which crystallises from dilute alcohol in lustrous white leaflets m. p. 2%- 239O consistiiig probably of benxylaminoacetobenzylamide hydrochloride C,H7*N H*CH,*CO-NH-C,H7,HC1. The amino-acid is converted by the action of phosphorus pentachloride and acetyl chloride (Fischer Abstr. 1905 i 263) into benxylamino- acetyl chloride hydrocldoride C,H7*NH*CH,-COC1,HCI which forms slender white needles and when heated in nitrobenzene solution yields 3 6-diketo-1 4-dibenzybiperazine C ? H ~ * N < ~ ~ ~ ~ ~ ~ > N . C ; I I crystallising in white needles m.p 1172-173'. CN,*TH CO-CHH,'i. 218 ABSTRACTS OF CHEMICAL PAPERS. 3 4-MethyZennsdioxybsnxylamine CH,:0,:C,H,*CH2*NH2 prepared by reducing piperonaldoxime with sodium amalgam and alcohol the solution being maintained continually acid by the addition of acetic acid is a colourless liquid b. p. 138-139"/13 mm.; on exposure t o air i t forms a solid carbonate ;. the hydrochloride lustrous white leaflets has m. p. 227'; the benxoyl and chloroacetyl derivatives crystallise in slender white needles m. p. 117-118O and 107-108' respectively. It reacts with ethyl chloroacetate yielding ethyl 3 4methylenedioxy- benzylaminoacetate CH,:0,:C,H,-CH,*NH*CH2*C0,Et which forms a hydrochloride white needles m. p. 157-158" and is hydrolysed by aqueous potassium hydroxide t o the corresponding acid.This has m. p. 206-207° and is converted by acetyl chloride and phos- phorus pentachloride into 3 4mctl~ylenedioxybenzylaminoacetyZchloride hydrocitloride C,,H,,O NCl ,. 3 6-Diketo-I 4-di-( 3 4')-met~ylenedioxybenzyl~i~~*azine CH, 0, C,H,.CI~~.N<~~~~~>N*CH,.C,H,:O:CH prepared by heating the preceding chloride hydrochloride in nitrobenzene solution forms white needles m. p. 234-235'. Ethyl benxylmethylaminoacetate C7H7*NRle*CH,-C02Et obtained from ethyl chloroacetate and henzylmethylamine has b. p. 1 38'/ 13 mm. ; the syrupy hydrochloride the orange platinichloride and the picrate crystallising in stout yellow needles m. p. 122-123" are described. When hydrolysed with concentrated hydrochloric acid it yields the corresponding acid C,,H,,?,N which forms a hydrochloride sintering at 174O m.p. 180-181 and a chloride hydrochloyide C7H7*NMe*CH,*COCI,HCl. The latter compound reacts with aluminium chloride at loo' yielding carbon monoxide formaldehyde and benzylmethylamine together with s-dibenzyldimethylmethylenediamine CH2(NMe*C7H7) a pale yellow oil b. p. 172-175'/8 mm. The coiistitution of the last-named compound has been established by its synthesis from benzyl methy lamine and f ormaldehyde. F. B. Preparation of Halogenated Dehydroindigotin Salts their Nuclear Eomologues and S u b a t i t u t i o n Products. BADISCHE ANILIN- Jz SODA-FABRIK (D.R.-P. 239314).-Halogenated dehydro- indigotin salts have previously been described and the preparation of higher halogenated derivatives is now recorded.l'richlorodehydroindigotin acetate a canary-yellow powder is prepared by passing chlorine into a cooled acetic acid solution of dehydroindigotin acetate until the product has completely separated ; when nitrobenzene is employed as solvent a tetrachlorodehydroindigotirt hydrochloride is obtained whilst under these conditions indigotin yields trichlorodehydroindigotin hydrochloride (isolated in the form of its bisulphits compound) and 5 5'-dibromoindigotin in acetic acid solution furnishes dichlorodibromodshydroindigotin hydrochloride. Other solvents such as acetyl chloride or carbon tetrachloride can be employed and the formation of other halogenated indigotins is discussed. F. M. G. M.ORGANIC CHEMISTRY. 1. 219 Action of Alkyloxides and Amines on Benzoyl isocyano- chloride [ Benzoylcarbylamine Chloride].TREAT B. JOHNSON and LEWIS H. CHERNOFF (J. Amer. Chem. SOC. 1912 34 164-170).- Benzoylcarbylamine ~hloride,~C~H,*CO*N:CCl obtained by Johnson and Menge (Abstr. 