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Proceedings of the Chemical Society, Vol. 27, No. 390 |
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Proceedings of the Chemical Society, London,
Volume 27,
Issue 390,
1911,
Page 201-256
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PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 27. No.390. The Council has ordered the following letter and report to be printed in the Journal and Proceedings of the Society: IMPERIAL OF AND TECHNOLOGY,COLT~EGESCIENCE ROYALCOLLEGEOF SCIENCE, SOUTHKENSINGTON, LONDON,S.W. October 4th, 1911 GENTLEMEN, I beg to forward you the Annual Report of the International Committee on Atomic Weights for 1912, to which I have appended, it9 deisired by them, the signaturm of Professors Clarke, Ostwald, and Urbain. Slight changes have been made in the atomic weighte of calcium, erbium, iron, mercury, tantalum, and vanadium, which are indi- cated, in accordance with a suggestion received from Germany, by asterisks. The only addition to the list of elements is that of niton (radium emanation), with the symbol Nt, and the atomic weight 222.4, as determined by Gray and Ramsay.This is in fair agreement with 20% the value calculated by Debierne from observations on the rate of flow of the gas. I have the honour to be, Gentlemen, Your obedient servant, T. E.THORPE. To the Hon. Secretaries, The Chemical Society, Burlington House, London, IT. Report of the International Committee on Atomic Weights, 1912. Since the report of the Committee for 1911 WM prepared, a number of important determinations of atomic weight have beer1 published, which may be summarised as follows : Xitrogen.-Guye and Drouginine (J. Chim. Phys., 1910, 8, 473), from seven analyses of N204,find, in mean, N=14*010.Sdphur.--Burt and Usher (Yroc. Roy. Soc., 1911, A, 85, 82), by analysis of nitrogen sulphide, N4S4,have determined the ratios S :N : : 1.0:0.43687. Hence, calculating with N =14.009, S=32-067, in good agreement with the accepted value. Chlorine.-Burt and Gray (Chem. Xews, 1911, 103,161 and 1T0j have continued their work upon the density of hydrochloric acid, and confirmed their f ormer determination of C1= 35.46. lodine.-Baxter (J. Amer. Chem., SOC.,1910, 32, 1591) haa re-determined the ratio of iodine to silver with extreme care. Com-bining his results with the previously-determined ratio of silver to iodine pentoxide, he finds Ag= 107,864 and II= 126.913. The value for silver varies from that found by Richards and Willard, and the discrepancy is as yet unexplained.Sodium-Goldbaum (J. Amer. Chern. SQC.,1911, 33, 35) has made analyses of sodium chloride and bromide by a new electrolytic method. The salts were electrolysed with a mercury anode and a weighed silver cathode, and on the latter the halogen was collected in weighable form. From the chloride, with Cl=35*458, Galdbaum found Na= 22,997 ;the bromide, with Br =79.920, gave Na= 22.998. Culcium.-Two papers by Richards and Honigschmid (J. Amer. Chem. SOC.,1910, 32, 1577; 1911., 33, 28) on the atomic weight of calcium have appeared. From analyses of calcium bromide, Ca= 40.070, when Ag =107.88. From analyses of the chloride, Ca=40.074. The value 40.07 is adopted in the table at the end of this report.Cadmium.-Perdue and Hulett (J. Physical Chem., 1911, 16, 155; see also Richards, J. Amer. Chem. SOC.,1911, 83,SSS), from 203 electrolytic analyses of cadmium sulphate, conclude that the atomic weight of cadmium is near 112.30. This is lower than the accepted value, but as the investigation is being continued with other salts of cadmium, any change in the table should be deferred. Mercury.-Xasley (J. Amer. Chem. SOC.,1910, 32, 1117) has continued his work on the atomic weight of mercury, varying his methods. New analyses of the chloride give Hg=200-63, in con-firmation of his former determinations. In a private communication he states that analyses of the bromide lead to the same value. The n0w figure, Hg=200*6, should be adopted.Vanadium.-McAdam (J. Bmer. Chem. SOC.,1910, 32,1603), by reducing sodium vanadate to sodium chloride, by heating in a stream of dry hydrochloric acid, finds V=50*967, or 51 in round numbers. The latter figure is as probable as any. Tantalum.-Ralke (J. Amer. Chem. SOC.,1910, 32, 1127), by hydrolysis of tantalum pentachloride, has determined the ratio 2TaC1, :Ta20,. The mean of five concordant determinations gives Ta= 181.52, when C1=35*46. The rounded-off value 181.5 should be accepted. TeZZum'urn.--Flint (Amcr. J. Sci., 1910, [iv], 30,209) has con-tinued the work reported by Browning and Flint in 1909 on the fractionation of tellurium by hydrolysis of the tetrachloride. With successive fractions the atomic weight steadily decreased.Seven analyses of the basic nitrate representing the tenth fractionation gave values for Te ranging from 124.25 to 124.42. As the work is still in progress, any acceptance of these low figures would be premature. Iron.-Baxter, Thorvaldson, and Cobb (J. Amer. Chem. SOC., 1911, 33,319), from analyses of ferrous bromide, find Fe=55-838 when Rg= 107-88. In another communication (ibid., p. 337), Baxter and Thorvaldson find Fe=55*836. The latter figure is the mean of two series, meteoric iron being taken as the starting point. The value 55.84 is given in the table. O-irar&m.-Oechsner de Coninck (Compt. rend., 1911, 152, 711 and 1179), by reduction of UO,Cl, and WO,,H,O to UO, in hydrogen, concludes that U=238.5. The work is only approximate in character.Scandium.-Mepr and Winter (Zeitsch. anorg. Chem., 1910, 67, 398), in a, preliminary series of experiments, find values for Sc ranging from 44.M to 45.37; in mea3, 45'12. This is higher than the recognised vdue, but ih adoption would be premature. More details are needed. Neodymium.-By extended and careful analyses of the chloride, Baxter and Chapin (Proc. Amer. Acad., 46, 215) have redetermined 204 the atomic weight of neodymium. From the ratio MdC1,:3Ag, Nd= 144.268. From the ratio NdC1, :3AgC1, Nd =144.272. A small correction raises the value to 144.275. The rounded-off value 144.3, given in the table, may be properly retained. Erbium.-Hofmann (Ber., 1910, 43, 2635), from analyses and syntheses of the sulphate of ‘(neoerbium,” finds Er =167.68.This may be rounded to 157.17. A rgom-Determinations of the density of argon,by Fischer and Froboese (Bet.., 1911, 44, 92), give a mean value of 19.95. Hence A =39.90. Nitom-Gray and Ramsay (Proc. Boy. SOC.,1910, A, 84, 536), with the aid of the microbalance, have determined the density of the gaseous emanation from radium, to which they give the name niton. The mean value found gives Nt=223, but the value 222.4 is preferred (compare also Debierne, Compt. rend., 1910, 160, 1740). The gas is a member of the argon group, and seems to be entitled to recognition in the table. The table of atomic weights for 1912 follows. In accordance with a suggestion received from Germany, the changed values are indicated by an asterisk.The changes are few in number, and only in two cases aro they large. F. W. CLARKE. W. OSTWALD. T.E.THORPE. G. U-AIN. 205 1912. International Atomic Weights. 0=16. 