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[Issued 18111 13 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 29. No.419. THE Council has ordered the following letter and report to be printed in the Journal and Proceedings of the Society : WHINFIELD, SALcOMBE, S. DEVON. Sept. 16th, 1913. GENTLEMEN, I have the honour to forward the Annual Report of the International Committee on Atomic Weights for 1914, which is submitted for publication in the Society’s Transactions and Proceed- ings, as hitherto. The Report deals with all the determinations of atomic weighta which have been published since the issue of the preceding Report, but, in accordance with the resolution passed at the Eighth Inter- national Congress of Applied Chemistry, it is not proposed to make any change in the official table of atomic weigh& until the meeting of the next Congress in 1915.Apart from this, the work of the past year has not shown any necessity for any addition to the existing list of Atomic Weights, or for any substantial alteration in the values last published. It is accordingly recommended that the table accompanying the Report for 1913should be reprinted it8 it stands. b 240 I have appended the signatures of Professors Ostwald and Urbain as desired by them. I am, Gentlemen, Your obedient Servant, T. E.THORPE. The Hon. Secretaries, The Chemical Society, London. Annual Report of the International Committee on Atomic Weights, 1914. At the Eighth International Congress of Applied Chemistry, held in New York in September, 1912, a resolution was passed favouring less frequent changes in the official table of atomic weights, Such changes are sometimes embarrassing to technical chemists, and the resolution adopted expressed a desire that the table for 1913 should remain, for legal and commercial use, the official table until the next Congress convenes, in 1915.With this wish the Committee can easily comply; at least, in its essential features, for changes which affect the industrial chemist are not likely to be important, and the text of each annual report will give all the refinements of data which may be needed in theoretical dis- cussions. Only such changes in the table as seem to be absolutely necessary need be made during the next two years, and that they should seriously affect the values in common use is highly improb.able. Since the annual report for 1913 was prepared, a number of important memoirs on atomic weights have appeared, which may be summarised as follows : Nitrogen.-Scheuer (Aneeiger TV'ien Akad., 1912, 49, 36), from analyses of nitrogen trioxide and tetroxide, and from measurements of ratios connecting the oxides of nitrogen, finds N=14.008 as the mean of five series of determinations. He also determined the densi- ties of ammonia and of sulphur dioxide, obtaining results in accord- ance with earlier investigations. The value assigned to N varies from the rounded-off figure given in the table by only one part in 7000. ChZorine.-By the synthesis of NOC1, by the direct union of nitric oxide and chloride, Wourtzel (Compt.rend., 1912, 155, 345) finds C1=35.4596, when N=14.008. He also (Compt. rend., 1912, 155, 152) determined the density of nitrosyl chloride, and found the weight of the normal litre to be 2.9919 grams. From this he deduced a molecular weight of 65.456, which is probably too low. From the ratio between ammonia and hydrochloric acid, remeasured 241 by Baume and Perrot (Compt. rend., 1912, 155,461), the authors found C1=35*463, an unusually high value. None of these new determinations warrants any change in the accepted figure for chlorine. Bromine.-By the direct synthesis of hydrobromic acid from weighed quantities of hydrogen and bromine, Weber (J. Amer. Chem. SOC.,1912, 34, 1294) finds Br=79.3066 when H=l.With 0=16, the value for bromine becomes 79.924. The accepted value differs from this by only 1part in 20,000. Phosphorus.-Baxter and Moore (J. Amer. Chem. SOC.,1912, 34, 1644), from analyses of phosphorus trichloride, find P= 31.018, in good agreement with previous determinations. This is slightly lower than the value given in the table. Iron.-By the reduction of ferric oxide in hydrogen, Baxter and Hoover (J. dmer. Chem. Soc., 1912, 34, 1657) find Fe=55-847. Cadmiunz.-The electrochemical equivalent of cadmium has been determined by Laird and Hulett (Trans. Amer. Electrochem. SOC., 22, 385), who precipitated cadmium and silver simultaneously in an electric current. From the data given, the atomic weight of cadmium is 112.31, a low value, but one in accord with the previous work of Hulett and Perdue on cadmium sulphate.The investiga- tion is to be continued with the chloride. Tellurium.-The supposed complexity of tellurium has been re- investigated by Dudley and Bowers (J. Amer. Chem. SOC.,1913, 35, 875), with negative results. They attempted to determine the atomic weight by the basic nitrate method, which they found to be unsatisfactory. A series of syntheses of the tetrabromide gave Te= 127.479. Uranium.-From calcinations of uranyl nitrate to uranium dioxide, Lebeau (Compt. rend., 1912, 155,161) found U=238.54. CEchsner de Coninck (Compt. rend., 1912, 155,1511), by calcination of uranic oxalate, obtained variable results, in mean, U =238.44.Scan&um.-Atomic weight redetermined by Meyer and Golden- berg (Chem. News, 1913, 106,12), who employed the sulphate method. In mean, Sc=44*14, in agreement with the accepted value. The higher figure given by Meyer and Winter was due to the pres- ence of thoria in the material employed. Yttrium.-Two determinations of the atomic weight by Meyer and Wuorinen (Zeitsch. anorg. Chem., 1913, 80, 7) gave Yt=88*6. The sulphate method was used. Egan and Balke (J. -4mer. Chem. SOC.,1913, 35,365), in a preliminary study of the ratio between yttrium chloride and yttria, found Yt =90*12. As their research-is to be continued, it would be unwise to use either of these investiga- tions as a basis for changing the table. The lower of the two values appears to be the more probable. 242 Ruthenium.-Vogt (Sitzungsber.phys. med. Soz. Erlangen, 43, 268), from reductions of ruthenium dioxide, finds Ru =101.63. Palladium.-Determinations of atomic weight by analysis of palladiammonium chloride have been made by Shinn (J. Amer. Chem. SOC.,1912, 84, 1448). The mean value obtained was Pd= 106.709, but the individual determination varied more than is satisfactory. Shinn supposes that the chloride is less definite than it has been assumed to be. Radium.-From analyses of radium bromide, Honigschmid (Monatsh., 1913, 34, 283) finds Ra=225*97, in confirmation of his former analysis of the chloride. The discordance between this value and the higher value obtained by others is unexplained.The presumption is in f avour of Hijnigschmid’s determination, but a change in the table may well be deferred until more evidence is available. The following table is that of 1913, unchanged. (Signed) F. W. CLARKE. W. OSTWALD. T. E. THORPE. G. URBAIN. 243 1914. I&mu tio 71 al Atonaic Weight8. 0=16. 0=16. Alumiiiiuni ................. A1 27.1 Rlolybdenuin ...............Mo 96.0 Antimony .....................Sb 120.2 Neodymium .................Nd 144.3 Argon ..................... A 39.83 Neon ........................... Ne 20.2 Arsenic .....................As 74.96 Nickel ........................Ni 58'68 Barium ........................I3a 137.37 Niton (radium emanation) Nt 222-4 Bismuth .....................Bi 208.0 Nitrogen .....................N 14'01 Boron ........................E 11.0 Osmium ..................... 0s 130'9 Bromine .................... l3r 79-92 Oxygen ........................0 16'00 Cadmium ..................... Cd 112'40 Palladium .....................Pcl 106.7 Cmiuni .......................Ca 132.81 Phosphorus .................. P 31 '04 Calcium .....................Ca 40.07 Platinum .....................Pt 195.2 Carbon ........................C 12.00 Potassium..................... I< 39'10 Cerium ........................ Ce 140% Praseodymium ...............Pr 140'6 Chlorine .....................C1 35'46 Eadinm ........................ Ka 226'4 Chromium ..................Cr 52.0 Rhodium .....................Kh 102.9 Cobalt .......................Co 58.97 Rubidinm ....................Rb 85.45 Columbium .................Cb 93.5 Ruthenium .................. RU 101.7 Copper ........................Cn 63.57 Samarium ................. Sa 150'4 Dysprosium .................Dy 162.5 Scnii diuni ....................Sc 44'1 Erbium ..................... Er 167.7 Selenium ..................... Se 79'2 Euroyinm..................... Eu 152.0 Silicon ........................ Si 28-3 Fluorine .....................F 19.0 Silver ........................ Ag 107'88 Gadolinium .................. Gd 157.3 Sodium ........................ Na 23.00 Gallium .................... Ga 69.9 Strontium ..................Sr 87'63 Germanium ..................Ge 72.5 Snll)hur .....................S 39-07 Glucinuni ....................G1 9.1 Tantalum ................. Ta 181-5 Gold ........................... Au 197.2 Tulluriuin ..................... Te 127.5 Helium ........................ Ire 3.99 Terbium ..................... Tb 159-2 Holmium .....................€10 163.5 Thnlliu m ....................TI 204.0 Hydrogen ..................... €1 1'008 Thorium ..................... Th 232-4 Indium ....................... In 114.8 Thuliuni ..................... Tm 168.5 Iodine ........................ I 126'92 Tin ........................... Sn 119.0 Iridium ....................... Ir 193.1 Titani.nm ..................... Ti 48'1 Iron ...........................Fe 55-84 Tungsten .....................TV 184.0 Krypton .....................Kr 82.92 Uranium ..................... U 238.5 Lanthanum .................La 139 0 Vanndium ..................V 51.0 Lead ..........................Pb 207*1O Senon ........................ lie 130-2 Lithium ..................... Li 6.94 Ytterbium (Neoytterbium) Yb 172.0 Lnteciurn ....................Lu 174-0 I't tr ium ..................... Yt 89.0 Magnesium ..................Mg 24 '32 Zinc ........................... Zn 65.37 Manganese ..................Mn 54-93 Zirconium .....................Zr 90-6 Mercury ..................... Hg 200'6 c The following are abstracts of papers received during the vacation, and published, or passed for publication, in the Trans-actions : 212.The viscosity of cellulose nitrate solutions.” By Frank Baker. (Trans., 1913, 1658.) The viscosities of solutions in various solvents of different concen- trations of cellulose nitrates have been determined. The relation y=yo(l +ac)k was found to express the connexion between the concentration of cellulose nitrate (c) and the viscosity. Comparison between the results obtained with difierent solvents suggests that the values cjf the constants a and k depend on the solvent power of the liquid for nitrocellulose. The viscosity of solutions of nitrates of mercerised cellulose suggests that cellulose and mercerised cellulose are not identical, but that cellulose is degraded in the process of solution in ammoniacal copper oxide. The influence of molecular attraction on physical properties is discussed, and association in liquids ascribed to increased molecular attraction.213. ‘‘ Geranyl chloride.” By Martin Onslow Forster and David Cardwell. (Trans., 1913, 1338.) Geranyl chlorid2 has been prepared by the action of thionyI chloride on a mixture of geraniol and pyridine, and appears to be identical with linalyl chloride; reasons are given for regarding the C,oH17-nucleus as being that of geraniol rather than the tertiary linalyl group. The nitrosate, CloH,70,N,Cl, melting at lolo, is a convenient derivative by which to identify geranyl chloride, which has a distinct odour of hops, and boils at 103O/14 mm. The hydrocnrbon, C10H16, produced along with geranyl chloride, boils at 174--176O/763 mm., and yields a nitrosate, melting at 131°, whilst the hydrocarbon, ClOHI8,prepared by reducing geranyl chloride, boils at 161°/763 mm., and yields a nitrosate melting at 95O.Geranylamine, C,,H,,N, boils at 105O/19 mm., and forms definite derivatives with the usual agents, 214. ‘‘A new method of preparing m-chlorobenzoic acid and the investigation of its hydroxylamine salt.” By Wilhelm Qluud and Richard Eempf. (Trans., 1913, 1530.) m-Chlorobenzoic acid is prepared by heating benzoic acid with qua regia on a water-bath, the chloro-acid being separated from 245 the crystalline mass by means of its calcium salt. The hydroxyl- amine salts of m-chlorobenzoic and benzoic acids were also prepared and examined, especially with reference to their solubility and their behaviour on heating.Both salts are easily converted into the corresponding ammonium salts, which readily dissociate into their components, the m-chlorobenzoate apparently more readily than the benzoate. 215. *‘Contributions to our knowledge of semicarbazones. Part 111. Action of heat on the semicarbazones of phenyl styryl ketone and the preparation of the corresponding phenylsemicarb- azones.” By Isidor Morris Heilbron and Forsgth JamesWilson. (Trans., 1913, 1504.) The authors have investigated the action of heat on the photo- tropic semicarbazones derived from phenyl styryl ketone (compare T., 1912, 101, 1482). Both semicarbazones yielded, as main product, an isomeric compound melting at 189O, apparently cyclic in structure, for which the formula is suggested.The phenylsemicarbazones have also been investigated, having been prepared both directly by the interaction of phenyl styryl ketone and phenylsemicarbazide, and also by the action of boiling aniline on the original semicarbazones. The course of the latter action has been found to depend on the duration of the heating with aniline, prolonged heating producing from both semicarb-azones a compound melting at 169O, and apparently, deduced from spectrographic evidence, analogously constituted to the sub- stance melting at 189O. On the other hand, five minutes’ heating with aniline produces colourless plienylsemicarbazones, each semi- carbazone yielding its respective phenyl derivative.These phenylsemicarbazones are strongly phototropic, becoming intensely yellow in light, whilst their solutions show thermotropic properties. The action of sodium ethoxide on the phenylsemicarb- azones produces the same effect as light, yellow stereoisomerides being formed. Various attempts were made to hydrolyse the phenylsemicarb- azones, but these only resulted either in a partial conversion of the one stereoisomeride into the other or in the formation of the cyclic compound melting at 189O. c2 246 216. “Contributions to the chemistry of the terpenes. Part XVI. The oxidation of bornylene with hydrogen peroxide.” By George Gerald Henderson and William Caw. (Tians., 1913, 1543.) Bornylene, in solution in acetic acid, is slowly oxidised by hydrogen peroxide, with the production of a mixture of free acids ani esters.The acids were found to be (1) camphenanic acid, C,€I,,*COzH (m. 1). 