1904 i 949) by the action of chlorine on benzoyl thiocyanate is decomposed by water with formation of hydrochloric acid benzamide and benzoic acid. It combines with sodium alkyl- oxides to form compounds of a new class the acylimidocarbonatee and reacts with amines with produqtion of substituted guanidines which yield stable salts with mineral acids and are hydrolysed by alkali hydroxide with formation of the free guanidines and benzoic acid. Diethyl benxoylimidocarbonate NBz:C(OEt)2 b. p. 93-100'/20 mm. and 1 10-120°/32 mm. was prepared by the action of benzoylcarbyl- amine chloride on sodium ethoxide.Dimethyl benxoylimidocarbonate b. p. 95-102"/20 mm. is a colourless oil. Benzoyl-ay-diphenylgucmidine NBz:C( NHPh) m. p. 2 12' (decornp.) obtained by the action of benzoylcarbylamine chloride on a solution of aniline in benzene forms colourless needles. p-Benzoyl-ay-di-o- and -m-tolylguanidines NBa:C(NH*C,H,Me) have m. p. 126' and 177-1 78" respectively. Di-m-tolylguanidzne NH:C(NH*C,H,Me) m. p. 108-log" was obtained from the benzoyl compound by hydrolysis with potassium hydroxide. ,3-Benzoyl-ay-di-p-tolylguanidine m. p. 1 90° yields a hydrochloride m. p. 190-1 91" (decomp.). The following guanidines were also prepared benzoyltetraphenylguanidine m. p. 142-1 44' ; P-benzo yl- a y-diphen yl-a y-dirnethylguanidine m.p. 1 35' ; P-6en,xoyl-ay-di- p-anisylguanidine m. p. 12S0 and di-p-anisylguanidine m. p. 153' ; P-benxo y l-a y-di-a-naphth ylguanidine m. p. 1 62" and di-P-naphth yl- guanidine m. p. 197' (decomp.). E. G. Reduction of SernicarbazoneB. SIDONIUS KESSLER and HANS RUPE (Ber. 19 12 45 26-30).-Semicarbazones are readily reduced by sodium amalgam in dilute alcoholic solution at a slightly elevated temperature. In some instances for example those of cinnamaldehyde and styryl methyl ketone the influence of the constitution of the semicarbnzone prevents reduction to semicarbazide. Banz ylsernicarbaxide CH,Ph-NH*N H CO-NH from benzaldeh yde- semicarbazone crystallises in lustrous platelets m. p. 155'. It is distinctly basic dissolving in cold dilute acids and reduces Fehling's solution on boiling.The hydrochloride forms silky lustrous needles m. p. 17s-180'; the sulphate yields slender needles m. p. 158'; the picrate gives slender yellow needles m. p. 161-162' and the oxabate has m. p. 178-179' (decomp.). The acetyl derivative crystallises in beautiful colourless plates m. p. 207"; a diacetnte could not be obtained ; the benxoyl derivative forms colourless needles m. p. 230". 1YitrosobenxyZsemicarbccxide CH,Ph*N(NO)*NH*CO*NH prepared by the action of sodium nitrite and hydrochloric acid on benzyl- semicarbazide crystallises in long needles m. p. 1 3 3 O (decomp.). p-Methylbenxylsemicarbaxide crystallises in slender colourless needles m. p. 158'; the hydrochloride forms colourless needles m. p. 138' (decomp.) ; the rrulphate decomposes at 187" ; the picrate yields yellow needles m.p. 178' (decomp.) and the acid oxalate decomposes ati. 220 ABSTRACTS OF CHEMICAL PAPERS. 175'. The acetyl derivative crystallises in glistening colourless platelets m. p. 225' (not decomp.). Nitroso-p-inethyl6enxy~sem~ca;rbaz~de separates in colourless platelets and decomposes a t 126-127'. When cinnamaldehydesemicarbazone is reduced P-phenylprop- aldehydesemicarbazone m. p. 12S0 is the sole product. Similarly from the semicarbazone of styryl methyl ketone the product is the semicarbazone of phenylethyl methyl ketone. E. F. A. Reduction of Semicarbazones and the Preparation of Some Hydroxytriazoles. HANS RUPE and E. OESTREICHER (Ber. 19 12 45 30-38. Compare preceding abstract).-The property of semicarb- azones of being reduced to semicarbazide is closely dependent on their constitution.A phenyl residue must be attached directly to the group C:N. Aliphatic hydrocyclic and compounds i n which phenyl is replaced by benzyl cannot be reduced. The seniicarbazones of benzoy lpropionic acid and of p-benzoquinone could not be reduced. The semicarbazides vary considerably in their basic properties ; those from benzophenone aceto- phenone and deoxybenzoin dissolve in dilutle acids in the cold whereas those from salicylaldehyde or piperonal dissolve only when boiled with acids. 