0=16. Aluminiuni ................. A1 Antimony ..................... Sb 27 -1 120'2 Molybdenum ............... Mo Neodymium .................Nd 96 .0 144'3 Argon ...................... A 39-88 Neon........................... Ne 20.2 Arsenic ..................... As 74.96 Nickel ........................Ni 58.68 Barium ....................... Ba 137'37 Niton*(radiumemanation) Nt 262'4 Bismuth ..................... Ri 208.0 ru'itrogen .....................N 14-01 Boron ........................ 13 11'0 Osmium .....................0s 190.9 Bromine .................... Rr 79.92 Oxygen ........................0 16-00 Cadmium ..................... Cd 112'40 Palladium., ................... Pd 106 -7 Cesium .......................Cs 132.81 Phosphorus ..................P 31'04 Calcium" ..................... Ca 40.07 Platinum ..................... Pt 195.2 Carhon ........................ C 12.00 Potassium ..................... K 39'10 Cerium ........................ Ce 140.25 Praseodymium ............... Pr 140*6 Chloriue .....................C1 35'46 Radium........................ Ra 226'4 Chromium .................. Cr 52-0 Rhodium .....................Rh 102'9 Cobalt ....................... Co 58.97 Rubidium ....................Rb 85.45 Columbium .................Cb 93.5 Ruthenium ..................Ru 101.7 Copper ........................ Cu 63.57 Samarium ................. Sa 150'4 Erbium" ..................... ErDysprosium ................. DY 162.5 167-7 Scandium .................. Sc Selenium .....................Se 44'1 79.2 Europium ..................... Eu 152.0 Silicon .......................Si 28.3 Fluorine .....................F Gadolinium ..................Gd 19.0 157.3 Silver Ag Sodium ........................ Na ........................ 107'88 23.00 Gallium ....................Ga 69'9 Strontium ..................Sr 87'63 Germanium .................. Ge 72 '5 Sulphur ..................... S 32-07 Gluciiium ....................G1 9'1 Tantalum* ................. Ta 181'5 Gold ........................... Au 197'2 Tellurium ..................... Te 127.5 Helium ........................ He 3.99 Terbium ..................... Tb 159.2 Hydrogen .....................H 1'008 Thallium .................... T1 204'0 Indium ....................... In 114'8 Thorium ..................... Th 232'4 Iodine ........................ I 126'92 Thulium ..................... Tm 168.5 Iridium....................... Ir 193.1 Tin ........................... Sn 119'0 Iron" ........................... Fe 55.84 Titanium ..................... Ti 48'1 Krypton ..................... Kr Lanthanum ..................La a2.w 139.0 Tungsten .....................W Uranium ..................... U 184'0 238.5 Lead .......................... Pb 207.10 Vanadium* ..................V 51'0 Lithium ..................... Li 6 '94 Xenon ........................ Xe 130'2 Lutecium .................... Lu Manganese ..................MnMagnesium ..................Mg 174-0 24 *32 54'93 Ytterbium (Neoytterbium) Yb Yttrium ..................... Yt Zinc ........................... Zn 172.0 89.0 65'37 Mercury * ..................... Hg 200.6 Zirconium ..................... Zr 90.6 B The following axe abstracts of papers received during the vacation, and published, or passed for publication, in the Transactions: 192. ‘(Indicators of the methyl-red type.” By Hubert Howard and Frank Geo.Pope. (Trans., 1911, 1333.) Azcwompounds of the methyl-red type were prepared by combin- ing dimotised anthranilic acid with a-naphthylamine, dimethyl- a-naphthylamine, diphenylamine, and phenyl-a -naphthylamine. Contrary to the statement of Tizard (Trans., 1910, 97, 2485), t,he potassium salt of methyl-red can be obtained in a crystalline form, and is not deliquescent. 193. ‘(Dihydrocinnamenylcarbimide(P-Phenglethyl isocyanate) ,” By Martin Onslow Forster and Hermann Stotter. (Trans., 1911, 1337.) 13ih~d~ocinnamenylcarbi~ide,C,~H,-CH,*CH,*N:C:O, and some of its derivatives were studied, and in the course of their examination it was noticed that whilst this isocyanate converb menthol into the corresponding carbamate, cinnamenylcarbimide transforms that alcohol into menthyl carbamate, a change which involves the disappearance of phenylacetylene.194. ‘(The synthesis of histidine.” By Frank Lee Pyman. (Trans., 1911, 1386.) A preliminary aocount of the synthesis of r-histidine has already appeared (this vol., p. 92). The synthesis of histidine itself, that is, the naturally-occurring hvo-modification of this base, has now been completed by the resolution of r-histidine. Both the d-and 1-varieties have been obtlained in a practically pure state by crystallisation of the hydrogen tartrates. 195. (‘The action of benzylamine on 8-dibromosuccinicacid.’’ By Edward Percy Frankland. (Trans., 1911,1775.) When benzylamine reacts with s-dibromosuccinic acid in alcoh6lic solution it gives rise successively to the following compounds: (I)the dibensylamine salt of dibromosuccinic acid, (11) the mono-b enzylamine salt of bromomaleic acid, (111) the monobensylamine salt of b eltsrylaminobromosvccinnic acid, C02H*CH(NH-C7H7)-CHBr-C‘02H, and (IV) the monobenzylamine salt of dibenzylaminosvccinic acid, CO,H-CH(NR-C,H,)*CH(NH.C,R,)-CO,H, from which the free 207 acid can be obtained by dissolving in hydrochloric acid and precipitating with water.When the reaction is carried out in aqueous solution the products isolated are the dib en,zyZamine salt of dibenzylaminwuccinic acid and the dibenzylamide of &tartaric acid. This formation of an amide in aqueous solution is to be accounted for by an intra- molecular rearrangement demonstrated by Lutz (Diss., Rostock) in the action of ammonia and other amines on monohalogen succinic acids, whereby amides of malic acid are produced.186. (‘8method of determining carbon and nitrogen in organic compounds.” By Edward Percy Frankland. (Trans., 1911, 1783. ) The Frankland-Armstrong vacuum combustion process (Journ. CIwn. SOC.,1868, 21,77) can be adapted for the estimation of carbon and nitrogen in organic compounds. The gases (carbon dioxide and nitrogen) evolved during the combustion of a known weight of substance, generally 0.1 gram or less, are collected, and measured over mercury in a graduated vessel; the carbon dioxide is then absorbed with aqueous potassium hydroxide, and the residual nitrogen transferred to a narrower graduated tube and measured over water.The process can be carried out in less time than is required by the ordinary carbon-hydrogen combustion method, and the figures obtained both for nitrogen and carbon in a variety of organic compounds are in good agreement with theory. The presence of bromine in the molecule, even up to 80 per cent., has not been found to affect the accuracy of the results, hence this method appears to be of especial advantage in connexion with organic substances containing both nitrogen and halogen. 197. ‘‘ The synthesis of derivatives of thioxanthone from aromatic diaulphides.” By Effie Owendoline Marsden and Samuel Smiles. (Trans. 1911, 1353.) The synthesis of thioxanthones may be accomplished by heating di-o-t,hiobenzoic acid or its derivatives with a suitable aromatic compound in presence of concentrated sulphuric acid, the interaction which ta.kes place being summed up as follows: + H2S04=2C02H*C6H4*S*OH(C02H*C6H4*S), + SO,.CO HCBH4<5.& +C(+,R, =C,H4<!~>C6HZR, +2H@. The method may be modified by arranging that the carboxyl group is present in the simple aromatic compound instead of in B2 the disulphide ; thus on heating p-dithidimethylaniline with m-hydroxybenzoic acid and sulphuric acid, the corresponding thioxanthoae is formed. 