95”), (2) the isomeric Isocainphenanic acid (m. p. 74O), and (3) a liquid acid, whicli, from the analysis of its methyl ester and silrer salt, appears to have the formula HO*C,Kl2*CO,H. When distilled under diminished pressure this liquid acid is converted into a crystalline unsaturated acid (m. p. 80°), which has not been further examined. The mixture of esters was separated by steam distillation into a volatile and a non-volatile part. The former yielded on hydrolysis (1) acetic acid and, in much smaller quantity, the three acids already mentioned, and (2) a mixture of two alcohols of the formula C,,H17*OH.The alcohol present in largest quantity proved to be borneol, whilst the other was identified as epiborneol. The non-volatile esters when hydrolysed gave (1) acetic acid with much smaller quantities of the other acids, and (2) a mixture of two isomeric uZco7zols of the formula CloH,,O,. These alcohols are crystalline solids, whicli melt at 247-248O and 235-236O respec-tively ;the quantities hitherto obtained were not sufficient to permit of a satisfactory examination of these compounds. The formation of camphenanic and isocamphenaiiic acids from bornylene is of particular interest, becausa these acids have already been obtained by oxidising camphene with hydrogen peroxide (compare T.,1911, 99, 1539).Thus further evidence is afforded of the very close similarity between the molecular structure of boriiylene and that of camphene. 217. The relative activities of certain organic iodo-compounds with sodium phenoxide in alcoholic solution. Part 11. iso-, sec.-and tert.-alkyl iodides.” By David Segaller. (Trans., 1913, 1.121.) The reactivities of isobutyl, isoamyl, isopropyl, sec.-butyl, sec.-amyl, sec.-hexyl, sec.-heptyl, sec.-octyl, tert.-butyl, and tert.-amyl iodides with sodium phenoxide in alcoholic solution have been measured. Ally1 iodide was also included to give some indication of the effect of unsaturation. iwCoinpounds are much less reactive than the normal primary isomerides, whereas the normal secondary iodides are only slightly less reactive than the normal primary iodides.The reactivity decreases gradually with increase in molecular weight. The tertiary iodides are the most reactive of 247 the alkyl iodides, and yield olefines when treated with sodium phenoxide. 218. Non-aromatic diazonium salts. Part 11. Azo-derivatives from antipyrinediazonium salts Itnd their absorpi ion spectra.” By Gilbert T. Morgan and Joseph Reilly. (Tynlls., 1913, 1491.) The condensation products from antipyrinediazonium salts and acetylacetone, benzoylacetone and ethyl acetoacetate and the corre- sponding sodium derivatives exhibit very similar ultraviolet ahsorptior, spectra, their extinction curves being characterised by one persistent. band comparable with the band shown by the P-diketones t,hemselves and their metallic derivatives.It is there- fore suggested t’liat these condensation products and their sodium compounds are azo-derivatives, having the following co-ordinated configuration : 0 The corresponding azo-B-naphthylamine and its derivatives were also examined spectroscopically. 219. ‘‘ The ten stereoisomeric tetrahj drcquinaldjnomethylene- camphors.” By William Jackson Pope and John Reed (Trans., 1913, 1515.) The d-and I-tetrahydroquinaldines condense with the d-and Z-oxymethylenecamphors, yielding four simple optically active tetrahydroquinaldinoinethylenecamphors; any two of these latter compounds are capable of combining together to form a stable solid double compound. There are thus obtainable four partly racemic and two fully racemic compounds.The ten isomeric substances formed have been investigated, and, in spite of the facility with which the partly racemic compounds are produced, externally compensated tetrahydroquinaldine can be resolved by means of its condensation products with d-oxymethylene- camphor. The method of resolution is based on the fact that d-tetrahydroquinaldine condenses much less rapidly than Z-tetra-hydroquinaldine with d-oxymethylenecamphor. 248 220. *‘The isomerism of the oximes. Part I. The diphenylcarbamyl- oximes.” By Oscar Lisle Brady and Frederick Percy Dnnn. (Trans., 1913, 1613.) A detailed description of work of which a preliminary account has already appeared (P., 1911, 27, 239). 221.“The isomerism of the oximes. Part XI. The nitrobenzald- oximea.” By Oscar Lisle Brady and Frederick Percy Dunn. (Trails., 1913, 1619.) The authors have investigated the action of sunlight on the nitrobenmntialdoximes, and have shown that in all cases they are converted into the corresponding syn-oximes. Hence Ciamician and Silber’s statement that the meta-compound does not undergo this change is incorrect. It has also been shown that the O-methyl ethers of the nitrobenznntialdoximes are transformed into the syn-derivatives by the action of sunlight, but not so readily as are the oximes themselves. Experiments have also been made on the stability of the nitrobenzsynaldoximes. 222. The azo-derivatives of 2 :2’-diphenol.” By Philip Wilfred Robertson and Oscar Lisle Brady.(Tram., 1913, 1479.) 5 :5/-Bisbenzencazo-2 :2/-diphenol, exists in two modifications, yellow and red, both containing half a molecule of water of crystallisation, which is lost only at 160°, the colour of the compounds being unchanged after dehydration. Several other derivatives have been obtained by the action of 2 :2I-diphenol on various diazonium salts, although only the simple benzeneazo-compound has been found to exist in two forms. It has been noticed, however, that these compounds almost invariably separate with water of crystallisation, which is retained with unusual persistency, being driven off but slowly at 160O. 223. L4 The constitution of the trinitro-p-aminophenols and trinitro-p-anisidines.” By Raphael Meldola and Frhd6ric Reverdin.(bans., 1913, 1481.) The trinitroacetylaminophenol described in 1906 (T., 89, 1935) is the 2 :3 :G-trinitro- and not the 2 :3 :5-trinitro-compound, as appeared from the evidence formerly available. The trinitro-p anisidine melting at 127-128O (Qrch. Sci. phys. nat., 1909, [iv], 27, 383) has now been proved by direct evidence to be the 2 :3 :5-trinitro-compound, and the trinitroanisidine melting at 138-139O (T., 1910, 97, 444) the 2 :3 :6-trinitro-compound. The position of the “ mobile ” nitro-group in the different series has been shown to be as formerly determined, namely, the 3-nitregroup in the 2 :3 :6-series, and in the 2 :3 :5-series the 2-nitro-group under the influence of bases, sodium acetate, etc., or the 3-nitro-group on diazotisation of the 4-amino-group (T., 1910, 97, 1204).224. 66 A new method for the determination of the concentration of hydroxyl ions. By Francis Francis and Frank Henry Qeake. (Trans., 1913, 1722.) The decomposition of nitrosotriacetonamine into phorone, water, and nitrogen, under the influence of various bases has been fully investigated, the course of the reaction being followed by observing the volume of nitrogen evolved. The rate of the reaction is proportional to the concentration of the hydroxyl ions, and the results show that, up to a, concentration of 0.05A7-and beyond O’SN-hydroxyl ion, a new method has been found for the determination of the concentration of such ions.The utility of this method is indicated by the fact that the effect of neutral salts in moderate concentration on the course of the reaction appears to be negligible. 225. (( The relation between residual affinity and chemical constitution. Part IV. Some open-chain compounds.” By Hans Thacher Clarke. (Trans., 1913, 1689.) Some measurements have been made of the reactivity of tertiary amines of the general f ormulze Me,N*[CH&*NMe, and MeO*[CH,],*NMe, towards ethyl bromoacetate under standard conditions. It was found that the reactive power of the members of both series increases with increasing length of chain ; furthermore, in both cmes exaltation of reactivity was observed when the atoms of nitrogen and oxygen were situated in the critical positions (n=3 and 4).These results thus tend to confirm the hypothesis of “spatial conjugation ” in open-chain compounds. In two control series of the general formulae CHMe,*[CH,],*NMe, and Et*[CH,];NMe,, only slight variations of reactive capacity were observed in the different members. 250 226. “The reduction of mercuric chloride by sodium formate.’ By Alexander Findlay and Morton James Pryce Davies. (Trans., 1913, 1550.) The reduction of mercuric chloride by sodium formate has been studied kinetically at 40°. From the results it appem that the reaction is a bimolecular one, similarly tothe reduction of mercuric chloride by phosphorous acid. 227. “The volatile constituents of coal. Part 111.” By Arthur Herbert Clark and Richard Vernon Wheeler.(Trrns., 1913, 1704.) Coal can be separated into two substances, differing widely in their characteristics, by the solvent action, first of pyridine and then of chloroform or benzene. The portion of coal soluble in pyridine appears to consist of the resinous constituents, together with some of the humus substances. The latter are insoluble in chloroform or benzene, whereas the resinous constituents are soluble. A separation can thus be made. Destructive distillation at different. temperatures of the separate portions of a bituminous coal obtained by use of these solvents supports the view already put forward (T., 1910, 97, 1924; 1911, 99, 649) that coal is conglomerated of two main types of substances, “hydrogen-yielding ” and “paraffin-yielding,” the former being the degradation products of the celluloses (humus substances), part of which are insoluble in ppridine, and part soluble in pyridine but insoluble in chloroform; and the latter being the resinous constitu- ents, soluble in both pyridine and chloroform.In an addendum to the paper [with CLAUDE BERNARDPLATT] attention is drawn to the results obtained by W. J. Russell (Proc. Roy. SOC.,1908, B, 80, 432) when investigating the action of resin and allied substances on a photographic plate in the daxk, and it is shown that the several portions into which coal can be separated by the solvents pyridine and chloroform a~ffect a sensitised plate in different manners, the results supporting the conclusions drawn from the results of their destructive distillation.228. “The volatile constituents of coal. Part IV. The relative inflammabilities of coal dusts.” By Richard Vernon Wheeler. (Trans, 1913, 1715.) If coal be regarded as a conglomerate of two main types of compounds, the one readily yielding inflammable gases and vapours on heating to a comparatively low temperature, the other requiring 251 a higher temperature of more prolonged duration to decompose it freely, it can be understood that variations in the proportions in which these different types exist in different coals should cause corresponding variations in the chemical and physical properties of the coals. A property, common to all CO~~S,which would appear to depend essentially on the proportion of readily-decomposed constituents present, is their “inflammability ” when in the form of dust. It is shown that for a number of coal dusts tested the relative inflammabilities varied directly with the relative proportions of readily-decomposed constituents in the coals.229. (‘The methylation of cellulose.” By William Smith Denham and Hilda Woodhouse. (Trans, 1913, 1735.) When alkali-celluloss, prepared by mixing cellulose with suffi- cient 15 per cent. solution of sodium hydroxide to give a mixture in which the proportions of the constituents are represented by the ratio C6Hlo0, : 2NaOH, is treated with excess of methyl sulphate a methylated cellulose is obtained, which retains the fibrous structure of the original material and has the composition represented by the empirical formula C,~,,O,*OMe.If this substance is subjected to a repetition of the sa.me treatment the composition of the new product is given by the formula C,T3,04*OMe, whilst another repetition of the process yields a substance the composition of which is given by the formula C2,H,0,,(OMe),. All therse substances can be acetylated, giving derivatives in which the methyl group is still present. The substance CkH,O,*OMe has been converted into a material. which resembles viscose. 230. “The structure of the salts of nitrophenols.” By John Theodore Hewitt, Rhoda Marianne Johnson, and Frank George Pope. (Trans., 1913, 1626.) An attempt has been made to attack the problem of the constitu- tion of the nitrophenolates on chemical grounds. The sodium deriv- atives of true phenols react in absolute alcoholic solution with ethyl chloroacetate at water-bath temperatures, giving ethyl aryloxyace- tates.Even 2 :4:6-tribromophenol is not sterically hindered, but o-and (pnitrophenols do not react under the conditions mentioned. Sodium m-nitrophenolate, however, gives a good yield of ethyl m-ni trop henoxy acet ate, The nitro-group in the nitrophenolates is evidently also affected ; d 252 whilst sodium methoxide reduces nitrobenzene to azoxybenzene and nitroanisole to azoxyanisole, the nitrophenols are not converted into azoxyphenols. 231. “The neutral and acid oxalates of potassium.” By Harold Hartley, Julien Drugman, Charles Archibald Vlieland, and Robert Bourdillon.(Trans., 1913, 1747.) A further study has been made of the equilibrium of the system potassium hydroxide-oxalic acid-water, confirming in the main the results of previous investigators, but explaining some discrepancies in their work, for example, the anomalous solubility curve of the neutral oxalate, the degree of hydration of potassium hydrogen oxalate, and the transition temperature of the two modifications of the latter salt. A crystallographic examination has been made of tetrapotassium dihydrogen oxalate, and of a twinned form of the neutral oxalate. 6i232. Adiabatic and isothermal compressibilities of some liquids between one and two atmospheres pressure.” By Daniel Tyrer.(Trans., 1913, 1676.) A method is described by which the adiabatic compresibility of a liquid can be accurately determined at a pressure of 1 to 2 atmospheres. This consists in principle of compressing the liquid contained in a suitable vessel and observing directly the volume change. which occurs, in a calibrated capillary tube. Measurements have been made over a temperature change of Oo to the boiling point for the following nine liquids : Ether, chloroform, carbon tetrachloride, benzene, toluene, chlorobenzene, carbon disulphide, ethyl alcohol, and water. By aid of the following thermodynamic equation values have been obtained for the isothermal compressibility : where B is the isothermal compressibility, a the adiabatic compressi- bility, T the temperature on the absolute scale, v is the specific volume, J the mechanical equivalent of heat, and Ca is the specific heat at constant pressure.The results are compared with the few results already determined by the direct method at low prwsuree, and a fairly good agreement is found. 