3 4-MethyZe~dioxybenx?/lse?nicarbazide CH,O, C,H3 CH,*NH*NH*CO-NH from piperonalsemicarbnzone forms transparent prisms m. p. 184'. The acetyl derivative crystallises in slender transparent needles m.p. 203-204O ; the formyl derivative forms long transparent rhorribic plates m. p. 204-205'. 3-Hydroxy-(rnp-rnethylenedioxyben=yl)-5-methyl-l 2 4-triazoZe CXle:N CH$j02:C(3H3* CH,"<~ ~ - - b 09 prepared by boiling the acetyl derivative with 30% sodium hydroxide and decomposing the sodium salt formed with hydrochloric acid forms opaque square crystals with stunted ends m. p. 190'; i t forms characteristic metallic salts. From the formyl derivative of the semi- carbazide 3-hydroxy-(mp-mclthylenedioxybenxyl)-l 2 4-triaxole is ob- tained ; it crystallises in stout transparent plates m. p. 246-24'7'. a- Phenylethylsemicarbaxide CH MeP h NH- N H - CO NH from acet o- phenonesemicarbazone crystallises in four-edged transparent prisms m. p. 142-143O. The acetyl derivative forms platelets m.p. 228-230° the formyl derivative crystallises in slender matted needles. m. P. 187" 3 - Hydrox y - 1 - a-phen y Zeth y 2-5 -meth y 2 tqiazo Ze CMe' CHMePh*.N<F-LC .OH crystallises in short well formed prisims m. p 146-147O. 3-Hydro~y-l-a-phanyZetAyltriaxo/e is obtained in transparent slender intergrown prisms m. p. 140'. Diphen ylmethylsemicarbaside CH Ph NH*NH* CO N H cry s fa1 I ises in long lustrous transparent needles m p. 164-165O; it gives anORGANIC CHEMISTRY. i. 221 in tense yellow coloration with concentrated sulphuric acid. The acetyl derivative crystallises in small transparent prisms m. p. 23'7' ; theformyl derivative yields small colourless needles m. p. 182'. The nitrosoamine CHPh,*K'(NO)*NH-CO*NH forms slender faintly yellow-coloured needfes A.p 122'. CMe:r 3-Hydroxy-l -diphen ylrnethyl-5-methyltriazoZe CHPh,*N<N== c. crystallises in glistening needles which appear under the microscope as prisms with two superposed pyramids. 3-Eydroxy-l-diphenylrnethyltriazole forms slender matted needles m. p. 253'. ap-D;phcnylethylsemicarhazide prepared from deoxybenzoinsemicarb- azone crystallises in long slender transparent needles grouped in st.ellar aggregates m. p. 139'. The acetyl derivative forms slender woolly needles m. p. 196'; the formyl derivative gives small trans- parent prisms m. p. 194'. o-Hydroxybenzyt?semicarbazide from salicylaldehydesemicnrbazone crystallises in four-edged prisms m. p. 128'. The acetyl derivative separates in slender needles m. p. 204'; the formyl derivative forms flat transparent plates m.p. 183-184'. 3- Kydroxy- 1-04 ydroxp benz yl-5-rnethyltriazole forms crystals m. p. 192' and gives a reddish-violet coloration with sulphuric acid. 3-Hydrozy- 1-0-8 ydroxy benzyltriaxols forms platelets of silvery lustre m. p. 211' (decomp.). 3-Hydroxy-5- bcnxyl- 1 -meth yltriaxole crys tallises in transparent prisms m. p. 168'. 3- Hydyoxy-1-benzyltriaxole forms lustrous nacreous platelets m. p. 147-148'. * E. F. A. DFtermination of Configuration of Stereoisomeric Hydr- azones. MAX BUSCH (Beq-. 19 12 45 73-85).-Stereoisomeric diphenylsemicarbazones of unsymmetrical esters of dithiocarbonic acid NHPh*CO*NPh*N:C(SR)-SR' analogous to the stereoisomeric phenylhydrazones (Abstr. 1911 i 811) have been obtained. Ethyl d ithiocarbonate-diphen ylsemica bazide NHPh*CO-NPh*NH*CS,Et stout needles m.p. 149-150° obtained from equal molecular quan- tities of phenylcarbimide and ethyl phenyldithiocarbazinate in warm benzene dissolves readily in aqueous alkalis and is decomposed by prolonged boiling with alcoholic potassium hydroxide yielding ethyl mercaptan and after acidifying 3-thiol- 1 4 - diphenyltriazolone (Abstr. 1911 i 689). By treating its alcoholic solution with equi- valent quantities of potassium hydroxide and methyl iodide i t yields (a) methyl ethyl dithiocarbonatediphenylsemicarbazone NHPh*CO*NPh-N :C(SMe)*SEt m. p. 93-94' rhombic needles. The stereoisomeric ( b ) methyl ethyl dithiocarbmate-diphmylsemicarbaaone m. p. 87-88' monoclinic needles or prisms is prepared in a similar manner from methyl dithiocarbonate- diphenylsemicarbazide ethyl iodide and potassium hydroxide.Thesei. 