198. (‘Trialkylammonium nitrites and nitrites of the bases of the pyridine and quinoline series. Part 11.” By Pafichiinan Neogi.(Trans., 1911, 1598.) k’icolinium nitrite is obtained, together with the nitrate, by con- centrating an ice-cold solution in a vacuum desiccator. Quinolim’um nitrite exists in solution, but not in the solid condition. Piper& dinium nitrite has been obtained in colourless plates. Pyridime methonitrite is a reddish-yellow liquid. Piperidine methonitrite crystallis-in colourless plates. Yicoline methonitrite forms red crystals, and puinoline methonitrite dark red cryst.als. 199. “The density of liquid sucrose and of its solutions in water.’’ By Frederik Schwers. (Trans., 1911, 1478.) By melting sucrose under paraffin the author has succeeded in determining Lhe density of liquid sucrose at temperatures between -153 and 115O. The densities of aqueous solutions of sucrose containing 10, 20, 30,40,50, 60,and 70 per cent.of sucrme have also been determined. 200. ‘‘The condensation of crotonaldehyde.” By Ida Smedley. (Trans., 1911, 1627.) The condensation of crotonaldehyde under the influence of alkaline condensing agents has been studied. By oxidising the condensation product with silver oxide, and subsequently reducing with phm- phorus and hydridic acid, n-octoic acid has been identified. The y-carbon atom of one crotonaldehyde molecule must therefore have reacted with the aldehyde group of a second molecule. 201. (‘Ionisation in non-aqueous solvents. Part I.” By Harry Medforth Dawson and May Sybil Leslie. (Trans., 1911, 1601. Measurements of the electric conductivity of non-aqueous solution8 of alkali metal iodides and the corresponding polyiodides have shown that, in general, the polyiodides are ionised to a greater extent thm the simple iodides.In methyl and ethyl acetate solutions the observed conductivity differences are very large, and in the latter solvent the polyiodides of potassium conduct from 209 twenty-five to fifty times as well as the simple iodide. Evidence has been obtained in favour of the formation of definite polyiodides in such solutions, and the conductivity differences must be ascribed to differences in the degree of ionisation of the dissolved electrolyte. The simple a-lkali iodides would appear to be abnormally weak electrolytes when dissolved in methyl and ethyl acetates. 202.“The formation of glgoxalines from acyl derivatives of a-keto-p-anilino-ap-diphenylethane.By Arthur Ernest Everest ” and Hamilton McCombie. (Trans., 1911, 1746.) Glyoxalines can be prepared from acyl derivatives of a-keto-B-anilino-afbdiphenylethane by heating these compounds in sealed tubes with aqueous ammonia: CPh-NPhCOPh*CHPh*NH*COR--+ gPh-N >CR. From ths benzoyl, acetyl, and formyl derivatives respectively there have been prepared by this method 1 :2 :4 :5-tetraphenyl-glyoxarline, I :4 :5-triphenyl-2-rnethylqlyoxaZine,and 1 :4:5-triphenyl-ylyoxalke. The hydrochlorides, picrates, and pZcat,inichZoridesof these substances have also been prepared. In the formation of all these glyoxalines there was obtained, in varying quantities, 2 :3 :5 :‘6-tetraphenylpyrazine : 2Ph*r;J*gPh CPh-N*CPh’ dome curious colour changes of a-ketotB-anilino-aB-diphenylethaiie and its xyl derivatives have been noticed in the course of this work.a-Keto-~-anilinw+3-diphenylethaneitself is yellow, and gives a yellow solut,ion in alcohol, but this solution becomes colourless on the addition of a drop of acid. The acyl derivatives, on the other hand, are colourIess, and yield cdourless solutions, but these solutions become strongly yellow on the addition of a drop of alkali. The probability is that there exist ketonic and enolic modifications of these substances. 203. (‘The osmotic pressure and conductivity of aqueous solutions of Congo-red, and on reversible membrane-equilibria.” By Frederick George Donnan and Albert Bnckley Harris.(Trans., 1911, 1554.) Measurements of osmotic pressure and electrical conductivity show that, although aqueous solutions of Congo-red are very con-siderably ionised, they exhibit an osmotic pressure corresponding 210 very closely with the value calculated for single undissociatd molecules. On dialysis, solutions of Congo-red suffer a gradual '' membrane-hydrolysis." Constant values of osmotic pressure can only be obtained in prwnce of smdl concentrations of alkali hydroxide. The effect of various concentrations of sodium hydroxide and sodium chloride on the osmotic pressure has been studied. It has been shown experimentally and theoretically that a non-dialysing electrolyte such a.s Congered causes an unequal distribution of sodium chloride on either side of the membrane (in this case, parchment paper).204. '' Triketohydrindene hydrate. Part V. The analogues of nramil and pnrpnric acid." By Biegfried Rnhemann. (Trans., 1911, 1486.) Diketohydrindamine, C,H,<:>CH*NH,, which is formed by the reduction of oximinodiketohydrindene, C,H,<~~>C*NOH, by means of stannous chloride (Trans., 1911, 99, 1306), could not be obtained pure, owing to the ease with which it is oxidirjed by the oxygen of the air. It mas characterised, however, by the condensation products which it yields with aromatic aldehydes. These substances, which may be represented by the general formula C,H,<~;>CH*N: CHR, are not very stable, and are readily hydrolysed to the compoundsfrom which they are formed.The blue coloration which is produced on exposure of diketohydrindamine to moist air is due to the formation of the analogue of murexide, which is the ammonium salt of diketo-hgdrindg Zidenediketoh ydrindamine, This can bo prepared from hydrindantin under conditions similar to those which served for the production of murexide from alloxantin (Piloty and Finckh, Annalen, 1904, 333,27). The ketone, corresponding with this salt was also isolated ; it is, however, readily decomposed by mineral acids. By the action of triketohydrindene hydrate on uramil dissolved in potassium hydroxide, the potassium salt of diketohydrindylideneuurama'l, is produced ; it dissolves in water to yield reddish-violet solutions, which are decolorised by dilute hydrochloric acid.211 It was found that the colour-reaction which the triketone gives with amino-acids is based on the formation of the ammonium salt of diketohydrindylidenediketohydrindamine. 205. The constitution of the organic ferrocganides.” By Ernald George Justinian Hartley. (Trans., 1911,1549.) In order to throw some light on the constitution of the f orrocyanida, the decomposition of tetramethyl ferrocyanide, (CH&F~C~NG,and hexamethyl f errocyanogen dihydrogen sulphate, (CH3)6Fe~6N,H2(S04j2(Trans., 1910, 97, 1066, 1725), has been studied. The former, on heating with concentrated sulphuric acid, gave a mixture of ammonium and methylammonium aulphates, whilst the latter, under similar conditions, gave only methyl- ammonium sulphate.Decomposition of the hexamethyl compound with sodium hydroxide also led only to the formation of methyl- amine derivatives. From this the conclusion is drawn that all the methyl groups are attached directly to nit’rogen atoms in both the substances examined. 