253 233. (‘The constitution of aconitine.” By Oscar Lisle Brady. (Trans., 1913, 1821.) A detailed description of work of which a preliminary account has already appeared (P., 1912, 28, 289). 234. ‘(The methylation of quercetin.” By Arthur Cleorge Perkin. (Trqns., 1913, 1632.) Although owing to the presence of an hydroxyl group adjacent to the carbonyl group it has not hitherto been considered possible fully to methylate quercetin by means of methyl iodide and alkali, no difficulty in reality exisb in preparing a quantity of quercetin pentamethyl ether by this method, provided that an excess of the reagents is employed.This substance is to be found dissolved in the aqueous liquid obtained when the product of the reaction is diluted with water, and may be separated therefrom by treatr ment with salt. Small amounts of substances soluble in ether are simultaneously produced, namely, methylpuercetirt tetramethyl ether, C,H2,07, yellow needles (m. p. 184--185O), which yields an acetyl derivative, C20H1005A~, colourless needles (m. p. 178-180°), and a yellow potassifim salt, decomposed by water, and methgl-quercetin pentamethyl ether, C,,H,O,, colourless needles (m.p. 213-215O). By hydrolysis the former gives methylphloroglucinol- monomethyl ether (T., 1900, 77, 1318) and veratric acid, whereas from the latter a substance considered to be methoxymethglfisetol dimethyl ether, colourless needles (m. p. 188-149°) (compare Herzig, Ber., 1909, 42, 155), and veratric acid are produced. 235 ‘‘ The absorption spectra of various derivatives of aniline, phenol, and benzaldehyde.” By John Edward Purvis. (Trans., 1913,1638.) A comparative study has been made of the absorption spectra of the vapours and alcoholic solutions of o-, m-, and p-bromoaniline, o-, m-, and piodoaniline, 2 :4-dichloroaniline, p-bromophenol, piodo- phenol, 2 :4 :6-trichlorophenol, 2 :4 :6-tribromophenol, m-amino-phenol, m-dimethylaminophenol, p-aminobenzaldehyde, and pdi-meth ylaminobenzaldehyde.236. ‘(The chemistry of the glutaconic acids. Part VIII. P-Phenyl-glntaconic acid and the /3-phenyl-a-methylglataconicacids.” ByJocelyn Field Thorpe and Arthur Samuel Wood. (Trans., 1913, 1569. ) B-Phenyl-a-methylglutaconic acid has been isolated in three distinct modifications, which can be represented by the following formulz : d2 254 C02H*$Me *y?d9*C02H GMe*C0,H QPhCH,*CO,H FHPh CH*CO,H $!Ph CH ,*C02H (trans-Labileacid, m.p. 155”.) (Normal acid, m. p. lZOo.) (&Labile acid, (m.p. 108”.) The trams-labile acid is stable towards acetyl chloride, but both the normal acid and the cis-labile acid are converted by this reagent into the hydrosy-anhydride (I) (m.p. 94O), which yields the anilic (111.) acid (11) (m. p. 143O) and the hydroxy-anil (111) (m.p. 216O) with aniline. The trans-labile acid is converted into the sodium salt of the cis-labile acid by alkali hydroxide, and both the cis-labile acid and the trans-labile acid are converted into the normal acid by hydro- chloric acid. The hydroxy-anhydride is converted into the normal acid by boiling water and into the cis-labile acid by alkali in the presence of casein. The three modifications of t7he acid are readily distinguished by the aid of their barium salts. The acids of this type readily undergo decomposition when boiled with dilute mineral acids, and yield the corresponding hydro- carbon, thus : -$!H*C02H p 2 YHPh -+ 2C02 + QPh *CH CO,H CH,(6-Phenylglutaconic acid.) (isoPropeny1benzene.) 237. “The chemistry of the glntaconic acids. Part IX. A method for distinguishing between the esters of the normal and labile acids.” By Jocelyn Field Thorpe and Arthur Samuel Wood. (Trans., 1913, 1579.) The ester of a labile acid can be readily distinguished from its normal isomeride by the capacity it possesses of forming a con-densation product with ethyl sodiocyanoacetate ;thus the labile ethyl ester of 6-methylglutaconic acid forms the condensation product (I) to the extent of 60 per cent., whereas the corresponding normal ester under similar conditions yields no trace of this substance : 255 zH* C0,Et yH,*CO,Et ?H,*CO,H $lMe*CH(CN)C0,Et ~Me*CH,*CO,H$!MeCH24lO,Et CE12*C0,Et CH,*CO,H (Labile ester.) (1.1 (11.1 The condensation product yields ~8-dimethyllrropanetricarboxy2ic acid (11)on hydrolysis, and derivatives of this compound have been prepared. Several normal esters of the series were investigated, but were found to yield no trace of a condensation product. Normal ethyl glu taconate, which is capable of passing, with considerable ease, into derivatives of the unstable labile ester, yields with ethyl sodiocyanoacetate about 5 per cent. of the condensation product (111)) from which isobutane-ayyl-tricnrboxylicacid (IV) can be isolated on hydrolysis : FH*CO,Et $H*CO,Et yH,*CO,Et FH,*CO,H FH 7H*CH(CM) C0,E t $JH*CH,*CO,H p2CH*CO,Et CH,*CO,Et CH,*CO,Et CH,=CO,R (Normal ester.) (Labile ester. ) (111.) (IV.1 238. “The chemistry of the glutaconic acids. Part X. The alkyl-atioas of the ethereal salts.” By Jocelyn Field Thorpe and Arthur Samuel Wood. (Trans., MS, 1752.) The formation of alkyl derivatives from esters of the glutaconic acids is controlled by the following generalisations : (1) The formation of the sodium derivative of an ester of a glutaconic acid, and hence the formation of an alkyl derivative, takes plam through the labile form of the ester alone. (2) The normal esters, as such, do not react with sodium ethoxide. (3) The formation of a sodium derivative of a normal ester is therefore dependent on the tendency for the ester to pass into the labile modification under ths experimental conditions employed.(4) The formation of a sodium derivative from a normal ester of a monoalkylated dicarboxylic acid involves the passage of the mobile hydrogen atom to the carbonyl system not affected by the substituting group. The second alkyl group therefore enters on the carbon atom of the three-carbon system most remote from that bearing the existing alkyl group. (5) Those esters which contain two or three potentially mobile hydrogen atoms can be made to yield dialkyl derivatives having the alkyl groups on the same carbon atom by alkylating them under conditions which prevent the passage of the labile monoalkyl derivative, which is first formed, into its normal isomeride. This 256 can be effected by the presence of excess of sodium ethoxide throughout the alkylation.(6) Esters, although they may have the labile structure, will not react with sodium ethoxide if the nature of the groups carried by the carbon atoms of the three-carbon system is such as to prevent the movement of the hydrogen atom within the molecule. 239. The formation and reactions of imino-compounds. Part XVIII. The condensation of cyclohexanones with cganoacet- amide involving the displacement of an alkyl group.” By Jocelyn Field Thorpe and Arthur Samuel Wood. (Trans., 1913, 1586.) Whereas 3-methylcy clohexanone and 4-methylcyclohexanone yield condensation products with cyanoacetamide from which 3-methyl- cyclohexane-1 : l-diacetic acid (I) and 4-methylcyclohexane-1 :l-di-acetic acid (11) can be prepared in large quantity, 2-methylcyclo- hexanone and 1: 3-dimethylcyclohexane-4-onecondense with the amide to form cyclohexane-1 :l-diacetic acid (111) and 4-methyl- cyclohexane-1 :l-diacetic acid (11) respectively. Since great, care wm taken to use these ketones in a very pure form, it follows that the presence of the methyl group in the 2-position inhibits condensation, but that the tendency for the formation of a condensation product is so considerable that it is effected through the displacement of this group, probably as methyl alcohol.The by-products formed to the extent of about 10 per cent. in the reactions between the ketones and cyanoacetamide are the cyano-imides (IV) formed in accordance with the equation : CN*CH,*CO*NH, C N.7H GO COR, -3- YR2 >N H + H,O + NH,.CN*CH2*CO*N€3, CN*CH*CO W.> 257 240. ‘‘The replacement of alkyl groups in tertiary ardmatic bases.” By Jocelyn Field Thorpe and Arthur Samuel Wood. (Trans., 1913, 1601.) Experiments are described showing the unsuitability of the bases diethyl-and dimethyl-aniline for the purpose of eliminating hydrogen haloid from substances capable of parting with these elements. It is shown, for example, that there is always a tendency for the base to combine with the halogen derivative, forming a quaternary salt, and that when once this sdt is formed a decom-position represented by the equation Ph=rR2Br -+ Ph*?J*R + RBrCH,R*CH*CO,Et CH,R’C H*CO,Et (Quaternary salt.) ensues on heating.In the case of those substances which are not capable of elirnin-ating hydrogen haloid, the formation of the quaternary salt and its decomposition in accordance with the equation Ph*yR,Br -+ Ph.7.R +RBI*C H,-C0,Et C H,*CO,Et is quickly completed. The reactions between the dialkylanilines and both trimethylene bromide and ethylene dibromide are also described. 241. (‘Conmaranone derivatives. Part 11. The conatitution of ethyl conmaranoneoarboxylate.” By Richard William Merriman, (Trans., 1913, 1838.) Several distinct observations indicate that ethyl coumaranone-carboxylate normally exists in the enolic form (a) Dizring many subsequent attempts to prepare the phenyl-hydrazone described in Part I.(T., 1911, 99, 911), an isomeric substance, c(JH4<C(NH.Nmh)‘->C*CO,Et, was always obtained. (b) An oxime could not be isolated. (c) Exactly one equivalent of sodium hydroxide wm required to neutralise the ester. (d) It reacts towards Grignard’s reagent entirely in the enolic form. (e) The absorption curves of the ester and its acetyl derivative are practically identical. The addition of alkali completely alters the character of the absorption spectrum. This fact has been explained by the modification of Hantzsch’s theory proposed by Brannigan, Macbeth, and Stewart (T., 1913, 103, 415). 258 *Car bamylphen0xyacetic acid, NH,-CO C,H,* 0 CH,*CO,H, was prepared during this investigation. 6‘242. Coumaranone derivatives.Part 111. Acylazo-derivatives of coumaranonecarboxylic acid.” By Richard William Merriman. (Trans., 1913, 1845.) Benzeneazocarbonylcoumaranone, C6H4<Ggii> C-CO-N :NP h, and its phenylhydrazone, CoH4<zN:NHph) >CH*CO-N:NPhO--(Part I.,T., 1911, 99, 911), have been subjected to further investi- gation, the results of which confirm the formulze assigned to them. An acetate and metallic derivatives of benzeneazocarbonyl-coumaranone have been prepared. By reducing an alkaline solution of the orange azo-compound with zinc dust the colourless hydrazo- derivative, C,H4<2i> CH*CO=NH*NHPh,was obtained. When stannous chloride or sodium hyposulphite was used as the reducing agent, the azo-group was broken, with the liberation of aniline.The red azophenylhydrazone also forms an acetate and metallic derivatives. This phenylhydrazone is extremely resistant towards all hydrolytic agents, except fuming hydrobromic acid, which con- verts it into the parent azo-compound. Similar colourless hydrazo-compounds, orange azO-compounds, and red hydrazones of the latter have been prepared by using the three tolylhydrazines in place of phenylhydrazine. The absorption spectra of the above compounds have been measured and compared with those of s-benzoylphenylhydrazine, NHBzONHPh, and Fischer’s benzoylazobenzene, NBz:NPh. 243. ‘(The dynamics of bleaching.” By Sydney Herbert Higgins. (Trans., 1913, 1816.) Experiments on the bleaching of linen cloth containing a large excess of colouring matter, by means of very dilute bleaching powder solution, show that the bleaching action proceeds in accord- ance with the equation: HOCl= HC1+ 0, and is thus a unimolecular reaction.The influence of adding lime-water or hydrochloric wid to the bleaching solution was also studied. 259 244. “Note on the structure of certain lactones formed by the fission of the gem-dimethylcyclopropane ring.” By William Henry Perkin, jun., and Jocelyn Field Thorpe. (Trans., 1913, 1760 ) The constitution of the lactone-dicarboxylic acids A and B described in a former paper (T., 1901, 79, 764) and of lactone-dicarboxylic acids prepared by Baeyer (Ber., 1896, 29, 2792) and by Aschan (Annalen, 1913, 398,299) is discussed. 245.(( The resolution of 2 :3-diphenyl-2:3-dihydro-1:3 :4-naphthn-isotriazine into optically active components.” By William Jackson Pope and Clara Millicent Taylor. (Trans., 1918, 1763.) The resolution of this base is effected by crystallisation with d-bromocamphor-n-sulphonic acid ; the fractional crystallisation of the mixed salt which results yields two salts of the optically active acid, containing the cl-and the 2-base respectively. The liberation of the optically active base from the salts is accompanied by its complete optical inversion. 246. “The mutual solubilities of ethyl acetate and water and the densities of mixtures of ethyl acetate and ethyl alcohol.” ByRichard William Herriman. (Tram., 1913, 1774.) The mutual solubilities of ethyl acetate and water have been determined by a method which enables a test of the accuracy of the results to be applied.Although contraction occurs in the form& tion of both of the saturated solutions, yet the solubility of ethyl acetate in water increases with rise of temperature, but the solu- bility of water in ethyl acetate decreases with rise of temperature. There is no point of maximum density of water saturated with ethyl acetate above Oo. When alcohol is mixed with ethyl acetate a small expansion takes place; the maximum percentage expansion occurs when the two liquids are approximately in equimolecular proportions. A table of densities of mixtures of the two liquids is given. 247. (‘The azeotropic mixtures of ethyl acetate, ethyl alcohol, and water at pressures above and below the atmospheric pressure.Part I.” By Richard William Merriman. (Trans., 1913, 1790.) The change in composition of the azeotropic mixture of ethyl acetate and water ha been traced from 26 mm. to 1500 mm. e 260 pressure. The percentage of water increases continuously with the pressure, and there is no evidence of a constant value being reached at higher pressures. Assuming that the expreesion 2~,/p2.-X/(~-x>, where p, and p2 are the partial pressures and x and (1-z)are the molecular proportions of the two substances, holds for the azeotropic mixture, the partial pressure of the water has been calculated. At all temperatures this partial pressure is almost exactly equal to the vapour pressure of pure water at the same temperature.The Duhem-Regnault law, which etates that in the case of partly miscible liquids the total pressure of the heterogeneous mixture is equal to the vapour pressure of the more volatile component in the pure condition, has been found to be erroneous. 