222 ABSTRACTS OF CHEMICAL PAPERS. two stereoisomeric semicarbazones behave very similarly. However when warmed at 80-60° with alcoholic potassium hydroxide the former yields ethyl mercnptan and the methyl thio-ether of 3-thiol- 1 4-diphenyltriazolone whilst the latter yields methyl mercaptan and the ethyl thio-ether m. p. 111-112° of the same triazolone; in both cases the alkyl group which was introduced first is eliminated as a mercaptan. Another pair of stereoisomeric semicarbazones are described. p:Nitrobenzyl phenyldithiocarbazinate and phenylcarbimide in benzene yield p-nitrobenxyl dithiocarbonate-diphenylsemicarbaxide NHPh* CO*NP h*NH*CS,* C,H,*NO m.p. 11 9-120" colourless needles which is converted by alcoholic potassium hydroxide and methyl iodide into (a) p-nitrobenxyl methyl dithiocarbonate-diphen ylsemicarbazone NHPh CO*NPh-N :C( SMe)-S*C7H,*N0 m. p. 126" stout yellow needles. The stereoisomeric ( b ) p-nityobenzyl methyl clit~iocarbonate-~~p7~e~ylse~~carbaxon~ m. p. 1 47" colourless plates is prepared in a similar manner from methyl dithiocarbonate- diphenylsemicarbazide and p-nitrobenzyl chloride. Either of these semicarbazones is converted when fused or heated in alcohol for one to two hours into an equilibrium mixture of approximately equal quantities of both forms. When warmed with alcoholic potassium hydroxide the yellow form yields the methyl thio-ether of 3-thiol- 1 4-diphenyltriazolone whilst the colourless form yields methyl mercaptan and the p-nitrobertxy2 thio-ether m.p. 178-179O of the same triazolone; in both cases again the nlkyl group which was first introduced is eliminated by the action of the alkali. c. s. Influence of the Acridine Ring on the Colour of Certain Colouring Matters. A. E. PORAI-KOSCHITZ Y. I. AUSCHKAP and N. K. AMSLER (J. Russ. Phys. Chem. Xoc. 1911 43 15S7-1603).- I n order to decide between the chromophore and dynamic theories (compare von Baeyer Abstr. 1907 i 757) of the colour of triphenyl- methane colouring matters the authors have prepared and studied acridylmalachite-green and acridylpyronine. The results obtained are distinctly in favour of the latter of the two hypotheses since the absorption spectra of the two colouring matters scarcely differ from those of malachite-green and rosamine the absorption bands being displaced towards the red end of the spectrum to an extent approxi- mately such as is usually observed with any more or less considerable increase in the molecular weight.A further consequence of the replacement of the benzene ring by an acridine nucleus consists in a marked diminution in the " permanency " of the spectral bands this being expressed in a decrease in the dyeing properties of the colouring matters. I n the case of acridylmalachite-green the quinonoid base was obtained in the pure state. The action of 5-aldehydoacridine (compare Abstr. 1911 i 688) on dimethylaniline in presence of zinc chloride and subsequent treatment with dilute hydrochloric acid followed by oxidation of any leuco- compound with lead dioxide yield a small quantity of a violet colour-ORGANIC CHEMISTRY.i. 223 ing matter which mas not investigated further and dimethylaminophenyl- acr~dylmethylensqu~nonodimethp~~mon~um chloride NqC s 4 H C6.H4*NMe2 ’ which is a green colouring matter with a bronze lustre dissolving slightly in water and readily in alcohol. It dyes cotton a somewhat bluer green than malachite-green whilst wool is dyed only very faintly in neutral solution but more strongly in presence of borax or ammonia. The first portions of wool immersed are coloured green with a slight blue tinge but if successive portions are introduced into the same bath the colour approaches more and more nearly to blue; this is found to be a result of the presence of alkali.TetramethyZdia~ninodiphenylacridylmethane (leuco-base of acridyl- malachite - green) N~CGH4~C.CH(C6H,*NMe2~2 C H forms yellow acicular crystals m. p. 171-172O insoluble in water but readily soluble in acids or organic solvents. forms The qzcinonoid base N%6H4 H ;NMe greenish-golden plates. In neutral aqueous solution the maximum intensity of the absorp- tion band of acridylmalachite-green lies at X = 64’2 pp whilst according to Formanek that for malachite-greeu is a t X = 618.5 pp ; the displace- ment caused by the sirbstitution of an acridine nucleus for a benzene ring is hence 23.5 pp. Acridylp yi*onine N<22>G* C<C6H3(N C6H3( :NEt,*OH) ‘2)- >O obtained by condensing 5-aldehydoacr%d;ne with m-diethylaminophenol in presence of sulphuric acid dissolves in very dilute acids giving a violet-red colour changing to cherry-red on addition of concentrat,ed acid.It dyes silk and wool reddish-violet and cotton blue with a red tinge no mordant being necessary. The absorption bands are almost identical in aqueous and in alcoholic solution and in both cases little change is produced by acidification with nitric acid or addition of potassium hydroxide ; this behaviour is characteristic of all colouring matters of the pyronine series. The absorption spectrum of acridine lies in the ultra-violet close to the visible part of the spectrum and the introduction of the pyronine residue results in the displacement of this absorption into the violet. The maximam intensities of the absorption bands lie a t 580 pp and 534.8 pp whilst Biehringer (Abstr.1897 i 73) found for tetra-ethylrosamine 563.5 and 527.5 pp; the displacements caused by the replacement of the benzene ring by an acridine residue are hence 16.5 pp and 7.3 pp. Relation between Constitution and Phototropy. MAURIZIO PADOA and F. BOVINI (Atti R. Accad. Lincei 1911 [v] 20 ii 712-717. Compare Padoa and Graziani Abstr. 1910 i 778 ; Pitdoa and Srtnti Abstr. 1911 i 693 1029).-The phototropy of the com- pounds described in t h e present paper r”ol1ows the regularities previously discovered. ~-~s?~z~Z-a-naphtAyZosazone C,Ph,( :N*NH*CloH7)2 obtained by C6H4>C. C<C6H4:NMe2C1 6 4 C6H4>(3.C<C6 C €I 4 :NMe,*OH T. K. P.1. 224 ABSTRACTS OF CHEMICAL PAPERS. Purgotti's method (Abstr.1893 i 354) forms lemon-yellow crystals m. p. 175O and is not phototropic. /3- Pipei*il-a-naphth,ylosaxone C,(C,R,:O,:CH,),( :N*NH*CIoH7) pre- pared by MacNair's method (Abstr. 1890,1245) crystallises In yellow needles m. p. lS9" and is prototropic. P-An~sil-a-naphth yloaaxono C,(C,H,*OMe),( N *NH *C nH7)2 prepared like t h e preceding compound cryst,allises in golden-yellow needle@ m. p. 155" and is prototropic. Piperonaldehyde-a-naphth y Mpdrazone CH, 0, C,B,*CH N*NH*CloH7 cry~tallises in greenish-yellow needles m. p. 147" and is not phototropic. HO*C,H,*CH:N*NH*CloH7 forms lustrous golden-yellow needles m. p. 134" and is not phototropic. Vc~niZZin-a-naphth~Z~ydr~zon(J OMe*C,H,(OH)*CH:N*NH*Cl~H7 is an unstable yellow crystalline powder which i R not phototropic.p - ToZuddahyde - a - naphthylhydrazone C,II,Me*CH:N*NH*Cl,H7 crysttsllises in greenish-yellow needles m. p. 152" and is not pbototropic. /3-BanziZ-1 3 4-xyl~Zosazone C,Ph,( :N-NH*C,H,hle,) is an orange- yellow crystalline substance m. p. 7 1 -72" and is phototropic. Piperil- I 3 4-xyZylosaxone C2( C,H,:O,:CH,),( :N*NH*C,H,Me,) forms lemon-yellow prisms in. p. l87" and IS phototropic. A n i d - I 3 4-xylyZosazone C2(C,H,*OMe),( :N*NH*C,H,Me,) is an orange-yellow crystalline substance m. p. 75" and is phototropic. Cunzinil-1 3 . 4-xyZyZosnzone C,( C,H,PrP),( :N*NH* C,H,Me,),,. is a yellow crystalline substance m. p. 64-70" and is not phototropic. R. V. S. Salicylaldehyde - a - naphthylhydrazone Researches on Purines. IV. 2-Oxypurine and 2-0xy-8- methylpurine.CARL 0. JOHNS (J. Biol. Chem. 1912 11 67-72).- 6-Oxypurine (hypoxanthine) was first isolated by Scherer in 1850 and nearly fifty years later was synthesised by Fischer. 