206. i6Contributions to the chemistry of the terpenes. Part IX. The oxidation of camphene with hydrogen peroxide.” By George Gerald Henderson and Maggie Xillen Jeffs Sutherland. (Trans., 1911, 1539.) Camphene, when dissolved in glacial acetic acid, is oxidised by a 30 per cent. aqueous solution of hydrogen peroxide, yielding a mixture of products, which includes both acids and neutral com-pounds.The acid present in largest quant?ity, camphy2ic acid, CgH,,*C02H,is a crystalline solid, m. p. 95*, and when heated with acetic anhydride is transformed into the isomeric isocamphenilanic acid. From the chloride OP camphylic acid, CgH,,*COC1, by bromination and subsequent treatment of the product with water, bromocamphylic acid, CgH,4Br*CY)2H, was obtained in crystals, melting at 210O. When heated with aqueous sodium carbonate the bromcmcid is converted into the crystalline hydroxycamphylk acid, CgH,,(0H)*C02H,m. p. 245O. The latter does not give a ketone when oxidised with lead peroxide. Camphenilone, C9HI40, a ketone which has been prepared from camphene in other ways, is the chief component of the mixture of neutral oxidation products.isoC‘ampheiziZanaldehycle, C9H,,*CH0, which is also present, is very similar in properties to the isomeric camphenilanaldehyde, but yields isocamphenilanic acid on exposure to the air. Its semicarbazone melts at 191--192O, and the semi- 212 carbazone prepared from camphenilanaldehyde appears in reality to be this compound. Among the other neutral products, together with a very little camphene glycol, C,,H,,(OH)2, and a trace of a crystalline substance which melts at about 69*, there occurs a compound which apparently has the formula C9H,$02.When heated to a high temperature with phthalic anhydride this compound yields a crystalline ester, from which, by hydrolysis, an dcohol of the formula CgH,,O is obtained. 207. r6 Synthesis of derivatives of thioxanthone.Part 111. 1 :4-Di-hydroxg thioxanthone.” By Hans Thacher Clarke and Samuel $milen. (Trans., 1911, 1535.) When pbenzoquinone is allowed to react with o-thiolbenzoic acid, 2’-carboxy-2 ;5-dihydroxydiphenynyl sulphide is produced ; C6H,02+ HS*C6H4*C02R== C6H,(OR),*S0C,H4*CO,H. The latter on treatment with cold sulphuric acid loses water, and is converted into 1:4-dihydroxyti~ioxantnone, C,H4<!g>C6H,(OH),. This substance and ih salts are strongly coloured, but do not appear to be of practical value as dyestuffs. 208. ‘(Optically active derivatives of l-methylcycZohexylidene-4-acetic acid.” By William Henry Perkin, jun., and William Jackson Pope. (Trans., 1911, 1510.) The optical activity of d-and Z-1-methylcyclohexylidene-4-acetic acid is due to the configuration of the molecule exhibiting a parti-cular type of enantiomorphism unassociated with asymmetry of any particular atom present; the authors give the name centroasym-I‘ metric ” to this type of enantiomorphism.They now describe the conversion of optically active centroasymmetric compounds into substances containing an asymmetric carbon atom, and also the reverse change; they show that the optical activity of the original substance is preserved during the change in either direction. The change from the one to the other type of enantiomorphous configuration is thus unaccompanied by optical inversion. 213 209. ‘(Substitution in aromatic hydroxy-compounds. Part I.The action of nitric acid on gallic acid trimethyl ether and pyrogallolcarboxylic acid trimethyl ether.” By Victor John Harding. (Trans., 1911, 1585.) Gallic acid trimethyl ether on treatment with nitric acid under varying conditions undergoes the following reaction : Me0 Me0 Me0 MeOOMeO f-- MeO()ONe --3 MeO(>OMe VN02uO,H \/C0,H \/NO2 Yyrogallolcarboxylic acid trimethyl ether under similar conditions yields only the nitreacid: MeO Me0 MeO/\OMe !,)CO,H.!\//CO,H -+ M~O/\OM~ NO2 NO substitution of the carboxyl group was observed. As the substitution of carboxyl groups by the nitregroup is partly dependent on its position in the molecule, the hypothesis is put forward that carboxyl-substitution is governed by those forces in the molecule which direct substitution in the parent phenol ether, and that there is no red difference between hydrogen-substitution and carboxyl-substitution.210.(‘The solubility of cuprous oxide in aqueous ammonia solutions, and the composition of the cuprous-ammonia complex.” ByFrederick George Donnan and John Bmeath Thomas. (Trans., 1911, 1788.) The solubility of crystalline cuprous oxide in solutions of ammonia of different concentrations has been determined at 25O. It is found that for a certain range of ammonia concentrations ths concentration of total copper is approximately proportional to the square root of the “ free” ammonia. From this result the conclusion is drawn that in these solutions the cuprousammonia hydroxide present is mainly of the type (Ch-NHJOH.211. “The acid character of gallotanxh acid.” By Ramni Paniker and Edmund Stiasny. (Trans., 1911, 1819.) The authors have applied Bredig and Fraenkel’s method to the determination of the hydrion concentration of gallotannic acid. C ‘214 This method is based on the dissociation of diazoacetic ester by the catalytical action of hydrions, the concentration of which determines the speed of the development of nitrogen. Different samples of gallotaanic acid, prepared by diff erent--and partly new----methods of purification, were used, arid tlieir acid c2iaract8er was found distinctly greater than could be explained by the presence of phenolic groups only, thus leading to t,he conclusion that free carboxylic groups are present.This confirms the views of Schiff and Nierenstein, but does not agree with those of Bottinger (Ber., 1884, 17, 1503), Walden (Ber., 1898, 31, 3170), and Dekker (Ber., 1906, 39, 2497). The authors are of the opinion that even the purest gallotannic acid obtainable is no single substance, but n mixture of at least two components of allied character. 212. Synthesis of polypeptides of a-amino-n-nonoic acid with glycine, alanine, valine, leucine, asp aragine, and aspartic acid.” By Arthur Hopwood and Charles Weizmann. (Trans, 1911, 1577.) As polypeptides of a-amino-u-nonoic acid with glycine and other amino-acids probably occur in the degradation products of the proteins contained in beetroot, the leaves of Pelargonium roseurn, and other plants, the authors have prepared the following derivatives of a-amino-n-nonoic acid : a-Bromo-n-nonoyl cldoride, C,H,,Br*COCl, prepared by heating a-bromcm-nonoic acid with phosphorus pentachloride, is a colourless liquid boiling at 108-110°/9 mm.When condensed with glycine in the presence of sodium hydroxide it gives a-bromo-n-nonoyl-glycine, CyRIGRr*C0*NH*CH2.CO2~~,which forms a mixture of colourless, rhombic plates and rhombic prisms, melting at 115*5--117O. The crystals are only sparingly soluble in cold water or benzene, but readily so in alcohol, ether, or alkalis. a-dniino-n-nonoylylycine, is pre- NH,*C8EIl,*CO*NH*CH2*C02H, pared by heating a-bromen-nonoylglycine with concentrated aqueous ammonia.It forms a mixture of colourleas, monoclinic needles and rhombic plates, which sinters at 205O, and melts and decomposes at 215-216”. It is fairly soluble in water, almost insoluble in alcohol or benzene, but readily soluble in alkalis or mineral acids. Like the proteins, it yields a white, amorphous precipitate with phospho- tungstic acid, but unlike the corresponding