248. “The azeotropic mixtures of ethyl acetate, ethyl alcohol, and water at pressures above and below the atmospheric pressure. Part 11.” By Richard William Merriman. (Trans., 1913, 1801.) The alterations in composition of the ester-alcohol binary mixture and the t’ernary mixture have been studied at pressures ranging from 25 mm. to 1500 mm. There is no evidence of constant composition being attained at any pressure. Although the vapour-pressure curves of ethyl alcohol and ethyl acetate cross at a pressure of 948 mm., yet the percentage of alcohol in the azeotropic mixture increases continuously with the pressure, and shows no break at the point of crossing of the vapour-pressure curves.The following general rule for the change of composition of a binary azeotropic mixture of minimum boiling point has been deduced from the present investigation: The percentage of the liquid, for which dp/clt is the smaller, increases as the pressure decreases. The rule is followed in seven different cases. The only exception that has been found is the ethyl alcohol-water mixture (Wade and Merriman, T., 1911, 99, 997). 248. ‘(The mechanism of the condensation of glucose with acetone.” By James Leslie Auld Macdonald, Experience in the preparation of glucose-monoacetone and -diacetone has shown that, however prolonged the treatment with acid acetone may be, glucose monoacetone may always be isolated at the end of the reaction, and, moreover, the two condensation products are obtained in very variable yields.The conclusion is drawn that the formation of these compounds does not depend on the hydrolysis of glucose dimethylacetal, followed by condensation in definite stages with two molecules of acetone. 26 1 By arresting the condensation of glucose dimethylacetal with acetone at an early stage, glucose dimethylacetal-E[-rrionoacetone* has been isolated as the main initial product. This compound is highly unstable towards heat and acids, and readily loses methyl alcohol, with the formation of metlzylglucoside-e~-monoacetone.The position of the acetone residue in this compound was established by methylation by the silver oxide method, and subsequent hydro- lysis of the product in two stages.In this way, By-dimethyl methyl- glucoside-Ec-momace tone, fi y-dimethy1 methylglucoside, and lastly By-dimethyl glucose were obtained. On the other hand, prolonged treatment of glucose dimethyl- acetalmonoacetone with acid acetone results in simultaneous hydro- lysis and condensation taking place, and the formation of glucose diacetone. The di-derivative thus produced has therefore the acetone residues linked to the two pairs of carbon atoms, aB and €3 respectively, a conclusion which harmonises with all the evidence available regarding the structure of this compound.The condensation reactions of glucose dimethylacetal are thus extremely complex. When left in contact with acetone containing hydrogen chloride the initial produch are glucose monoacetone and glucose. dimethylacetalmonoacetone, the latter compound prob- ably furnishing the chief source of glucose diacetone. 250. bbCondensatio~of acid chlorides with the ethyl esters of (a) oyanoacetic acid, (b) rnalonic acid, and (c) acetoacetic acid. Part I.” By Charles Weizmann, Henry Stephen, and Ganesh Sakharam Agashe. (Trans., 1913, 1855.) A detailed description of work of which a preliminary account has already appeared (P., 1912, 28, 103). 251.‘‘2-Phenyl-6-styryloxazole.” By Robinson Percy Foulds and Robert Robinson. (Time., 1913, 1768.) In order to characterise 2-phenyl-5-styryloxazole the authors have prepared the substance by treating styryl b enzoylaminomethyl ketone with concentrated sulphuric acid. 252. “The action of sulphur chloride and of thionyl chloride on metallic salts of organic acids : preparation:of anhydrides.” ByWilliam Smith Denham and Hilda Woodhouse. (Trans., 1913, 1881.) The reaction between sulphur chloride and metallic salts of organic acids in the presence of an indifferent solvent, which is represented for the case of silver benzoate by the equation 2C,H,*C0& +SzC1,= (C,HS*CO&S, +2AgCl * The nomenclature adopted is that used in T., 1913, 103, 564.e2 (T., 1909, 95, l237), has been found to be general for many types of acids. Salts of hydroxy- and amino-acids behave exceptionally. The compounds of the type (R*CO,),S, are in all caees unstable, and decompose spontaneously with separation of sulphur and forma- tion of sulphur dioxide and the anhydride of the acid. Under similar conditions thionyl chloride usually yields sulphur dioxide, the acid anhydride and the chloride of the metal (P., 1909, 25, 294), but in the case of hydroxy-acids intermediate compounds are formed, which, on loss of sulphur dioxide, give rise to anhydro-compounds. A crystalline ma& anhydride has been prepared in this way. The respective behaviours of sulphur chloride and thionyl chloride in these reactions are consistent with their possessing similar constitut,ions.253. “The action of magnesium aryl haloids on glyoxal.” By Henry Wren and Charles James Still. (Trans., 1913, 1770.) isoHydrobenzoin, aj3 -dihydroxy -ap-di-p -tolylethane (m. p. 161*8-162~6°), and aP-dihydroxy -aB-di -o -tolylethane (m. p. 116*5--118O) have been prepared by the action of magnesium phenyl bromide, magnesium p-tolyl bromide, and magnesium 0-tolyl bromide respectively on unimolecular glyoxal (Harries and Temme, Ber., 1907, 40, 165). In no case could definite evidence of the formation of the second theoretically possible isomeride be obtained. The acetyl derivatives corresponding with the two latter glycols melt at 105-106° after softening at 103-104°, and 99-looo after softening at 98’5O respectively.254. (( The miscibility of solids. Part 11. The influence of chemical constitution on the thermal properties of binary mixtures.” ByErnest Vanstone. (Trans., 1913, 1826.) The method of thermal analysis has been applied to binary mixtures of the type PhaSPh. Pascal and Normand (Bull. SOC.chim.,1913, [iv], 13, 151, 201) have shown that dibenzyl, stilbene, tolane, azobenzene, and hydrazo- benzene are miscible in all proportions in the solid state; also that with benzylanihe, benzylideneaniline, and phenyl benzyl ether eutectic diagrams are obtained, and solid-solution formation is limited. A series of thermal diagrams for benzoin and benzil with these substances has been determined. In each case the diagram shows a single eutectic point and limited formation of solid solutions.The eutectic point depends on the melting points of the con- 263 stituents. It is always found nearer the substance of lower melting point. The molecular volumes at the temperatures of their melting point6 of ten substances have been determined. Substances con-taining oxygen have the greatest molecular volumes. The exceptional behaviour of benzil, when compared with other symmetrical compounds of the type PhaaPh, is discussed, and the greater molecular domain of benzil is suggested as the cause of its lower degree of miscibility. 255. “The solubilities of alkali haloids in methyl, ethyl, propyl, and isoamyl alcohols.” By William Ernest Stephen Turner and Crellyn Colgrave Bissett.The solubilities, in methyl, ethyl, propyl, and isoamyl alcohols, of lithium chloride and iodide, sodium chloride and iodide, potass- ium chloride, bromide and iodide, and rubidium chloride have been determined. Measurements were made at a common ternpera- ture of 25O, and in the case of lithium chloride in ethyl alcohol, also over the range from Oo to 60°. The existence of the compound LiC1,4C2H,O, first indicated by Simon, was confirmed, and its transition point into lithium chloride fixed as 17’4O. A compound, LiI,4C,H80, stable at 25O, was also found, and another, NaI,3C‘H40, stable at 15-16O. The solubilities at 25O proved that solvent action, on the above salts, decreases continuously in passing from water through the series of alcohols; that the order of solubility is iodide>bromide) chloride; and that, in all the solvents, the solubility of the alkali chlorides is in the order : lithium ch1oride)sodium chloride> rubidium ch1oride)potassium chloride.256. ‘(Nitration of 1-chloro-2:4-dinitronaphthalene.” By Max Rindl. A solution of 1-chloro-2:4-dinitronaphthalene in cold concen-trated nitric acid deposib on keeping prismatic crystals of l-chloro-2 :4 :5-tri?zitro7taphtha.lene7 melting at 143-144O. After several weeks 1-chloro-2 :4 :8-trinitronaphthalene begins to be deposited, along with the l-chlore2 :4 :5-trinitronaphthalene. The chlorine atom in both of these compounds is mobile. By treatment with aqueous solutions of alkali hydroxides they are converted into the corresponding trinitronaphthols.Only the 2 :4 :5-trinitro-a-naph-tho1 can be reconverted into the corresponding chlorotrinitronaph- thalene by means of ptoluenesulphonyl chloride and diethylaniline. Other reactions depending on the mobility of the chlorine atom 264 are the formation of 2 :4:5-trinitro-a-naphthyl methyl ether and of amines, for example, 2 :4:5-trinitro-a-naphthylamine,aa well as mono-and di-substituted alkyl- and aryl-amines. Gopper powder removes the chlorine, and two molecules join together, forming dinaphthyl derivatives. In the case of 1-chloro-2:4 :5-trinitro-naphthalene a seconda.ry reaction takes place, resulting in the elimination of chlorine and its replacement by hydrogen, with the formation of 1:3 :8-trinitronaplithalene.257. (( The decomposition of carbamide.” By Cleorge Joseph Burrows and Charles Edwaxd Fawsitt. Previous investigations on the decomposition of carbamide in aqueous solutions by one of the authors (Zeitsch. physikal. Chem., 1902, 41, 603) have been extended to solutions in aqueous alcohol. Addition of alcohol decreases the velocity of decomposition, but does not alter the mechanism of the reaction, which is a uni-molecular one. The theory already put forward that carbamide is not hydrolysed by water or aqueous solutions of acids is confirmed. Carbamide decomposes primarily into ammonium cyanate, and is then decomposed into carbonate. The authors believe that the decomposition of carbamide is the first chemical reaction to be investigated (1902), the mechanism of which demands the assumption of intermediate products, the existence of which has been proved.258. ‘‘The viscosity of sugar solutions” By Charles Wilfrid Roberts Powell. The results of an investigation into the viscosities of aqueous solutions of sucrose, dextrose, and laevulose are given, dealing first with simple solutions containing only one of the sugars, and then with complex solutions containing mixtures of them. The effect of temperature on the viscosity of these solutions is found to be well expressed by Poiseuille’s equation: where qo is the viscosity at Oo, qt is the viscosity at to, and a and B are constantas. If the concentration of the solution is expressed as grams of solute per grams of solvent, the relation between viscosity and concentration is a logarithmic one, and may be repre-sented by the equation qc=-45, where x is the concentration and A a constant.A new method of calculation of the viscosity of simple solutions is discussed, the time of flow of each of the constituents of the solution being calculated. By this means it is thought possible to examine the change in viscosity of the solute in concentrating solutions, as distinct from the change in viscosity of the solution. A possible explanation of the deviation of the increase in viscosity of solutions with increasing concentration from any simple law is outlined. The theory given does not attempt to explain fully the question of viscosity, but indicates how the friction between different groups of molecules in the solution may definitely characterise the order of the change in viscosity with change in the composition of the solution.It was found that for aqueous solutions of the three sugar3 mentioned, the two equations : qx= AX, may be used conjointly with a fair degree of accuracy to calculate the viscosity of a solution containing two or more of the sugars. 259. 6' The rate of hydration of acid anhydrides : acetic, propionic, butyric, and benzoic." By Bernard Howell Wilsdon and Nevi1 Vincent Sidgwick. The velocity of this change was measured by Rivett and Sidgwick's method (T., 1910, 97, 732) by observing the rise in conductivity of the solution.The conductivity of acetic acid was measured at 18O, of propionic at 18O and 25O, and of butyric at 25O. Approximately constant values of the dissociation constant are obtained in dilute soIution if the conductivity of the water used is added to that of the solution. The rate of hydration of the corresponding anhydrides was measured at the same temperatures, and also that of benzoic anhydride at 25O. The velocity of change of acetic anhydride is about twice that of propionic, about four times that of butyric, and about eight times that of benzoic. With acetic anhydride at 18O, as wits previously observed by Rivett and Sidgwick at 25O, tha velocity decreases steadily with increase of concentration above about 0*2N;the same occurs with propionic anhydride above about 0.02N.The correction for the diminution in the concentration of the water only accounts for a small part of this fall. If, however, the activities of the two reacting molecules (water and anhydride) are assumed to be propor- tional to the fluidity of the solution, and the observed velocities are multiplied by the square of the viscosity, the results are found to be constant (for both anhydrides and at both temperatures) wit,hin the limits of experimental error. Monochloroacetic anhydride was found to be hydrated with a velocity too great for measurement-at least one hundred and fifty times that of acetic anhydride. 