8-Oxypurine was prepared by Pischer and Ach. 2-Oxypurine was prepared by Tafel and Ach from guanine but they did not offer any proot of its structure. In the present research it was prepared from 5 6-di- amino-2-pyrimidone and the product agrees in all respects with that of Tafel and Ach. When 5 6-diamin0-2-pyrinriidone is heated with formic acid a morwformyl derivative i u obtained; this yields a potassium salt which when heated gives off water and changes to the potassium salt of 2-oxypurine ; 2-oxypurine cryhtallises with 1H20 and does not lose it until heated t o 120". The picrate nitrate and hydrochloride were prepared.When 5 6-diamino-2-pyrimidone is boiled with acetic anhydride i t forms chiefly a monoacetyl compound together with some of the diacetyl compound. When the potassium salt of the former is heated it yields the potassium salt of 2-0xy-B-methylpurine ; this substance forms a picrate decomp. 250° and a nitrate decomp. 205O which may be used for its identification. W. I). H.OHGANlC CHEMISTRY. i. 225 Preparation and Reactions of Aeo-acyl Compounds. ROBEHT STOLLL~ [with J. MAMPEL J. HOLZAPFEL and I(. C. LEVERKUS] (Ber. 1912 45 273-289).-Azodiacyls of the type R*CO*N:N*CO*R (where R = H Me CHEt,,. Ph C,H,Cl and a-CIoH7j have been pre- pared by the action of iodine or bromine in ethereal solution on the mercury or silver salts of symmetrical diacylhydrazides K*CO*NH*NH*COK.The azodiacyls prepared from hydrazides of aromatic acid3 are com- paratively stable whilst those derived from aliphatic acids are unstable and could only be obtained iu ethereal solution or in a n impure condition as red oils. They are converted by reducing agents such ae hydriodic acid hydrogen sulphide and phenylhydrazine into the original hydrazides. When treated with water they yield tri- acylhydrazides the decomposition taking place according t o the following scheme 2N,(CO*R) + H,O = R*CO,H + N2 + R*CO*NH*N(CO*R),. It is supposed that the first stage in the reaction consists in the partial hydrolysis of the azodiacyl t o the compound (I) which instantly decomposes thus (I) NH:N*CO*R -+ H + N + *CO*R ; this is foliowed by addition of H and *COX to a second molecule of the azodiacyl with the formation of a triacylhydrazide.Evidence in support of this view is furnished by the production of triacyl- hpdrazides by the reaction of azodibenzoyl and azodi-a-ethylbutpryl with benzaldehyde and also by the formation of benzoylhydrazobenzene NPhBrNHPh by heating azobenzene with benzaldehyde for fifteen hours a t 110'. The decomposition of the azodiacyls by heat has not yet been thoroughly investigated but with azodibenzoyl and azodi-a-naphthoyl the decomposition occurs t o a small extent as follows COR-N:N*CO*R -+ COR*COR + N,. Azodicarboxylimide and several of its derivatives of the formula (I) below (where R=H P h NH N:CHPh) have also been prepared by the action of iodine in ethereal solution on the silver salts of the corresponding hydrazo-compounds (11) ; they are decomposed by water as follows Ph*CHO + R*CO*N:N*CO*R -+ R*CO*NBz*NH*CO*K #::~>NR + ZH,O = ;YH"!O>~~ + N + zco + R-NH,.NH*CO (1.) (11.1 The mercury salt of 8-dibenzoylhydrazide CPh<gZ.g>CPh obtained by the action of mercuric chloride on the hydyazide and sodium ethoxide in alcoholic solution is converted by bromine in etbereal solution into azodibenzoyl (Stoll6 and Benrath Abstr. 1900 i 531; 1904 i 935). When heated at 270' i n an atmosphere of carbon dioxide this decomposes yielding small quran tities of benzil and 2 5-diphenyl-1 3 4-oxadiazole. It combines with benzaldehyde at llOo to form tribenzoylhydrazide a small amount of the above-i. 226 ABSTRACTS OF CHEMICAL PAPERS.mentioned oxadiazole being produced simultaneously. aniline yielding benzanilide and s-dibenzoylhydrazide thus It reacts with (1) NBLNBz + NH2Ph = NHPhBz + N2 + 2H (2) 2H + NBLNBz = NHEz*NHBz and with dimethylaniline to form 8-di benzoylhydrazide the dimethyl- aniline being oxidised to tetramethyldiphenylinpthane and other products not yet investigated. s-Bi- p- chlorobenzoylh ydrazide prepared from h y drazine