dipeptide, a-amino-laurylglycine, it. is not hydrolysed by enzymes or bacteria. Somcwhat. similar bromo-compounds are prepared by the con-densation of a-bromo-n-nonoyl chloride with alanine, valine, leucine, asparagine, and aspartic acid, and these on heating with ammonia yield the corresponding dipeptides. Similarly, the tripeptide Zeucyl- 215 a-amino-n-nnitoylglycineis prepared by condensing a-amino-n-nonoyl- glycine with a-bromoisohexoyl bromide, and then displacing the bromine by a.11 amino-group through the action of ammonia.b6213. Latent heats of vaporisation of mixed liquids. Part I.” By Dan Tyrer. (Trans., 1911, 1633.) In order to determine the latent heats of mixed liquids the liquid is contained in a bottle provided with a thermometer ground into its neck. In the liquid is immersed a coil of platinum wire of known resistance, through which is passed a known current. The liquid, which has first been heated to its boiling point by an external bath, immediately boils, and the amount of liquid evaporated by the known amount of electricity is determined by weighing before and after. This gives all the necessary data.As, however, with mixed liquids the boiling point rises as the evaporation proceeds, a correction must be made for heat used in raising the temperature of the liquid. This is determined in a second experiment by determining the heat capacity of the liquid with the containing vessel. Measurements have been made for three cases of normal mixtures. The latent heat cannot be regarded as a linear function of the composition of the mixture, but depends also on the composition of the vapsur. 214. ‘‘ isoQuinoline derivatives. Part VI. neooxyberberine.” By Frank Lee Pyman. (Trans., 1911, 1690.) Berberiaeacetone, C23H230,N,yields on oxidation with perman‘ ga.nate in aqueous acetone neoozyberber~neace~one, C,H,O,N (I).When this substance is hydrolysed by dilute acids, salts of neoozyOerberi.ne, C201r1,70,N(11),are obtained : (1-1 (11.1 The phenolbetaine constitution assigned to rreooxyberberine is supported by its general properties, anci particularly by itis behaviour with methyl iodide, when rnethoxyberb erz’nium iodide is produced. neoOxyberberine is readily reduced to tetrahydrober- c2 216 berine, and its chloroform solution suffers spontaneous oxidation in the air, with formation of l-keto-6 :7-methylenedioxytetrahydroiso-quinoline and 1-ethyl hydrogen hemipinate. 215. ‘‘The system : palmitic acid-sodium palmitate.” By Frederick George Donnan and Albert Simpson White. (Trans., 1911, 1868.) The compositions of the solid and liquid phases in equilibrium with each other have been determined over the temperaturerange 60-82O.The solid phases consist of three series of solid solutions. No pure acid salts appear to separate as stable phases in the region of temperature and concentration investigated. 216. The P-chlorocinnamic acids.” By ThomasCampbell James. (Trans., 1911, 1620.) The various methods for the preparation of the two 0-chloro-cinnamic acids have been examined, and the proportion of the isomerides obtained in each case determined. A quantitative separation is possible by means of the barium salts in aqueous solution ;the, do-acid is readily, and the other sparingly, soluble. The transformation of the acid melting at 132’5O into that melting at 142O under the infiuence of heat and of sunlight, and the rate of elimination of hydrogen chlcrride by means of alkali, establishes the acid melting at 132.5O as the allo-isomeride.217. (‘Substances related to cochenillic and carminic acids. Part I. Synthesis of the methyl ether of p-and of y-coccinic acids.” ByAndrew Norman Meldrum. (Trans., 1911,1712.) Starting with 5-hydroxy-m-toluic acid (I), the author haa synthesised two methoxyphthalic acids which are related to cochenillic acid (IV). One of them is the methyl ether (1118) of 6-cocciaic acid (11 @), whilst the other is the methyl ether (111 7) of an unknown substance (I1y), which may be called y-coccinic acid. cop CO,H /\Me(\CO,H ,11e/)0O2H Mel \i \/ \/OH OH OMe (I1 B.) 217 218.(6 The synthesis of hydrocarbons at high temperatures.” By John Norman Pring and Dorian Macefield Fairlie. (Trans., 1911, 1796.) A method has been applied for the detection of the synthesis of traces of hydrocarbons produced when pure carbon, in the form of a rod, is heated electrically in an atmosphere of hydrogen. At 12000, and at pressures from 10 to 60 cm., carbon combines with hydrogen to give methane and ethylene, the rate of formation of the latter being about ljl00 that of the methane. No acetylene could be detected by this method at this temperature (1200°). Measurements made of the rate at which acetylene and ethylene react with hydrogen to give methane show that sufficient time was not allowed in the above experiments for any large interaction of ethylene or acetylene with hydrogen to occur, so that the formation of the hydrocarbons must have been direct.At 1400°, and at pressures between 10 and 40 cm., methane and acetylene are obtained, the rate of formation of the latter being about 1/10 that of the former. At 1650° methane, ethylene, and acetylene are obtained, and, as at higher temperatures, the quantity of ethylene is about twice that of the acetylene. Palla,dium, in contact with the carbon, was found to assist cata- lytically the formation of methane to the same degree as platinum, whilst silicon had no appreciable effect. The presence of a highly charged electric field surrounding the carbon made no appreciable difference to the rate of formation of methane at temperatures between 1200O and 1600°, so that no complication is produced in the reaction by ionisation from heated carbon.The formation of ethylene, which has not before been observed at these low temperatures, can just be detected by the special method employed for the analysis, at 1200°, and at 1400O it is comparable with the methane formed. 219. 2 :2-Di-bromodiphenyl and 2 :2’-dichlorodiphenyl.” By James Johnston Dobbie, John Jacob Fox, and Arthur Josiah Hoffmeister aauge. (Trans., 1911, 161 5.) The authors have studied the action of cuprous bromide on the tetrazonium salt derived from 2 :2?-diaminodiphenyI. They show that, according to the conditions, the products are, on the one hand, mainly diphenyleneazone, (C,H,N),, and carbazole, and, on the other, a small amount of 2 :2’-clibromodip?~e?~~Z,large quantities of carbazole, and traces of diphenyleneazone.218 2 :2/-Dibromodiphenyl crystallises from alcohol in long, colourless prisms, melting at 81O. Diphenylene is formed by the action of sodium on the substance dissolved in dry ether (Tmns., 1911, 99, 683). Fluorene results from the action of sodium on a mixture of 2 :2/-dibromodiphenyl and methylene dibromide. 2 :2’-DichZorodiphenyZ, formed similarly to the dibromo-compound, crystallises from light petroleum in nodular masses of crystals, melting at 590. 220. “The absorption spectra of various chlorine and bromine derivatives of benzene and of toluene as vapours, in solution, and in thin films.” By John Edward Purvis.(Traiiu., 1911, 1699.) The general results are that : (1) each vapour possesses a consider-able number of bands which can be divided into groups, regulated by the type and number of the side-chains; (2) alcoholic solutions of the substances give considerably fewer bands, and of a different type from the vapour bands; and (3) the bands observed through very thin films are not unlike t,he solution bands, and differ only in position. 