260. “Investigations on the dependence of rotatory power on chemical constitution, Part IV.The rotatory powers of the secondary alcohols of the formula C,H,*CH(OH)*lL” By Robert Howson Pickard and Joseph Kenyon. A description is given of the synthesis and resolution of thirteen alcohols of the series C,H,*CH(OH)*R. These optically active carbinols have been examined polarimetrically in the homogeneous state, and in alcoholic and in benzene solution. The results show that, whilst the molecular rotatory powers gradually increase as the series is ascended, there are further exaltations when the growing chain contains about five and about ten carbon atoms. It has been shown also that a similar effect on the molecular rotatory powers of the series CH,*CH(OH)*R is only noticeable when these are determined in solution as in the homogeneous state the molecular rotatory powers of the carbinols of this series increase regularly with the mass of the compounds.The optical rotatory dispersive power of the higher members of the series is a constant, and is independent of the temperature (from 20° to 160O). The following communications have been received during the vacation : 261. ‘‘The mechanism of the benzoin synthesis.” (Preliminary note.) By Gertrude Maud Robinson and Robert Robinson. The investigation originated with the observation that cotarnine condenses with many aromatic aldehydes to form bases which are probably benzoylhydrocotarnines. With tho idea of improving the yield and guided by Lapworth’s well-known explanation of the benzoin synthesis, the authors attempted to prepare benzoyl hydro- cotarnine (or its cyanohydrin) by the condensation of cotarnine with mandelonitrile in alcoholic solution ; the products were, however, cyanohydrocotarnine and benzaldehyde.Cyanohydro-cotarnine wm also obtained when benzoylmandelonitrile (Francis and Dale, T., 1909, 95, 1404) was mixed with an equimolecular amount of cotarnine in alcoholic solution. In this case the expected benzaldehyde and benzoic acid were produced in traces only; the main products were benzoylbenzoin (m. p. 125O) and ethyl benzoate, as well as a small proportion of benzyl benzoate. A similar result was achieved when the cotarnine was replaced by sodium acetate, potassium carbonate, or sodium ethoxide. With the latter the reaction is complete, and may be expressed by the equation: 2BzO*CHYh*CN+2NaOEt = BzO*CKPh-COPh+Ph*CO,Et -f-EtOH +2NaCN.cW( r:N)>O .a-Cya n onze c onine, C,H 0Me)2<co Opianic acid (1 mol.) and potassium cyanide (1 mol.) react in aqueous solution with the production of the potassium salt of the cyanohydrin of opianic acid. The acid is a syrup readily soluble in water, and passes very slowly into the corresponding lactone, a-cyanomeconine; the loss of water occurs rapidly on boiling its solution in dilute hydrochloric acid. The substance crystallises from methyl alcohol in prismatic needles melting at 1OO---10lo, and is sparingly soluble in alcohol or ether. It is quantitatively hydrolysed to meconinecarboxylic acid (Fritsch, Annalen, 1898, 301, 358) on boiling with concentrated hydrochlGric acid for thirty seconds.This remarkable ea,se of hydrcl lysis must be ascribed to the recognised effect of a ring structure in increasing the reactivity of groups attached to it. The ready conversion of a-cyanomeconine to tetramethoxydiphthalyl by alkaline agents is analogous to the above production of benzoyl-benzoin, and is best effected by potassium cyanide or cotarnine. The meconine hydrogen atom may be partly substituted by potass-ium (or cotarninium), and this intermediate substance may then condense either with itself: or with a molecule of cyanomeconine, in which case a further substitution of hydrogen by potassium, follo~wed by loss of potassium cyanide, must occur before tetramethoxydiphthalyl is reached.A similar series of reactions may explain the more complicated pro- duction of benzoylbenzoin, although there are alternative methods of expressing t110 elimination of ethyl benzoate. The authors consider that the formation of benzoin itself is concerned entirely with the aldehydecyanohydrin in its double function a,s reactive cyanide analogous to ethyl iodide, and as a phenylacetonitrile with a hydrogen atom displaceable by alkali metals. 268 The action of potassium cyanide on mandelonitrile in boiling alcohol yields an oil which is probably benzoincyanohydrin ; on treatment with sodium hydroxide in the cold, benzoin is produced. Many attempts to prepare mixed benzoins by different methods have been unsuccessful.Incidentally, tho authors have investigated the hydrolysis of acyi cyanohydrins, and find that these compounds are very well adapted for the preparation of mandelic acids. Benzoylmandelo-nitrile gives a good yield of benzoic and mandelic acids on prolonged boiling with concentrated hydrochloric acid, whilst on solution in sulphuric acid and subsequent dilution with water, benzoylmandel- amide, BzO*CHPh*CO*NH,, is obtained. The latter crystallises from ethyl alcohol in feathery needles melting at 160-161O. Saturation of a solution of benzoylmandelonitrile (1 mol.) and ethyl alcohol (2 mols.) in dry ether with hydrogen chloride at Oo, and decomposition after twelve hours with alcohol and water, produces ethyl bensoylmandelate, BzO*CHPh*CO,Et, a viscid oil boiling at 227O/20 mm., together with a relatively small quantity of benzoyl- mandelamide.RetizoyZ-~~itrornnle~orLitrile?obtained in excellent yield from o-nitrobenzaldehyde, aqueous potassium cyanide, and benzoyl chloride, crystallises from alcohol in pale yellow needles melting at 89O, and yields on hydrolysis with concentrated hydrochloric acid, ber-zoic and o-nitromandelic acids. 262. ‘‘Some derivatives of phenanthraquinone.” (Preliminary note.) By Kshitish Chandra Mnkerjee and Edwin Roy Watson. An investigation has been undertaken with the object of prepar- ing derivatives with valuable dyeing properties from phenanthra- quinone. Up to the present the following compounds have been obtained : Nitro-2:7-diace t oxyphe,nant hmquinone, C,,H,0,(OAc),*N02, pre-pared by dissolving 2 :7-diacetoxyphenanthraquinonein cold nitric acid (D 1-39) and plunging the containing vessel for one and a-half micutes into boiling water, crystallises from a mixture of acetic acid and acetone in yellowish-brown, rhombic prisms, which do not melt below 290O.Nitro-2 :?-dihydroxypheel~anthrapz~i?ione,C,,H,O,(OH),*NO,, is obtained by hydrolysing the above acetyl derivative as a brown powder, which does not melt below 290O. A mino -2 :7 -dihydroxyphenanthraquinone, C’,,H,O,(OH),*NH,, prepared by reducing the nitrodiacetoxyphenanthraquinonewith tin and hydrochloric acid and treating the product with warm 269 ferric chloride solution, consists of deep brown, small, rectangular plates, is insoluble in all ordinary organic solvents, dissolves in alkali hydroxide with a brown colour, and does not melt below 290O.Its triacetylderivative, C,4H,02(OAc)2*NHAc, does not melt below 295O. 3 : 7 : 1 -Trihydroxyyhenant~raapzLinone, C,4H,02(0H)3.-The aminodihydroxy-compound is diazotised in ice-cold 10 per cent. sulphuric acid, and the filtered diazo-solution on boiling precipitates tho trihydroxyphenanthraquinone as a reddish-brown substance, which does cot melt below 290°, can be dissolved in pyridine and precipitated by alcohol, and dissolves in alkali with a brown colour. Its tm’metyl derivative, C14H502(OA~)3, deposited as a reddish-brown, microcrystalline powder from glacial acetic acid, melts at about 280O.2 :7-~nhcety~am~nophenunthraquinone,C,,H,O,(NHAC)~, is pre- pared by heating 2 :7-diaminophenanthraquinonewith acetic anhy- dride and fused sodium acetate at 160° for one hour in a sealed tube. It is a chocolate-brown coloured substance, readily soluble in acetic acid, sparingly so in alcohol, and does not melt below 295O. Phenanthraquinone-2 :7 -bisasophenol, C,4H602(N,gC6H,*OH)2,prepared by diazotising 2 :7-diaminophenanthraquinone in 5 per cent. sulphuric acid and coupling with phenol, crystallises from a mixture of alcohol and nitrobenzene in brown, lenticular crystals, which do not melt below 295O, and dissolve in alkali with a brown colour. The diacetyl derivative, Cl4H,O,(N,~C,H,~OAc),, crystalks from acetic acid in brick-red, rhombic prisms, melting at 274O.263. ‘(Some derivatives of 2 :3 :4 :2-tetrahydroxybenzophenone.” (Preliminary note.) By Narendra Nath Sen Qnpta and Edwin Roy Watson. This investigation has been undertaken with the object of prepar- ing dyes of deep colour by replacing the ketonic group of the polyhydroxybenzophenones by the arrangement CR(0H). Up to the present the following derivatives of 2 :3 :4 :2/-tetrahydroxy-benzophenone have been prepared : 2:3 :4 :2f-Te~rahydroxy-4~~-~~met?~~Lcim~notripheny~carbilzolanhy-dro-hydrochloride, C,H,(OH),*C‘(C,H4*OH):C),H,:N(~H,),C1( ?),pre-pared by the action of a mixture of dimethylaniline and phosphoryl chloride on the tetrahydroxybenzophenone, is a crimson, amorphous Substance, melting at 184--185O, and decomposing at 200°, which dyes crimson shades on wool mordanted either with chromium or tin, 270 2 :2t-nihydrox:y-3 :4-dimethoxybemmphenone, HO*C6R2(OMe)20CO*C6H4*OH, obtained by the interaction of o-methoxybenzoyl chloride and pyro- gallol trimethyl ether in the presence of anhydrous aluminium chloride, crystallises from alcohol in yellow, needle-shaped crystals, melting at 127O.2 :3 :4:2/-Tetrun~ethoxybenzophenone, C,~,(OMe),~CO~C,II[,=~~e, obtained by the action of methyl sulphate and potassium hydroxide on tetrahydroxybenzophenone or 011 2 :2'-dihydroxy-3 :4-dimethoxy-benzophenone, crystallises from dilute alcohol in colourless prisms, melting at 83O.Its pherzulhydrazone, C,R2(0Rle)3*C(:N*NHPh)*C',H, Ohle, crystallises from alcohol and melts at 153O. Its oxime, C,H,(OMe),*C(:NOH)-C,H,*OMe, crystallises from alcohol and melts at 166O. The phacone, C6H,(OMe),*C(c,H,*OMe)(OH)~~(~6H4*OMe)(OH)*~~H,(OMe)3, obtained by the action of zinc dust and acetic acid on the tetr;c methoxybenzophenone, is purified by crystallising in succession from glacial acetic acid and alcohol, and forms colourless, needleshaped crystals, melting at 185-186O. 264. '' The constitution of phenolphthalein and its alkali salts." By Morris Fort and Frank Leslie Barrett. Green and Perkin (T.,1904, 85, 398) have described a method of titrating a cooled, colourless solution of phenolphthalein in a knuwn excess of potassium hydroxide with acetic acid.Using 0-5 gram of phenolphthalein, they found 17.6 per cent. of potassium hydroxide to remain unestimated by the acid, that is, the amount calculated for C20H,,05R. The titrated solution was clear and colourless, becoming deep red and alkaline to litmus on heating, whilst a precipitate of phenolphthalein also separated out, and on again cooling these features persisted. It does not appear from the account of this work that the possible reaction between phenol-phthalein and potassium acetate had been taken into account, whereas it is now found that a colourless mixture of these two substances in solution becomes red and alkaline to litmus on heating, remaining so on keeping until cold. The reaction is by no means unique, and belongs to the class of " neutral salt reactions '' due to the operation of mass law (Fort, J.SOC.Dyers, 1912, 28, 314; 1913, 29, 80, 120, 269; Chenz. Neiiis, 1913, 108,1). The mere colour changes occurring on heating after titration as described have since been instanced in support of the quinonoid theory of colour (Green, J. SOC.Chem. Id.,1908, 27, 4), but now lend no support apart from the quantitative results, which appear liable to a considerable working error, being calculated from 0.65 c.c., where 0.1 c.c.=3-7 per cent. ICOH. Green and Perkin’s experilpent was therefore repeated, using also larger amounts of phenolphthalein up to 3 grams, and a series of results was obtained varying within the limits of error assigned above, for example, 16-65, 18-14, 16.10, etc.The average of ten successive experiments gave 17.54 per cent. of potassium hydroxide (CwH3[,,05Krequires 17.6 per cent. KOH). (a) The amount of potassium combined with phenolphthalein as a colourless salt was also estimated directly with acetic acid, after heating and recooling with ice, and found tr, agree with the above indirect estimation. (b) At the same time, to decide as to the condition of phenol-phthalein and the equilibrium obtaining in the red alkaline solution, the colourless solution of the monopotassium salt was closely imitated with a red solution containing fresh phenol-phthalein, potassium hydroxide, and potassium acetate, and these intensely red and colourless liquids were heated side by side until of a similar intense red, behaving quite similarly on cooling with ice and titrating with acetic acid.There can therefore be little doubt as to the isomeric change taking place from the less stable, colourless monopotassium salt of phenolphthalein, to the coloured quinonoid salt. (c) Neutral salt reactions are greatly retarded by lowering of temperature as in the titrations in (a) and (b); how-ever, in order to determine the highest possible error from this cause, a blank experiment with phenolphthalein and potassium acetate was performed alongside (a) and (b), showing that the quantitative results are liable tlo be affected by the neutral salt reaction to only a small extent. The experiments were made in duplicate, comparative through- out.The potassium hydroxide solution contained 177.184 grams of the alkali per litre, and 25 C.C. of the acetic acid were equivalent to 20.6 C.C. of potassium hydroxide solution. (a) One gram of phenolphthalein and 20 C.C. of potassium hydr- oxide solution were taken; after preparation of the colourless salt it wae heated in the water-bat.h one hour under an air condenser, cooled with ice, and titrated to a permanent pale pink colour requiring 1-20 C.C. of acetic acid=17.5 per cent. KOH. The faint pink at the end-point can be removed with a considerable excess of acetic acid, and is ascribed to the presence of potassium acetate : (&0Hi@,K +C&&O, zzC&&@& +CzJI160,. (b) One gram of phenolphthalein, 9.95 C.C.of potassium hydr- 272 oxide solution, and 6.1968 grams of anhydrous potassium acetate were used; the volume was as in (a) after the preparatory titration. The solution was heated, cooled, and titrated as in (a) to a pale pink: 1.2 C.C. of acetic acid were required=17.5 per cent. KOH. (C’2,H,,0,K =1‘7.6 per cent. KOH.) (c) One gram of phenolphthalein and 6.1968 grams of potassium acetate were used, the volume being as in (a) and (b), alongside which the solution was heated, cooled, and titrated to a pale pink: 0.12 C.C. of acetic acid was required=l.7 per cent. KOH. The intense red colour given on heating is largely retained at the ordinary temperature, but much reduced at Oo. The figure obtained from a duplicate experiment titrated at the boiling point after an hour’s heating in the water-bath was 0.29 C.C.of acetic acid= 4.23 per cent. KOH. These results support the main conclusions drawn by Green and Perkin, and are in agreement with the quinonoid formulz adopted by them for coloured phenolphthalein salts. 65. (‘Complex metal ammonias. cis-Sulphonyldiaoetatodiethylene-diaminecobaltic hydrogen sulphongldiacetate.” (Preliminary note.) By Thomas Slater Price and Sidney Albert Brazier. In his investigations of the complex cobalt ammonias, Werner has prepared a number of salts of the type [A*Coe%]X, where A is the radicle of a dibasic acid. So far the sulphito-, carbonate, oxalato-, and malonato-radicles have been introduced into the complex, but Werner has not been able to obtain crystalline com- pounds containing the next higher homologue to the malonato- radicle, namely, the succinato-radicle, or containing the radicles of malic and tartaric acids (Annulen, 1911, 386,81).It occurred to the authors that the introduction of the sulphur atom into the chain of carbon atoms in the acid used might lead to interesting results in this connexion, and Prof. Werner having kindly informed them that he did not contemplate working with such compounds, and would leave the field open to them, an investigation was com-menced, using thiodiacetic acid, S(CH,*CO,H),. Definitely crystal- line compounds were obtained, but the results were complicated by the fact that during the preparation, partial reduction of the cobalt compound took place, and the authors have not yet been able to characterise the compounds formed. In order to avoid this com- plication, the Lhiodiacetic acid was replaced by sulphonyldiacetic acid, SO,(CH,*CO,H),, and the compound cis-sulphonyZdiucetato- diethylenediaminecobaltic hydrogen sulphonytdiacetate, 273 [oaS<g2: Eg: g>Co en CO, *CH,*SO,*CH,*CO,H, has been prepared. The method of preparation was similar to that used by Werner for the corresponding malonato-compound (loc.cit., p. 79). Four grams of cis-carbonatodiethylenediaminecohalticbromide were dis- solved in 80 c.