sul phate p-chlor obenzoyl chloride and aqueous sodium hydroxide crystallises in felted needles m. p. 289" and reacts with sodium hydroxide in aqueous alcoholic solution to form the sodium salt C6H4C1*C( ONa) N * NH*CO*C6H4CI which crystallises in lustrous pale yellow leaflets and is oxidised by iodine in ethereal solution to uxodi-p-chlorobensoyl N,(CO*C,H,Cl) yellow needles m.p. 147" (decornp.). s-Di-a-naphtiLoylhydraxide prepared in a similar manner has m. p. 260° and forms a silver salt C,,H,*C(OAg):N*NH*CO-CloH7 which is oxidised to uxodi-a-waphthoyZ N,(CO-C1,H7)2. This crystallises in orauge-red needles m. p. 1484 and when heated at 140-150° loses nitrogen yielding di-a-naphthyldiketone C,,H7*CO*CO*CIOH7 m. p. 187" ; it reacts with water to form a-naphthoic acid s-di-a-naphthoyl- h j drazide and tri-a-naphthoylhydraxide C,,H CO* NH*N( CO C,,H7) which has m. p. 188O and has also been prepared by the action of a-naphthoyl chloride on the silver salt of s-di-a-naphthoylhydrazide. The sodium salt of s-benzoylacetylhydrazide CgHg02N2Na is converted by mercuric chloride in alcoholic solution into the mercury salt C,H,O,N,Ng.Benxoylccxoacetyl NAcZNBz obtained in an impure condition as a red oil by the interaction of iodine and the preceding mercury salt in ethereal solutioo is decomposed by water yielding benzoic acid s-di benzoylhydrazide and dibe?zxoyZacetylhydraxide NAcBz*NH Bz m. p. 171". 2-Phenyl-5-mtetl~y/E-l 3 4-oxadiaxole CMe<F.y>OPh prepared by heating s-benzoylacetylhydrazide with phosphoryl chloride crystallises in lustrous plates m. p. 67"; it forms with silver nitrate an additive compound crgstallising in lustrous needles m. p. 185"; a n additive compound with mercuric chloride is also described. Dibenxoyldiacetyl~~ydruzii~e N AcBz*NAcBz prepared either from acetyl chloride and the mercury salt of s-dibenzoylhydrazide or from benzoyl chloride and the mercury salt of s-diacetylhydrazide crystallises in leaflets m.p. 109". s-Diformylhydrazide yields a crystalline silver salt C,H202N2Ag2 which explodes when heated and a rnercurw salt Azodvyormyl N,(CHO) prepared from the preceding mercury salt could not be isolated on account of its instability; its ethereal solutions have a raspberry-red co our. The mercury salt of s-diacetylhydrazide C,H602N,Hg prepared fromORGANIC CHEMISTRY. i. 227 the hydrdzide sodium ethoxide and aqueous mercuric chloride reacts with iodine in ethereal solution in the presence of magnesium or barium oxides yielding azodiacetyl NAcINAc in an impure condition as a dark red oil. s- Di-a-ethylbutyrylthydruzide N,H,(CO*CHEt,) prepared from the corresponding acid chloride and hydrazine hydrate in the presence of sodium carbonate crystallises in white needles m.p. 230O. Azodi-a-ethylbutyryl N,(CO*CHEt,) obtained from the mercury salt C,,H,,O,N,Hg of the preceding compound as a red oil is decomposed by water into a-ethylbutyric acid and tri-a-ethylbutyryl- hydrazide CHEt,*CO*NR*N(CO*CHEt,) which crystallises in colour- less prisms m. p. 95O and has also heen prepared by the interaction of a-ethylbiityryl chloride and s-a-diethylbutyrylhydrazide in pyridine solu- tion at 100'. It combines with benzaldehyde yielding benzoyldi-a-ethyl- butyrylhydrazide CHEt,*CO*NBz*NH*CO*CHEt crystallising in small prisms m. p. 123O. The latter compound may also be prepared from benzoyl chloride and s-di-a-ethylbutyrylhydrazide in pyridine solution. N-CO N*CO Axodicarboxylimide [diketodihydro-1 3 4-triaxole] I I >NH ob- tained as a violet oil by the action of ethereal iodine on the silver salt of hyclrazodicarboxy limide in the presence of barium and magnesium oxides is instantly decomposed by water yielding nitrogen carbon dioxide and hydrazodicarboxylimide.Hydrazodicarboxylphenylimide yields the silver salts C,H,O,N,Ag and C8H,0,N3Ag of which the latter is converted in the usual manner into azodicarboxylphenylimide. This forms carmine-red crystals (compare Thiele and Stange Abstr. 