221. “The effect of heat on a mixture of benzaldehydecyanohydrin and aniline.” By Arthur Ernest Everest and Hamilton McCombie. (Trans., 1911, 1762.) The following substances were found to be produced in this reaction : (1) After half an hour’s heating a, quantitative yield of anilino-phenylacetonitrile, CN-CJJPh-NHPh, is obtained.This substance has not been prepared previously without the use of either a sealed tube or a, catalyst. (2) If the heating is continued for forty-eight to ninety-six hours, ~ibenzoyldiunilinostilbene(I) is formed : gPh*NPhBz flPh.NPh>CPhCPh NPhBz CPh--N (1.) (11.) (3) Mixed with compound (I)was generally 1:2 :4 :5-tetraphenyl-glyoxaline (II). These two compounds were separated by taking advantage of the insolubility of the former in hot ether. (4) a-Keto-/3-anilino-&diphenyIethane was sometimes isolated in the reaction. (5) Benzanilide was also found to be present. Diberzoyldianilinostilbene can be decomposed quantitatively by potassium hydroxide, yielding the monobenzo~71 compound and benzoic acid.219 The constitution of these two compounds (the dibenzoyl and the monobenzoyl) was established by the decompositions undergone by m,onobenzo~ldianili.nostilhe.ne(a) in solution, (b) on heating. A solution of benzoyldianilinostilbene undergoes atmospheric oxidation, yielding benzanilide and dibenzoylaniline : $Ph*NPhBz + 0, ---+ COPh*NPhBz + COYh*NHPh.CPhoNHPh Benzoyldianilinostilbene when heated undergoes decomposition, regenerating the dibenzoyl compound, and forming benzanilide and benzildianil in addition : fiPh*NPhBz SPh-NYhBz CPh*NHPh CPh*NPhBz 2COPh-NHPh fiPh*NHPh gPh*NHPh / RPh:NPh+ICPh*NPhBz -+ CPh*NHPh 71 CPh:NPh Benzoyldianilinostilbene is strong iy yellow, but a mlourless modi- fication has been prepared. By spectroscopic means it has been estabiished that the salts are derived from the colourless variety, and not from the yellow form.222. imino-compounds.ofThe formation and reactions 4'Part XVI. Reactions leading to the formation of tricarballylic acid." ByFerdinand Bernard Thole and Jocelyn Field Thorpe. (Trans., 1911, 1684.) Cyaneamides having the nitrile group in the y-position readily pass into imino-derivatives of the five-membered ring; thus the condensation of iodoacetonitrile and the sodium compound of cganoacstamide gives the imino-compound (I), from which the imide (11) can be produced by the actdon of acids, and ultimately tricarballylic acid (111) : CN*y(CH,*CN)*CO*yH CN *~(CH,*CN)*CO*~H CH,---C:NH CH,---co (1.1 (11.)CO,H*$!H*CH,-CO,H CH,*CO,H (111.) The imino-compound (IV) is produced when the sodium compound of ethyl cyanoacet'ate is condensed with iodoacetamide. It yields the imide (V) when treated with acids, and tricarballylic acid on further hydrolysis : 220 There is no tendency to form either the three- or the four-carbon ring through the agency of the imino-group. 223.6L Composition of the essential oil of Myrica Qale, L.” By Samuel Shrowder Pickles. (Trans., 1911,1764.) The oil of Npricn Gale, L. (bog myrtle, sweet gale, etc.) required for this investigation was distilled from specimens of the plant collected in Argyllshire. Two separate consignments of hhe raw material contained different proportions of leaves and twigs, and the oils obtained in the two cases consequently varied somewhat in character.The oil obtained from a sample consisting mostly of leaves was pale yellow. It had a pleasant, herb-like odour, and possessed the following chemical and physical characters : Yield of oil on air-dried material, 0-203 per cent.; Di! 0.912; a, -11O26’; acid valus=4-0 ;total saponification value =23.2 ;ester value =19.2;saponification value of acetylated oil =56.4. The constituents of the oil were found to include the following substances : (1) a crystalline paraffin hydrocarbon, m. p. 63-64O, having probably the composition C,,H,, (0.75 per cent.); (2) free palmitic acid (2.5 per cent.) ; (3) terpenes, including dipentene ; (4) cineole; (5) esters of fatty acids; (6) a mixture of alcohols of high boiling points; and (7) a, sesquiterpene.Ths cineole and terpenes together constitute approximately 50 per cent. of the oil. 224. Trimercuridieth ylammonium nitrite .’’ By Prafulla Chandra Ray and Jitendra Nath Rakshit. By the interaction of ethyla<mine and mercuric nitrite, both dimercuriammoi~ium nitrite and trimercuridiethylammonium nitrite are obtained; a large excess of ethylamine favours the formation of the latter. This new compound is of interest as being the alkyl- substAuted product of mercuriammonium nitrite. 225. “The chlorine derivatives of pyridine. Part XI. Some interactions of 3 :4 :5-trichloropicolinic acid and of its deriv- atives.” By William James Sell.(Trans., 1911, 1679.) One of the chief compounds obtained by the chlorination of a-picoline has the constitution represent,ed by the formula : 221 This substance has been shown to produce by the action of sulphuric acid-besides 3 :4 :5-trichloropicolinic acid and 3 :4:5-tri-chloropyridine already described-a small qu mtity of another substance, most probably 4 :5-~~ci~Eo~~o-3-hy~t~~~~~~colinicacid. This substance is resolved by heat into the corresponding dichloro-i~ydroz~y/iyi,idiiic.The above hexachloropicoline also reacts with alcoholic sodium hydroxide, and yields 3 :5-dicIdo~o-4-h~droxypico-Zirzic ucid, also resolved by heat into the corresponding dichloro-hydroxyppridine, isomeric with the above dichlorohydroxypyridine. It is also shown that 3 : 4: 5-trichloropicolinic acid yields, when heated with ammonia at 140°, 3 :5-~ichZo~o-4-aminop~colinicacid, whkh, when heated, gives 3 :S-dzchloro-4-aminopyridine.Further, the last-mentioned compound forms, when the amino- group is replaced by the hydroxyl group, the same dichlorohydroxy- pyridine as is obtained by the action of alcoholic sodium hydroxide on the original hexachloropicoline and heating the dichlorohydroxy- picolinic acid thus produced. 226. An application of Kirchhoff‘s equation to solutions. (A contribution to the thermodynamic theory of solubility.) ’I ByRobert Taylor Hardman and James Riddick Partington. (Trans., 1911, 1769.) It is shown that a general differential equation of van’t Hoff may be integrated by an application of a theorem of Kirchhoff relating to the influence of temperature on heat of reaction.The resulting equation gives the solubility of a substance in terms of the absolute temperature and three constants : logs=A-3 T-ClogT, and is shown to agree very closely with the results of experiment. 