~. of warm water, and, after cooling, 2-20 grams of freshly prepared silver oxide were added to the solution.The mixture was well shaken for half an hour, and then filtered from the silver bromide into an aqueous solution of 5.63 grams of sulphonyldiacetic acid, the proportions being 2 mols. of the acid to 1 mol. of the carbonato-base. The resulting solution, after evapor- ating to a small bulk on the water-bath, deposited crystals of the desired compound. One recrystallisation from water gave the pure salt, in dull, rose-coloured, microscopic crystals, which are readily soluble in hot, but somewhat sparingly soluble in cold water : 0.2687 gave 0.0767 CoSO,. Co= 10.86. 0.1797 ,, 16.65 C.C. N, (moist) at 19O and 749.3 mm. N=10*45. 0.3045 ,, 02618 BaSO,. S=11*81. C,,H,,O,,N,S,Co requires Go= 10.91 ; N = 10.37; S=11.87 per cent. The authors are extending the investigation to other sulphur compounds and complex metal ammonias.Extra Meeting, Thursday, October 23rd, 1913, at 8.30 p.m., Prof. W. H. PERRIN,LL.D., F.R.S., President, in the Chair. The Ladenburg Memorial Lecture was delivered by Prof. F. Stanley Kipping, D.Sc., F.R.S., and at the conclusion of the lecture a vote of thanks to Prof. Kipping was proposed by Prof. H. E. Armstrong, F.R.S., seconded by Prof. W. Jackson Pope, F.R.S., and acknowledged by the Lecturer. Thursday, November 6th, 1913, at 8.30 p.m., Prof. W. H. PERKIN, LL.D., F.R.S., President, in the Chair. The PRESIDENTreferred to the heavy loss the Society had suatained through death, during the vacation, of the following Fellows : 2’74 Elected. Died.E. L. Barret (Paris) ... ... ... February 4th, 1869 1912 J. C. Bell (5lnnchester) ... ... January 19th, 1865 July lst, 1913 A. Cantin (Mauritius) ... .._ .Tniie 21st, 1900 February 12th, 1912 T. Crossnian (Starbeck) . . . .. . February 21bt, 1895 July 13thJ 1913 J. Davidson (Holvwell Green). .. May 18thJ 18i6 June 9th, 1913 L. M. Deana (Ilkley) ... ... March 4th, 1886 July Xth, 1913 Sir W. N. Hartley (Dublin) ... Deceniber 20th, 1866 September llth, 1913 J. Lewkowitsch ( W. Hampstead) February 16th; 1888 September 16th, 1913 H. Marshall (Dundee) . . . ... Februayy 6th, 1890 September 6th, 1913 I. Patchett (Batley) .. . ... ... April 21st, 1870 April loth, 1913 M. G. Roy (Chintadrepettali) ... June 21st, 1900 April 8th, 1913 A. Wallace (Agra) ....., ... May 2nd, 1912 June 25th, 1913 The following announcements were made : 1. That a meeting of the Faraday Society would be held here on Wednesday, November 12th, from 4.30 to 9.30 pm., when a general discussion on ‘‘ The Passivity of Metals ” would take place. Fellows of the Chemical Society were invited to attend the meeting. 2. That, in future, a list of the papers to be read at each Ordinary Scientific Meeting will be advertised in the Morning Post on the Wednesday previous to the day of meeting. Messrs. C. K. Tinkler and E. Cahen were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Richard Watson AskeH, B.A., Brierley, Chelmsford Road, Durban, Natal, South Africa.Sankar Rao B. Badami, M.A., Badami House, Hulsurpet, Bangalore, India. Stanley Charles Bate, B.Sc., 50, Alexandra Road, Upper Nor- wood, S.E. Charles Maurice Berlein, B.A., Cross Oak, Berkhamsted. Arthur Bicknell, B.Sc., Balliol College, Oxford. Augustus Pearce Llewellyn Blaster, B.A., Chidham, Potters Bar, Middlesex. Adhor Krishna Bose, 90, Musjeed Baree Street, Calcutta, India. Arthur Bramley, B.Sc., 19. Cambridge Road, Barnes, S.W. Arthur Joseph Brearley, B.A., 13, Victoria Terrace, Exeter. Bertram Campbell, B.Sc., Beechover, Manor Avenue, Grimsby. Frederick George Carter, Amritsar Distillery, Amritsar, Punjab, India. Santi Pada Chowdry, Economic Research Laboratory, Rewa Slate Industries, Umaria, India. Francis William Clark, 35, Wilmington Square, W.C.275 Herbert Stoddard Coleman, 14, Dunsford Road, Bearwood Road, Smethwick. Thomas James Drakeley, B.Sc., 36, Mitchell Street, Newtown, Wigan. Cyril Duncan Fuller, 62, Hill Street, Totterdown, Bristol. Charles John Dickenson Gair, 39, Cranston Road, Forest Hill, S.E. Stanton Gibson, B.Sc., 28, Lordship Park, N. Richard Hargreaves, B.A., Chatburn, Clitheroe. George Alfred Hebden, 78, Norborough Road, Tinsley, Sheffield. Richard Pendarves Hodges, 42, Olive Road, Cricklewood, N.W. William Francis Hollely, 67, Ross Road, Wallington, Surrey. Alexander Bynd, M.A., B.Sc., 196, Baldridgeburn, Dunfermline. William Johnson, B.Sc., Walton, Stoneygate Avenue, Leicester. Harold Bramfield Jones, Broadway House, Northolme Road, Highbury, N.Gholam Rasal Khan, B.Sc., Lyallpur, Punjab, India. Sidney Oliver Leivesley, c/o W. Leivesley, Esq., Chillagoe, N. Queensland, Australia. William John Lewis, 10, Lightoaks Road, Pendleton, Manchester. Percival James Lycett, Castle Hill, Wolverley, Kidderminster. Frank Clifford Marchant, St. Kilda’s, Manor Road, Forest Hill, S.E. Kunerji Gosai Naik, M.A., B.Sc., Krishnath College, Berhampore, Dist. Murshidabad, Bengal, India. John Allen Nichols, Stanley Mount, New Mills, Stockport. John Thomas Pattison, 72, Bath Road, Southsea, B.O. Ports-mouth. Wilfrid Roberts Powell, B.A. ,14, Marlborough Road, Richmond, Surrey. Henry Edward Findlater Pracy, 25, Grosvenor Park, Camber- well, S.E. John McArthur Stuart, Balliol College, Oxford. Robert Tennant, 4, Park Terrace, Q~.ken,sPark, Glasgow.Henry Walker, 10, Melrose Terrace, West Kensington Park, W. Henry Wood, The Limes, 62, Culverden Road, Balham, S.W. Of the following papers, those marked * were read: “266. (‘The conversion of orthonitroarnines into isooxadiazole oxides (furoxans).” By Arthur George Green and Frederick Maurice Rowe. Whilst o-nitroaniline on alkaline hypochlorite oxidation is quan- N titatively converted into benzisooxadiazole oxide, C H ’(!!\O,4\h/ 276 and 2 :4-dinitroaniline (when an alcohol is present) into a chloro-methoxy-(or ethoxy-)benzisooxadiazole oxide; the presence of an amin+, acetylamino-, me,or sulphonic group in the para-position occasions a complete disruption of the benzene ring, and only in the case of the sulphonic acid was a small quantity of a benziso-oxadiazole oxide produced.The two isomeric o-dinitrobenzidines (Cain, Coulthard, and Micklethwait,, T., 1912, 101, 2298), when subjected to hypochlorite oxidation under like conditions, yield entirely different products. Whilst the isomeride melting at 275O (regarded by these authors as 3 :5’-dinitrobenzidine) produces a typical furoxan, readily convertible on reduction into a diphenoquinonetetraoxime, C6H,(:NOH),*C,H,( :NOH),, and a bisbenzisooxadiazole, the isomeric o-dinitrobenzidine melting at 233O, regarded as the 3 :3/-derivative, gives a reddish-brown, crystalline compound of the formula CI2H6o4N4, which is probably an internal azo-compound, (p,(NO,) *R C6H,(NO,)*N’ The above bisbenzisooxadiazole oxide (bisbenzfuroxan) crystal-lises from chlorobenzene in pale yellow, thin, hexagonal plates, melting at 21lo.The corresponding bisbenzisooxadiazole (bisbenz- furazan) forms yellow needles, which melt at 244O. The dipheno- quinonetetraoxime is a brown, amorphous powder, soluble in alkalis. The authors have also repeated and confirmed the work of Drmt (Annulen, 1899, 307,54) on the nitration products of benzisooxa- diazolec oxide. Both the mono- and the di-nitrobenzisooxadiazole oxides, which are thus obtained, have strongly marked acid proper- ties, turning Congo paper blue and dissolving readily in aqueous alkalis. “267. The constitution of miline-black.Part IV.” By Arthur aeorge Green and William Johnson. In further support of Green and Wolff’s formula for aniline- black base (chlorate oxidation) (P., 1912, 28, 250): N---NPh N--NPh N--NPh NH /\/\~~\/\/\/\~\/\/\,/\~\/\/\/\IIIIIIIIII IIIll \/ \/>A/ \Ad\/ \Ad\/ \/“Ha the following data have been obtained: 277 (I) On oxidation of aniline-black with lead peroxide and sul- phuric acid a yield of benzoquinone is obtained, which corresponds with that required on the assumption that all the mono-and di-substituted benzene nuclei, but not the tri-substituted, will yield benzoquinone. (2) In presence of an excess of mineral acid aniline-black absorbs one molecule of sodium nitrite corresponding with the formation of a monodiazonium salt.Hence the terminal nitrogen atom forms an amino- and not an iminegroup, and the chain must be an open one. (3) Titrations with hydrochloric acid have shown that aniline- black, in common with emeraldine and nigraniline, yields a non-hydrolysable dihydrochloride and a trihydrochloride, in which one molecule of hydrogen chloride is readily hydrolysed. Two of the nitrogen atoms are therefore strongly basic (quinonoid), whilst a third is weakly basic (amino-group). Leucoemeraldine, which contains no quinonoid nitrogen, does not give a stable hydro- chloride. (4) Nigraniline does not condense with secondary aromatic amines, but oniy with primary amines. (5) The variety of aniline-black produced in solution by oxid+ tion with chromic acid and known as “single bath black,” or (‘bichromate black,” has given results which indicate that it is the hydroxy-analogue of ordinary aniline-black : N--NPh N---NPh N--NPh NH It is less basic than ordinary aniline-black, forming a non-hydro-lysable dihydrochloride, but not a trihydrochloride.On oxidation it gives a yield of benzoquinone consistent with the formula given. In the above formulie the colouring-matters are represented as anhydro-bases, but in both cases analyeis indicates the presence of 1H,O mor0, a fact explainable_on the assumption that one phenyl- azonium group is present as an hydroxide or two such groups as an oxide. DISCUSSION. Professor J. T. HEWITTagreed with Dr. Lowry in not liking an orthequinonoid formula for the free anhydrous bases of the safranine series.The linking of a. quinquevalent nitrogen atom to a tervalent nitrogen atom attached to the same nucleus but in the meta-pwition seemed quite improbable, and when similar structures were given to aposafranone and its derivatives, the com-pounds were represented it5 betaines of a weakly acid phenolic 275 group with a quaternary ammonium (powerfully basic) compomd. This was at variance with the actual properties of aposafranone and its hydroxy-derivatives, since their basic properties were feeble. Arguments of a similar character might be urged against Professor Green’s quaternary ammonium oxide formula for the hydrates of compounds of aniline-black type. *268 “ The constituents of senna leaves.” By Frank Tutin.Three specimens of senna leaves have been submitted to examination, namely : (I) Tinnevelly senna leaves (Cassia angtcsti-folia, Vahl); (11)senna leaves from Lima, Peru, which were found to be botanically identical with the Tinnevelly leaves; and (111) Alexandrian senna leaves (Cassia acutifolia, Uelile). The Tinnevelly leaves yielded, in addition to a small amount of essential oil, chlorophyll, and resinous products, the following definite substances : (i) Salicylic acid ; (ii) rhein ;(iii) kaempferol ; (iv) aloe-emodin ;(v) kaempferiu, C,,H,,Ol6,6H~O (m. p. 185-195O), a new glucoside of kaempferol; (vi) a mixture of the glucosides of rhein and aloe-emodin ;(vii) the magnesium salt of an unidentified organic acid; (viii) dextrose; (ix) myricyl alcohol; (x) a phyto- sterol ; (xi) a phytosterblin, CBH,GOG ; (xi;) palmitic and stearic acids.The Peruvian and Alexandrian senna leaves contained the above- mentioned compounds, with the exception of the magnesium salt, and, in addition, isorhamnetin. The latter also occurred in the form of a glucoside. The statements of Tschirch and Hiepe (Arch. Pharm., 1900, 238, 427), that senna leaves contain “senna-isoemodin,” “sennachryso-phanic acid ” (chrysophanol), a “substance, C14H1005,”and “sennit rhamnetin,” cannot be confirmed, it having been ascertained that the anthraquinone derivatives present consist solely of rhein and aloe-emodin, whilst the flavone product is either kaempferol, or a mixture of the latter with isorhamnetin.“289. A series of mixtures of nitro-compounds and amines, which‘( are coloured in the liquid state only.” By Charles Kenneth Tinkler. Certain nitro-compounds, when dissolved in fused diphenylamins and other amines, give strongly coloured solutions. The colour, however, entirely disappears on complete solidification of the mixture. 279 The most suitable substances for the demonstration of this phenomenon are mixtures of diphenylamine with one of the follow- ing nitro-compounds : 0-, m-, and pchloronitrobenzene, m-and p-nitrobenzaldehyde, p-bromonitrobenzene, tetranitromethane. By enclosing one of these mixtures between two test-tubes placed one inside the other, the phenomenon is well demonstrated. Thus, a mixture of diphenylamine and pchloronitrobenzene, which is colourless at the ordinary temperature, acquires a reddish-yellow colour when held in the hand, and loses this colour when the temperature falls.A mixture of diphenylamine and pnitrobenzaldehyde shows a deep red colour at slightly above body temperature, returning to the colourless state on cooling. A mixture of diphenylamine (solid) and tetranitromethane shows a dark brown coloration, but in a freezing mixture this colour is entirely removed. From analogy to compounds of mines and nitro-derivatives, such as trinitrobenzene (Hepp, Annalen, 1882, 215, 344; Sud-borough, T., 1901, 79, 522; 1902, 81,587, etc.; Noelting and Sommerhoff, Ber., 1906, 39,76, and others), it is possible that the colour of these mixtures is due to the combination of the nitro- derivative and amine in the liquid state only.No direct evidence of compound formation has, however, so far been obtained from the various physico-chemical investigations which have been carried out. Certain phenols and other substances may be substituted for the amine in the demonstration of the phenomenon, and the investi- gation is being extended in this direction. DISCUSSION. In reply t,o the President, Dr. TINKLERsaid that the transient colorations produced were usually orange-red or red, although in the case of diphenylamine and tetranitromethane a very dark brown coloration was obtained. No transient blue or green colora- tions had been observed.With reference to Dr. Senter’s suggestion that the colour might be due to the presence of a small quantity of compound, Dr. Tinkler pointed out that, so far, no such indication had been obtained by the physicechemical investigations which had been carried out with the mixtures. If, however, a compound was formed at all, it did not exist in the solid state, or the mixture would remain coloured on solidification and precipitation from solution. 