1895 i 251) gives violet solutions in ether and decomposes when heated into phenylcatbimide and hydraxotetracarboxyldiphen yldi-imide * " co q? co>Np h Ph<Co N co which crystallises from glacial acetic acid in lustrous white leaflets subliming in needles without melting. Axodica?.boxylccmi~oi~ide (axodicai.box~l~~ydrazide) [I - amino - 2 5- fj*c0>N*NH2 prepared from the silw N-CO diketodihydro-1 3 4-triaxoZe] salt of aminourazole (Curtius and Heidenreich Abstr. 1896 i 143) C,H,O,N,Ag is an unstable violet powder ; it explodes at 7 2 O and is slowly converted by water into aminourazole. Azodicarboxylbenxylidmeh ydraside R'co>N*K CHPh obtained N-CO from the silver salt of benzylideneaminourazole (hydrazodicarboxyl- benzylidenehydrazide) C,H,O,N,Ag forms carmine-red crystals which become colourless when heated (at 135-138') owing to loss of nitrogen and conversion into hydraxotetracarboxyldibenxylide.necEihyds.- nxide CHPh N"<,O. The mercury salts of ethyl hydrazodicarboxylate yields with iodine in ethereal solution ethyl azodicarboxylate (Cur tius and Heidenreich CO*N*CO CO>N*N CHPb m. p. 2 85'.i. 228 ABSTRACTS OF CHEMICAL PAPERS. Zoc. cit.) and when heated with benzoyl chloride in carbon tetra- chloride solution at 1 OOO form8 ethyl diben,nxoyZhydrasodicar~ox~Za~ C20H2,,06N2 which forms white crystals m. p. 83'. F. B. Enzymic Decomposition of Hydrogen Peroxide. 11. PERCY WAENTIG and OTTO STECHE (Zeitsch. physiol. Chem. 19 12,76 177-2 13. Compare Abstr. 1911 i 759).-The behaviour of both animal and vegetable extracts in decomposing hydrogen peroxide is very similar and in far closer agreement with Senter's haemase than is generally stated. This is illustrated particularly by the influence of hydrogen and hydroxyl ions on the rate of reaction-any shift in equilibriurri from that prevailing in distilled water free from carbon dioxide causes a retardation. The reaction is however less sensitive when relatively large amounts of impurity are present in the extracts ; this may be due to the amphoteric character of the proteins in retaining acids or bases or t o a definite protective action of the impurities analogous to that of the so-called '' protective colloids." This insensi- tive character is specially marked in catalase solutions prepared from the alcohol precipitate of an aqueous extract of germinating barley. The enzyme extracts behave similarly at 0' and a t 30' ; at the higher temperature the hydrogen ion has less the hydroxyl ion more influence on the rate of change. The influence of temperature on the rate is very small. The course of change does not quite correspond witb the simple mass-action law; the value of K falls off even in very dilute hydrogen peroxide solutions at 0". Dialysis yields weaker extracts but with these a more constant value of R is obtained. The amount .of enzyme is roughly proportional to the rate of change. Exposure to ultra-violet light weakens the enzyme activity ; the effect is greater in alkaline than in neutral or acid solution. Complete precipitation of the enzyme from extracts of liver fat barley etc. requires an alcohol concentration of 55%. Animal extracts show a decline in activity when the concentration of hydrogen peroxide exceeds a certain point; this is not the case with plant c s t rac t s. It would appear that the active substance which brings about the decomposition of hydrogen peroxide is the same irrespective of origin. E. F. A. Preparation of Mercury p-Aminophenylarsinates. AKTIEN- GESELLSCHAFT FUR ANILIN-FABRIKATION (D.R.-P. 237787).-&fercury hydrogen p-arninophenylarsinate [NH,-C,H,*AsO( OH)*O],Hg a colour- less powder sparingly soluble in water islprepared by stirring together an aqueous paste of p-aminophenylarsinic acid (2 mols.) and mercuric oxide (1 mol.). The basic salt NH,*C,H,*AsO(OH)*O~Hg*OH is obtained when equimolecular proportions of the amino-acid and mercuric chloride in the presence of alkali (2 mols.) are employed. F. M. G. M.

ISSN:0368-1769    

DOI:10.1039/CA9120200149

出版商:RSC    

年代:1912

数据来源: RSC