227. ‘(The aerial oxidation (rusting) of metals.” By Wyndham Rowland Dunstan and John Richard Hill. (Trans., 1911, 1835.) In continuation of previous work, the authors have investigated the cause of the inhibiting effect of certain substances, for example, alkalis, potassium dichromate, etc., on the rusting of iron and other metals. It has been found that this effect is in all cmes the result of the establishment of a passive ” condition of the metal, during the continuance of which the inetal does not rust.The effect persisk long after the metal has been removed from the inhibiting solution a.nd carefully washed with water. Contact of passive iron with certain salts or dilute acids, including carbonic acid, more or less rapidly destroys the passivity, and rusting ensues. The authors D 222 point out that many of the results recently quoted in support of the caxbonic acid theory of rusting are invalidated by the facts now recorded, and further evidenct: is produced in favour of the cm-clusion maintained in previous pa,pers, that, t lie presence of carbonic acid is not essential to the rusting process. The authors record the results of experiments showing that the electrolytic theory of rusting cannot be maintained.It is also shown that other metals besides iron exhibit the phenomena of rusting, and are also capable of assuming the passive state. 228. “The passivity of iron and certain other metals.” By Wyndham Bowland Dunstan and John Richard Hill. (Trans., 1911, 1853.) The authors find that the passive state of iron is induced by solutions, in many cases by dilute solutions of a number of salts, such as potassium dichromate, chromate, iodate, chlorate, ferro-cyanide, and also by alkalis and alkaline salts, and that, besides iron and metals of the iron group, other metals, including mag-nesium, lead, zinc, and copper, are also capable of assuming the passive state under the same conditions. Passivity is destroyed more or less rapidly by contact with solutions of certain salts, such as sodium chloride, and also dilute acids, including carbonic acid.It can also be removed by scratching or brushing the surface of the passive metal, as well as by other mechanical means. The destructJon oE passivity by sodium chloride solution does not ta.ke place unless oxygen is present, and the effect is electrolytic, resulting in a slight electrolysis of the salt. In the absence of air, it is found that passivity is not destroyed by sodium chloride or by certain other salts. The evidence obtained points strongly to the conclusion that passivity is the result of the formation of a film on the surface of the metal.The results of experiments show that this film probably does not consist of “physically” altered metal or of a gas film. The passivity of iron is destroyed by heating in a vacuum to 400°, and disappears when passive iron is heated in hydrogen to 24O--25OG, at which temperature it is known that magnetic oxide of iron is reducible by hydrogen. The observed facts point to the conclusion that ‘‘passivity ” is probably the result of the formation of a sdid film of oxide on the surface of the metal. It has not, however, been hitherto recognised that certain metals, and especially iron, are capable of oxidation through cold dilute alkaline solutions. 223 220. “The reactivity of ketones towards iodine and the relative rates of tautomeric change.Part 11.” Ry Harry Medforth Dawson and Harry Ark. (Trans., 1911, 1740.) Further measurements have been made of the rate of tautomeric change of dialkyl ketones and substituted acetophenones. The experiments were made in 40 per cent. alcoholic solution with 0.1 molar sulphuric acid as catalyst, and iodine as speed indicator. The rate of change of the symmetrical dialkyl ketones diminishes with increase in the number of carbon atoms in the alkyl group. The data for methyl prop91 and methyl isopropyl, methyl butyl and methyl isobutyl ketones, show that substitution of the normal by the isoalkyl group reduces the reactivity of the ketone by about 25 per cent. The reactivity of methyl tert.-butyl ketone, in which the butyl group represents an inactive radicle, is only about twe fifths as great as that of the corresponding normal ketone.Sub-stitution of a hydrogen afmn of the phenyl group in acetophenone by a negative atom or group leads to a reduction in the rate of tautcmeric change, and similar substitution of one of the hydrogen atoms of the methyl group appears to prevent the change from taking place. 230. ‘‘The photochemical and thermal interaction of chlorine and carbon monoxide.” By David Leonard Chapman and Frank Houghton Gee. (Trans., 1911, 1726.) The authars have continued the inveatigation of the inhibition observed in photochemical changes when certain impurities are, present in very small amounts. The substances which hinder the photochemical interaction of carbon monoxide and chlorine are those which act as inhibitors towards the action of chlorine on hydrogen under the influence of light.The effect of oxygen on the former change has been investigated quantitatively. The thermal union of chlorine and carbon monoxide is homogeneous in character under the conditions prevailing in the experiments per- formed, that is, when the action proceeds in glass vessels and the area of glass is not extremely large in comparison with the size of the vessel in which the change takes place. The most important conclusion drawn from the results is that the afore-mentioned inhibition is limited to the photochemical change : the inhibitors in question have no influence on the thermal change. This fact was established by measurements being made of the rate of union of chlorine and carbon monoxide in the light and in the dark, at a temperature of 315O, both in the presence and in the absence of D2 nitrosyl chloride.When nitrosyl chloride was present, the rate of union was the same in the dark as in the light; but when it was absent, the rate of union in the light was the greater, the rate of union in the dark being the same as that observed when nitrosyl chloride had been admitted to the mixture. 231. “Decomposition of dry ozone.’’ By David Leonard Chapman and Herbert Edwin Jones. (Trans., 1911, 1811.) Ozone desiccated by long exposure to phosphoric oxide, and ozone dried by contact with concentrated sulphuric acid, decompose at the same rate under the same conditions.From this result, and from the results obtained in a previous research by the same authors (Trans., 1910, 97, 2463)) the inference is drawn that ozone can revert to oxygen without the intervention of any other substance. 232. “The absorption spectra of the isomeric hydrazones and semicarbazones of camphorquinone.” By Frederick Russell Lankshear and Arthur Lapworth. (Trans., 1911, 1785.) The spectra fall into two sets, suggesting a classification of the compounds into two series which are identica.1 with the a-and @-series into which they were grouped by Forster and Zimmerli (Tyans., 1910, 97, 2156; 1911, 99, 4’78). The points of difference between the two classes are not sufficiently marked appreciably to weaken the case in favour of the view that the relationship is stereochemical.233. ‘‘Bimolecular glycollaldehyde.” By Nial Patrick McCleland. {Trans,, 1911, 1827,) Thc author has investigated the behaviour of bimo3ecular glycollaldehyde in different solvents and in the state of vapour to ascertain whether it is a kind of acetal formed from two molecules, the hydroxyl group OC the one reacting with the aldehyde group of the other and vice versa, or whether the phenomenon is due to molecular association of an unusually intense kind. The conclusion is drawn that the latter is the case, and with the aid of the absorption spectrum of the bimolecular solution it is found possible to make a suggestion as to the character of association in geaeral.225 234. ‘(Myricetin. Part 111.” By Arthur George Perkin. (Trans., 1911, 1721.) Myricetin hexurnethyl ethey, C,,H,02(0Me),, which occurs in colourless, prismatic needles, melting at 154--156O, is readily pre- pared by the action of methyl sulphate on ths potassium salt of myricetin pentamethyl ether (compare Waliaschko, A P~L.Pharm., 1904, 242, 242), or by methylating myricetin with alkali and methyl sulphate. When hydrolysed with alcoholic potassium hydroxide, it gives gallic acid trimethyl ether and Z-hydroxy-fisetol trimethyl ether : OH MeO/-\C\-/ 0-CH 0Me, OMe identical with that obtained by Herzig from quercetin pentamethyl ether (Ber., 1909, 42, 158). Myricetin hexaethyl ether (Trims., 1902, 81,206) behaves similarly, with production of gallic acid triethyl ether and 2-hydroxyfiaetot triethyl ether, which forms prismatic needles, melting at 96--97O.These results confirm the hydroxy-quercetin constitution previously assigned to myricetin. 