280 270. (‘A study of some organic derivatives of tin as regard their relation to the corresponding silicon compounds. Part 11. Condensation products of dihydroxydibeneylstannane.” By Thomas Alfred Smith and Frederic Stanley Kipping. Organic derivatives of tin of the general formula SnR2(OH)2 are unknown, but various oxides, SnR20, insoluble in all organic solvents, have been prepared. The authors have attempted to obtain compounds of the dihydroxy-type in order to ascertain whether they are capable of existence, and, if so, whether they would give rise to open- and closed-chain condensation products analogous to those recently prepared from diphenylsilicanediol (Kipping, T., 1912, 101,2125).The first product of the hydrolysis of dibenzyldichlorostannane with dilute potassium hydroxide solution seems to be the potassium derivative of the dihydroxy-compound ;from the solution of this substance carbonic acid precipitates a solid, which is probably dibenzyldihydroxystannane,Sn(CH2Ph)2(0H),, but this compound is very unstable, and passes into a condensation product, which has probably the constitution : HO*Sn(CH2Ph)2*O*Sn(CH2Ph)2*O*Sn(CH2Ph)2*OH. This condensation product, unlike all the oxides, SnR20, is readily soluble in various organic solvents; when heated alone or in boiling bromobenzene solution, it passes into an insoluble oxide, which has probably the molecular formula [Sn(CH,Ph),O],.It may be concluded that all the insoluble oxides, [SnR2OIn, are condensation products of the unknown hydroxides ;similarly, the ill-defined acids of the composition H,Sn03 are probably mixtures of even more complex condensation products of stannic hydroxide. 271. (‘6’-Aminoquercetin.” By Edwin Roy Watson. A detailed description of work of which a preliminary account has already appeared (P., 1911, 27, 163).272. “Measurement of the rate of reaction by the change of volume in solution.” By Robert Wright. Although the alteration of volume resulting from chemical change has frequently been used to follow the course of a gaseous reaction -the formation of water vapour from its elements, for example- still it has seldom or never been applied to the case of reacting solutions. Such solution change is, as a rule, undoubtedly small, but even if it only amounts to about 0.2 per cent. of the total 281 volume, it gives a convenient physical method for the determination of reaction velocities. A few well-known reactions have been investigated in this manner, but in some cases the change of volume is too small to be of service.For example, on heating an aqueous solution of pyrophosphoric acid in a sealed tube for several hours at looo: only a very slight change in the density of the solution takes place; and the same negative result is obtained by a similar heating of a solution of potassium cyanide. The hydrolysis of methyl acetate by sodium hydroxide is accompanied by considerable con-traction in the reacting solution, but the change is inconveniently rapid, and the results are also masked by the rise of temperature which occurs. The rate of inversion of sucrose by an acid can readily be followed by means of the change of volume. A mixture of equal volumes of a 20 per cent. solution of sucrose with 2N-hydrochloric acid showed the following densities before and after inversion : (a) After mixing........ 1 0474 (G) After mixing........ 1'0476 After 48 hours ...... 1'0497 After 48 hoiirs ...... 1.0497 thus giving a contraction of volume equal to about 0.2 per cent. In the determination of the velocity-constant, the apparatus shown was used. A pipette of about 50 C.C. capacity has its upper tube of 1 mm. bore and 25 cm. long, the lower tube, which is fitted with a stopcock, passes through a rubber cork, and reaches almost to the bottom of a 150 C.C. flask; a side-tube open to the air also passes through the rubber stopper. The pipette is first charged with a 20 per cent. solution of sucrose, which is run into the flask, and a few grains of mercuric iodide are added as preservative; the pipette is then rinsed out and charged with 2N-hydrochloric acid, and the stopcock being closed, it is placed in position in the flask.The apparatus is now immersed in a thermostat at 25O, and allowed to attain the temperature of the bath; the tap is opened, and by applying suction to the side-tube the acid is drawn into the flask; the mixture is well stirred by drawing air through it, and is then forced back into the pipette until it stands at a level of a few cm. from the top of tshe capillary tube. It is absolutely essential to have some of thO mercuric iodide carried into the pipette along with the solution, otherwise fermentation of the sugar will cause minute bubbles of gas to be formed; for the same reason it is necessary to steam out the apparatus before u6e.The 282 pipette being charged, the tap is closed, and the level of the liquid in the tube read ;this gives the zero reading. The fall of the liquid is now read at definite intervals, and a final reading is taken after forty-eight hours, when the total fall should be from 10 to 20 cm. The velocity-constant may now be calculated in a manner quite analogous to that used with the polarimeter. In the following example a=final distance between the level of the liquid and the top of the tube, and 5, and x2are the distances corresponding with the times t, and t,. Then k, the velocity-constant, is given by: a-xk=-1 log 1. t,-t, a-x2 Time in h-. Reading from top.K. 0 0 15.0 mm. 0.011770 15 23.0 ,, 0 *004830 30 29’5 ,,0 45 35.5 ,, 0 *00479 10 41.3 ,, 0.00498 1 30 51.5 ,, 0 ‘00489 0.004702 0 60.0 ,, 0.004502 30 67-0 ,, 0.004733 0 73.5 .. 48 0 a = i16.0 ,, Leaving out of consideration the first value of X which is affected by the rise of temperature at the beginning of the reaction, it is seen that the numbers agree to within about 5 per cent. of each other, the true value given by tihe polarimeter being 0.00470. 273. Amalgams containing ailver and tin.” Li By William Arthur Knight and Reginald Arthur Joyner. It was again shown that the ageing of alloys of silver and tin is not due to superficial oxidation. A bar of alloy does not age appre- ciably even after fifteen days at 115O, whereas filings of the same bar are aged after half an hour at looo.Hence it is concluded that ageing is not due to any uncatalysed polymorphic change in the Ag,Sn contained in the alloy. It was also proved that ageing is not due to sorption of oxygen by the filings. A further hypothesis to be tested is that it may be due to catalytic action of the iron or products of iron introduced during the filing. The equilibrium of the metals silver, tin, and mercury at tem- peratures of 63O, 90°, 166O, and 214O has also been studied. The liquidus has been completely determined at these temperatures, and consists of a line roughly parallel to the Sn-Hg side of the equilateral triangle. At 63O this line only extends about one-tenth of the distance across the diagram, whereas at 214O it stretches 283 nearly the whole way across. The solidus has not, as yet, been determined accurately, but there are good reasons for considering that, commencing at the point Ag,Hg,, it extends acrcxs the diagram roughly in the direction of Ag,Sn.It has been proved that the substances represented by points on tlie solidus must be solid solutions. 274. “The action of chlorine on nz-iodoaniline and on mbromo-aniline.” By Hamilton McCombie and Percy James Ward. When m-iodoaniline is chlorinated in glacial acetic acid solution, 2 : 4: 6-trichloro-3-iodoaniline is treated with alcoholic etligl 2 : 4: 6-trichZoro-3-iodonnililze is produced. Under no conditions could an iododichloride be obtained; this is contrary to the expe- rience of Willgerodt and Wikander (Ber., 1907, 40, 4068), who considered that they obtained an unstable iododicliloride.Wlieii nitrite, 2 :4:6-trichloroiodobenzene is produced, which has been described previously by several observers. 2 : 4 : 6-Trichloro-3-10.30-aniline could not be converted into a hydrochloride, nor could it be benzoylated in presence of sodium hydroxide. The acyl derivatives of m-iodoaniline showed a slight tendency to the formation of iododichlorides, but these proved to be very unstable, and readily yielded ring substitution products. The prolonged action of chlorine on nz-iodoaniline resulted in the formation of 2 : 2 : 3 : 4 : 4 : 6-1~excrcizloro-5-iodo-A~-cyclohexeno~~e, /CH c1*cc12>C0.In this reaction the amino-group has been ccI,~cI==Cc, removed in the form of ammonium chloride, whilst the iodine atom still remains in the molecule. The constitution of this ultimate chlorination product is based on tlie following reactions: (1) On treatment with potassium iodide, the compound yields 2: 4:6-tri-chloro-3-iodophenol. (2) On treatment with potassium acetate in the presence of acetic acid, there results 2 : 3 : 4: 6-tetrachloro-5-iodophenol. (3.) Concentrated sulphuric acid converts the com-pound into 2 : 3 : 6-trichloro-5-iodo-p-benzoquinone. Analogous results have been obtained on chlorinating m-bromo- aniline under the same conditions as were employed for the iodo- compound. 275. Guanidinium nitrite and its decomposition by heat.” By Prafulla Chandra R&y,Manik La1 Dey,and Sarat Chandra JQna.Guanidinium nitrite, from the conductivity measurement of its aqueous solution, is found to behave like a typical alkaline nitrite with two ions. When heated, guanidinium nitrite yields ammonia, hydrocyanic acid, nitrogen monoxide, and nitrogen among the gaseous products, and leaves a residue which was proved to be melamine. 276. “The absorption of light by uranous chloride in different solvents.” By Thomas Ralph Merton. The absorption spectra of uranous chloride solutions in different solvents have been investigated, more especially in the presence of free hydrogen chloride. In some cases the presence of a small quantity of water produces a marked change in the absorption spectrum. It is concluded that the vibrators responsible for different bands or groups of bands are situated in different molecular aggregates.277. “The influence of solvents on the rotation of optically active compounds. Part XIX. The rotation of certain derivatives of lactic acid.” By Thomas Stewart Patterson and William Collins Forsyth. The rotation of several derivatives of lactic acid has been examined, over a range of temperature, both in the homogeneous state and in solution in two solvents, which usually differ widely in their action. 278. “The action of nitrogen iodide on methyl ketones.’’ By Frederick Daniel Chattaway and Robert Reginald Baxter. Ketones containing a methyl group react very readily with nitrogen iodide, iodoform, ammonia, an acid, and an amide being formed.In the reaction the methyl group appears to be com-pletely substituted by iodine, a tri-iodomethyl ketone being formed, which in presence of the ammonia simultaneously set free is hydrolysed to iodoform and an acid, a similar reaction between the substituted ketone and ammonia leading to the formation of iodoform and an amide. The reactions may be formulated thus: R*CO*CH,+ NH,*NI, =R*CO*CI,+2NH,. R.CO.CI, +H20=R*CO,H + CHI,. R-CO*CI,+ NH, +R*CO*NH, +CHI,. The reaction between nitrogen iodide and acetone is particularly striking, as the black solid in a few minutes is apparently trans- formed into a bright yellow one. 285 279. ‘‘Note on the constituents of commercial chrysarobin.” By Frank Tutin and Hubert William Bentley Clewer.In a recent communication (T., 1912, 101, 290) the authors described the results of the examination of several samples of commercial chrysarobin. During the course of this research the following substances were isolated : Chrysophanol (“ chrysophanic acid ”), Cl5Hl0O4; emodin monomethyl ether, Cl6Hl2O5; chryso-phanolant hranol, C15H1203; dehydroemodinanthranol monomethyl ether, Cl6HI2Q4;ararobinol, C23H1605;and emodin, C,,H,,O5. It was furthermore pointed out that commercial chrysarobin is subject to considerable variation in the relative proportions of its constituents, some samples being even entirely devoid of certain compounds which occur in others.In all the products examined, however, the first four of the above-mentioned compounds were invariably found to be present. Very shortly after the appearance of the above .communication a paper on the same subject was published by 0. Hesse (Annalen, 1912, 388,65). The results described in the latter paper, however, are such as would give the impression, at first sight, that the conclusions of Hesse and those of the present authors had very little in common. Some further explanation of the subject there- fore appears desirable. Hesse mentions as constitu2nts of commercial chrysarobin the following substances : “ Chrysophanol ” * (chrysophanolanthranol) ; “ emodinol ” (emodinanthranol) ; the methyl ethers of both these substances; and a new substance, C,,H,,O,, which is designated as chrysarobol.It is stated by Hesse, however, that of these five substances, only two, namely, “chrysophanol ” (chrysophanol-anthranol) and chrysarobol, had been isolated directly in a pure state from commercial chrysarobin, whereas all the constituents described by the present authors were directly isolated in a state of purity. Chrysophanolanthranol has long been known to be a constituent of commercial chrysarobin, but chrysarobol has not been obtained by the present authors. This is doubtless due to the varying com- position of the commercial product, since Heme remarks that he * It would appear unfortunate that Hesse should haw employed the name chrysophanol for the anthranol of “chrysophanic acid,” since the former name had already been employed by the present authors (Zoc.cit., p. 292), and previously by Tschirch (Arch. Pharm., 1911, 249, 222 ; and 1912, 250, 27), as the designation for pure “chrysophanic acid.” Moreover, since Hesse hiinself (AnnnZcir, 1899, 309,32) and Jowett and Potter (T., 1902, 81, 1577) have previously applied the name “chrysarobin ” to chrysophanolanthranol, the employment of jet a third name for this substance only adds to the confusion already existing. 286 only obtained this new substance from the chrysarobin occurring in commerce in the years 1905 and 1906. With regard to emodinanthranol (Hesse’s ‘‘ emodinol ”), no doubt can be entertained that this was derived chiefly from the mono-methyl ether of dehydroemodinanthranol ++ which was isolated and described by the present authors, since the material examined by Hesse had been heated with hydriodic acid.Hesse himself shows that he could not obtain “ chrysophanol methyl ether ” and “emodinol methyl ether ” in a state of purity, and the evidence he adduces does not seem to justify the conclusion that they are present. In the material examined by the present authors, the former compound certainly did not occur, but proof of the presence of small amounts of the latter was obtained. The statement made by Hesse that chrysophanolanthranol (Hesse’s “chrysophanol”) is insoluble in alkalis in the absence of air is incorrect. This substance dissolves fairly readily in 10 per cent.aqueous potassium hydroxide, yielding a bright yellow solution, which, on the admission of air, develops the deep red colour due to the formation of chrysophanol. 280. ‘‘Substituted dihydroresorcins. 1-Metbyldihydroresorcin and 2-methyldihydroresorcin.” By Charles Oilling. 1-Methyldihydroresorcin is a tautomeric substance, and it is suggested that this tautomeriqm prevents the existence of the two stereoisomeric forms, since it is apparent that I and I1 are mirror images of each other: 11 CH, 11 CII, H CH, \/ \/ \/c: u 0 (1.) (11.) The replacement of the labile hydrogen atom by an ethyl group destroys this tautomerism, and the ethyl ether can accordingly be isolated in two distinct forms. * In a footnote to his paper, added after the completion of the work, Hesse states that he has never observed the occurrence of the mononiethyl ether of dehydro-emodinanthranol described by the present authors, but this is obviously due to his having worked almost entirely with material tr hich had been demethylated by means of hydriodic or hydrochloric acid. In all the commercial samples of chrysarobiii examined by the present authors it was present to the extent of from 13’4 to 41.1 pcr cent;.287 2-Methyldihydroresorcin can be prepared from cresorcinol by reduction, but the product so obtained is impure, and it was only isolated in the form of crystalline derivatives. 281. (* Researches on the constitution of physostigmine. Part 111. The formation of substituted indoles from nt-4-xylidine, and the reduction of 3-11itr0-p tolylacrylic acid.” By Arthur Henry Salw ay. In this investigation the author has described some experi-ments, which were conducted with the object of ascertaining whether Madelung’s reaction for the preparation of substituted indoles from o-toluidides (Ber., 1912, 45, 1128, 3541) could be applied to acyl derivatives of nz-4-xylidine, according to the scheme : 11€0 nle/\-CH, c.R,IIe()NH.co R + @H> It has now been shown that aceto-?n-4-xylidide readily yields 2 : 5-dimethylindole by this method. The reaction, however, was found not to be generally applicable, rince 2 : 4-xylyZs~iccinnmic acid, C,H,Me,*NH-CO-CH2-CH2*.C02H, and its derivatives, which were of interest in connexion with the problem of the constitution of physostigmine, could not, be converted into indoles without disruption of the molecule.The reduction products of 3-nitro-p-tolylacrylic acid (I) have also been described. It has been ascertained that the nitro-group of this substance is more readily attacked by reducing agents than the cinnamyl residue, so that. the first product of the reaction is 3-nmi~zo-p-toZyZcrcr~Zicacid (11), which by further reduction is converted into ~-3-ami~zo-p-tolylpro~~olzic (111) :acid Ye/-\CH:CH*CO,H -+ Me/--\CH :CH-CO,H --+\-/ >-/h 0, h H, (1.1 (11.) ~-\c~u~.cH,-co,H\-/NH, (111.) 282. LLMechanismof the decompmition of carbamide and biuret by heat, and of the formation of ammelide.” By Emi Alyhonse Werner.In continuation of work recently published (T.,1913, 103,lOlO), a quantitative study of the decomposition of carbamide and biuret 288 by heat has been made, the results of which have thrown new light on the mechanism of the progressive changes. It was shown that the formation of biuret by the action of heat on carbamide is a reversible reaction in accordance with the eauation : (cnol) (keto) By heating pure anhydrous biuret for five minutes at 192O (m. p. 190°), as much as 30 per cent. of regenerated carbamide was extracted from the residue. The general idea that biuret decomposes directly into ammonia and cyanuric acid is therefore erroneous. No evidence could be obtained of the formation of tricyano-carbamide, C,N,(NH*CO*NH,),, described by Hantzsch and F.Hofmann (Ber., 1905, 38, 1010) as a product of the action of heat on carbamide; the properties of the substance described by them are identical with those of ammelide (cyanuric monamide), which has been long since recognised by Liebig and Wohler and others as a product of the decomposition of carbamide. Proof was obtained that this compound originates from the further inter-action of cyanic acid and biuret according to the equation: HN<:~:::; + HN:CO = HX<~'O:N~>C:NH orCO NH and hence is also formed during the decomposition of biuret, but in smaller quantity, since the conditions are less favourable. Thus it was shown that the whole cycle of changes which takes place during the decomposition of carbamide and biuret by heat can be simply explained by (1) dissociation, and (2) instability and reactivity of nascent cyanic acid, as illustrated by the following scheme : +By p~lymerisation= (HNCO),3(Cxauuiic wid.) HIS :C<tE2 HN :C*OH + +---L- AH + HN:CO CO*NH = NH<~~.~~>c:NH HOCN I HN:&OH Biuret ,pI Ammelide.+ H20 289 283.“Note on the mechanism of a-bromination in ketones.” By Arthur Lapworth. El. Leuchs has recently found that, by bromination of an optically active ketonic acid, a monobromo-derivative is obtained which exhibits some optical activity. As the activity of both compounds is dependent on enantiomorphism in the arrangement of the atoms and groups around the a-carbon atom to which the bromine attaches itself, Leuchs concludes that the enolic form of the ketone could not have been an intermediate stage in the sub- stitution process, and he suggests applying a similar test to active monalkylmalonic hydrogen esters (Ber., 1913, 46, 2438).Leuchs’s inference is not quite conclusive, for the facts admit of different interpretations ; for example, if the ketonic acid, like other carboxylic acids, is to any extent associated, and substitution takes place in one part of a polymolecule only, then the remainder of the polymolecule may retain its enantiomorphous arrangement during eiiolisation of the first portion, and consequently the formation of a new “asymmetric” carbon atom in the latter would naturally lead to the formation of some excess, however small, of atoms of one sign.In other words, a “partial asymmetric synthesis ” is possible. The bromination of active a-methylbutyric acid has previonsly been studied by Schutz and Marckwald (Ber., 1896, 29, 59), and of /3-phenylisobutyric acid by Lapworth and Lenton (P., 1902, 18, 35). In both instances the pro4uct mas inactive. 284. “Studies in the diphenyl series. Part V. Derivatives and substitution products of the two isomeric 0-dinitrobenzidines and synthesis of derivatives of benzerythrene.” By John Cannell Cain, Albert Coulthard and Francis Mary Gore Micklethwait. The authors have prepared a number of acyl and azo-derivatives of the two isomeric o-dinitrobenzidines (T.,1912, 101, 2298), and have submitted the two bases to the diazo-reaction.3 : 3’-Dinitrobenzidine gives the corresponding disubstituted 3 : 3’-dinitrodiphenyl, but 3 : 5/-dinitrobenzidine, in those cases where copper is employed, gives derivatives of benzerythrene : Of the numerous derivatives of the two bases that have been prepared, no two corresponding ones are identical. 200 285. “Harmine and harmaline. Part 11. The synthesis of {so-harman.” By William Henry Perkin, jun., and Robert Robinson. A detailed description of work of which a preliminary account has already appealed (P., 1912, 28, 154). ADDLTIOSS Td THE LIBRARY. Arup, Paul Seidelin. Industrial organic analysis. London 191 3. pp. xii+340. ill. 7s. 6d. net. (Recd.23/10/13.) From the Publishers : Messrs. J. & A. Churchill. Asch, TP., and Asch, I> The silicates in chemistry and commerce. 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Gildemeister, E.,and Hoffmann, Friedrich. The volatile oils. Authorised translation by Edward Rremers. Vol. I. London 1913. pp. xiii + 677. ill. 20s. net. (Recd. 6/8/13.) From Messrs. Schimmel and Ca. Harloff, V. 33. Th., and Schmidt, 11. Plantation white sugar manufacture. Translated from the second Dutch edition by James Pettigrew Ogilvie. London 1913. pp. vii + 138. 7s. 6d. net.(Recd. 10/9/13.) From the Translator. 291 Mackenzie, John E. The sugars and their simple derivatives. London 1913. pp. xvi+242. ill. 7s. 6d. net. (Recd. 21/10/13.) From the Publishers : Messrs. Gurney and Jackson. Mennicke, Eans. Die quantita tiven Untersuchungsmethoden des Molybdiios, Vanadiums und Wolframs, sowie deren Erze, Stahle. Legierungen und Verbindungen. Berlin 1913. pp. 231. M.8.-. (Recd. 16/9/13.) From the Publisher : 11.Krayn, Porritt, Benjamin Dnwson. The chemistry of rubber. London. London 1313. pp. vii+ 96. 1s. 6d. net. (Recd. 4/7/13.) Prom the Author. Pranke, Edward J. Cyanamid. Manufacture, chemistry and uses. Easton, Pa. 1913. pp. vi+ 112. $1.25. (12ecd. 2/8/13.) From the Publishers : The Chemical Publishing Company.Roscoe, The Right Ilon. Sir Henrp E., and Schorlemmer, Cad. A treatise on chemistry. Vol. 11. The metals. New edition com-pletely revised. London 1913. pp. xvi + 1470. ill. 30s. net. (Reference.) From the Right Hon. Sir Henry E. Roscoe, Royal Society of London. Catalogue of the Periodical Publications in the Library. London 1912. pp. viii + 455. 158. net. (Reference.) From the Royal Society. Smith, Harold Hamel [Editor]. The fermentation of cacao. With which is compared the results of experimental investigations into the fermentation, oxidation, and drying of coffee, tea, tobmco, indigo, etc., for shipment. Ey the following authorities : Axel Preger, Oscar Loew, Fickendey, Schulte im Xofe, J. Sack, Geo. 8. Hudson, and Lucius Nicholls.London 1913. pp. lvi+318, ill. 10s. net. (Recd. 1/9/13.) From the Publishers : Messrs. 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Leipzig 1913. pp. xviii+ 713. M.20.-. (Recd. 1/10/13.) Molinari, Ettore. Treatise on general and industrial organic chemistry. Translated from the 2nd Italian edition by Thomas Henrp Pope. London 1913. 248. net. (Red 6/10/13.) Nazari, Giovnnni Buttista. Della Tramutatione metallica sogni tre, . . Nel primo d’i quali si tratta della falsa tramutatione eofistica : Nel second0 della utile tramutatione detts reale usuale: Nel terzo della diuina tramutatione detta reale Filosofica.Con un copioso Indice per ciascun sogno de gl’ Auttori, & opre c’hanno sopra cio trattato. In Brescia 1572. pp. [viii] + 167 + [viii]. (Reference.) Thurneisser, Leonhurdt. II~oKuT~X~$Koder PrEoccupstio, Diirch zwolff verscheidenlicher Tractateo, gemachter Harm Proben. Das 59 Buch. Franckfurt 1571. pp. [iv] +lxxxv c [ii]. (Reference.) 111. Pamphlets. Anderson, C., and Mingaye, J. C. H. Description and analysis of the Binda meteorite, (From the Records of the Australiun Museum, 1913, 10.) Bovie, W,17. A preliminary note on the coagulation of proteins by the ultraviolet light. (From Scienci, 1913, N.S. 37.) --The temperature coefficient of the coagulation caused by ultra-violet light.(From Science, 1913, N.S. 37.) Drncker, Carl. 3Iolekularkinetik und Molarassoziation als physiko-chemische Grundvorstellungen. Leipzig 1913. pp. 33.. Eaton, Bertie Jurnes. Camphor from Cinnamomum Camphoi.a, (The Japanese Camphor Tree). Cultivation and preparation in the Federated Malay States. (Fed. Malay St,ates. Pep. of Agric. Bull., 1912, No. 15.) -The preparation of plantation Para rubber. (Fed, Malay States. Dept. of Agric. Bull., 1912, No. 17.) Fichter, PI*,,Stutz, Karl, and Grieshaber,Tritz. Ueber die elektro- lytische Bildnog ron Harnstoff und von Acetamidin-nitrat. (From the Verhccndl. LYaturforsch. Ges., Basel, 1912, 23.) Fischer, Emit?,and Klemperer, Georg. Ueber eine new Klasse von lipoiden Arsenverbindungen.(From the I’herapie der GegenNart, 1913.) Hooper, David. The ash of the Plantain (Muscs sapienturn). (From the J. and Proc. Asiatic Xoc., Bengal, 1912, 8.) 293 India. Report on the progress of Agriculture in India for 1911-12. Calcutta 1913. pp. 65. Schroder, 3. Ueber den Nachweis von weissem Phosphor in Zundwaren. (From the Arb. K. Gesundheit, 1013, 44.) OdQn,Xven. Der Kolloide Schwefel. (From the Nova Acta Regico Xoc. Xci. Upsala, 1913, [iv], 3.) Osterhout, W.J. V. Plants which require sodium. (From the Bot. Gax., 1912, 54.) Sabatier, Paul. Die Hydrierung durch Katslyse. Leipzig 1913. pp. 20. Tadokoro, 5". Ueber die Enzymatischen Wirkungen der Frischen Nahrungs-und Genussmittel. (From the J. Colt!.Agric., Tohoku Imp. Univ.,Sapporo, Japan, 1913, 5.) Vavon, Gustme. Reductions catalytiques en presence de noir de platine. Application a la. transformation en alcools des aldehydes et des cetones. Toulouse 1913. pp. 107. RESEARCJ3 FUND. A meeting of the Research Fund Committee will be held in December next. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on, or before, Monday, December lst, 1913. All persons who received grants in December, 1912, or in December of any previous year, whose accounts have not been declared closed by the Council, are reminded that reports must be in the hands of the Hon. Secretaries not later than Monday, December 1st. The Council wish to draw attention to the fact that the income arising from the donation of the Worshipful Company of Gold-smiths is to be more or less especially devoted to the encouragement of research in inorganic and metallurgical chemistry.Further-more, that the income due to the scm accruing from the Perkin Memorial Fund is to be applied to investigations relating to problems connected with the coal-tar and allied industries. PAPERS TO BE READ AT ORDINARY SCIENTIFIC MEETINGS. A list of the papers to be read at each Ordinary Scientific Meeting will be advertised in the Morning Post on the Wednesday previous to the day of meeting, and will appear on the front page, at the top of extreme right-hand column. 294 LAWES AND GILBERT CENTENARY FUND. It is proposed to erect at Rothamsted a Commemoration Laboratory to celebrate the centenary of the birth of Sir John Lawes in 1814 and of Sir Henry Gilbert in 1817.A sum of &12,000 is required for the purpose, but it is understood that if onehalf of this amount can be raised by subscription, the other half will be forthcoming in the form of a grant. An appeal is therefore being issued for the sum of &6000. Subscriptions should be sent to the Secretary, The Rothamsted Experimental Station, Harpenden, cheques being crossed Robarts, Lubbock and Co. At the next Ordinary Scientific Meeting on Thursday, November 20th,1913, at 8.30 p.m., the following papers will be communicated : “The interaction of sodium amalgam and water.” By H. B. Baker and %. H. Parker. ‘(The action of variously treated waters on sodium amalgam.” By L.H. Parker. “ Some derivatives of oleanol.” By F. Tutin ‘and W. J. S. Naunt’on. “Some derivatives of phorone. Part I.” By F. Francis and F. G.Willson. “ The porosity of iron.” By W. H. Perkins. “ The bleaching action of hypochlorite solutionz.” By S. H. Higgins. R. CLAY AND SONS, LTD., BRUNSWICK ST., STAMTORD ST., S.E., AND BUNGAY, SUFFOLK

ISSN:0369-8718    

DOI:10.1039/PL9132900239

出版商:RSC    

年代:1913

数据来源: RSC