235. The influence of inactive electrolytes on the optical activity ‘I of Z-malic acid in aqueous solution.” By Clifford Morgan Stubbs. The addition to an optically active solution of various salts and acids which themsdves are inactive and do not chemically combine with the active solute, provides a method of varying the solvent in a simple and more or less understood manner. Malic acid was selected as being a well-studied active substance, particularly sensi- tive to changes in the solvent. For comparative purposes a solution of malic acid of constant strength (20 per cent.) was used, to which the various anhydrous salts and acids were added in certain equiva- lent proportions, and their effect on the specific rotation, mainly for sodium light, determined.The influences observed were, in general, considerable, those for barium and calcium salts being extraordin- arily large, and showed the existence of simple relztions between the influence of the salt and its chemical nature. The main conclusions are : (1) The influence of sa.lts is not due to their affinity for water. (2) The influence is mainly a property of the radicles or ions; for salts of strong bases it is an additive ionic property. (3) The property is not due to chemical reaction or adjustment of ionic equilibrium.Ions within the sphere of influence of an active molecule appear to possess the specific power of affecting its degree of asymmetry to an extent depending mainly on their con- centration, and not on that of the malic acid. No connexion has been found between this power and any known physical properties of the solvent due to the dissolved electrolyte. (4) The divergencies of the alkaline maslates (according to Schneider’s da.taj from obeying Oudernan’s law appear explicable on the ground of the continued influence of the dissociated, but necessarily adjacent, metal ion. (5) Thomsen’s supposed complex-formation between sodium malate and excess of alkali seems explicable on the ground of ionic influence. 236.“New derivatives of diphenoquinone and a new variety of stereoisomerism’’ By James Moir. By oxidising 4:4/-dihydroxy-3:3I-ditolyl in various ways, ditolu- quinone has been obtained apparently in two stereoisomeric forms, namely, a 3 :3/-c.r cis-form (red) and a 3 :5’-or trans-form (yellow). Both modifications give an orange-brown coloration with sulphuric acid, and are quantitatively reduced by stannous chloride to 4 :4’-dihydroxy-3 :3/-ditolyl. On mild oxidation, dihydroxyditolyl gives ditolupuinhydrone, which forms black needles with a green reflex, and gives a blue coloration with sulphuric acid; the sodium derivative is a bluish-purple jelly. Ditoluqui?ioizedi-imine results by oxidising tolidine by Willstatter’s method, and is similar to his ‘‘ diphenquinonedi-imine,” but the properties of both are anomalous, and they are probably poIymerides of the true di-imines.The nitrate o€ the true ditolupuinhydronedi-imine is easily obtained from tolidine nitrate and ferric nitrate in a-queous solution ; it forms opaque, blue needles with a bronze lustre, and is hydrolysed by water, the blue solution depositing the basic nitrate as a bright blue jelly with a coppery lustre, which can be prepaTFd directly by the action of the theoretical amount of chromium trioxide on tolidine nitrate. When excess of potassium dichromate is used instead, the dichromate of ditoluquinhgdronedi-imine (~14H14N2+C14%K2 + H2Cr207)is obtained; this is the tetramethyl derivative of the secalled (‘beiizidine chromate,” which has recently been shown to be diphenoquinhydronedi-imine dichromate. Dibromodifoluquinone has been isolated in two modifications by oxidising 5 :5I-dibrorne4 :4’-dihydroxy-3 :3I-ditolyl; it forms scarlet needles with a faint green lustre, and paler lozenges.It gives a 227 scarlet coloration with sulphuric acid, becoming magenta on dilution. Like the parent substance, it is practically unaffected by sodium hydroxide. The corresponding puinhydrone (Cl,HlOO,Br2 + C,*H,,O,Br,)is obtained by reducing the quinone with bisulphite, or directly from dibromodihydroxyditolyl by oxidation with ferric chloride in dilute alcohol, or with bromine in acetic acid. It forms needles like graphite, giving a blue coloration in sulphuric acid; the sodium derivative is bright blue, and easily decomposed.The following new substances are described : 5 :5'-dibromo-4 :41-dibenzoylosy-3 :3'-ditolyl, m. p. 23g3 ; the 4:4f-diacetoxy-compound, m. p. 198O; 5-bromo-6-i~ydroxy-m-toZuicacid, m. p. 233O; 3-bromo-3/-nitro-4 :4'-dihydroxy-3 ; 3I-ditoZyZ; 5 : 51 -dinitro-4 :4I-dihydroxy-3 ; 3f-ditoZyZ; and barium 4:4'-dihydroxy-3 :3/-dito~ldiszcl~ho?ate. Thursday, October 19th, 1911, at 8.30 p.m., Professor PERCYF. FRANKLAND,LL.D., F.R.S., President, in the Chair. The PRESIDENTreferred to the loss sustained by the Society, through death, of the following Honorary and Foreign Members : Elected. Died. Prof. Albert Ladenburg Feb. 2nd, 1888 Aug.15th. Prof. Walthere Spring Jan. 2Oth, 1898 July 17th. Prof. Louis Joseph Troost ,, ,, ,, * Sept. 30th. It was announced that the Bcrthelot Memorial Lecture would be delivered by Professor Harold B. Dixon, F.R.S., on Thursday, November 23rd, 1911, at 8.30 p.m. Messrs. Irvine Masson, Edwin B. Hughes, H. Horace Ward, and L. 8. Newton were formally admitted Fellows of the Society. Certiiicates were read for the first time in favour of Messrs. : Arthur Cecil Bescoby, B.A., Guestling, Hastings. Bertram AIfred Bull, Government Road, Nairobi, British E. Africa. Joseph Beauchamp Bull, Bulawayo, S. Africa. Edwin Johnson Charlton, M.Sc., Morannedd, Beaumaris, North Wales. Barun Chandra Dutt, M.A., Rambogan Cottage, Rambogan, Calcutta.Arthur Josiah Hoffmeister Gauge, 2, Ashford Avenue, Hornsey, K. Sydney Hall, B.Sc., Birley House, Station Road, March. Cyril Vincent Hodgson, SO, Apedale Road, Chesterton. Henry ,James Hodsman, M.Sc., 2, Itiehmond Hill, Langley, Birmingham. Alexander Frederick Hogg, hf .A., 81, Clayemout Road, Forest Gate, E. Robert Mills, I’la~itation Uitolugt W.C., Demerara, British Guiana. €3. Wiswa Nath, 46, Nagappa Modali Street, Komaleswarapet, Madras, India. Thomas Peers Parkes, B.Sc., 22, Dalrymple Road, Brockley, S.E. David Henry Peacock, B.A., R.Sc., 40, Huddart Street, Bow, E. B. Venkaka Rao, E.A., Bangalore, Mysore, India. Joseph Reilly, B.A., 25, South Circular Road, Portobello, Dublin. Noel Douglas Ridsdale, Ravenscroft, Roman Road, Middles-Ibr oug h .William Bristow Saville, 117, Vassal1 Road, Brixton, S.W. Bernard Charlie Smith, 62, Filey Avenue, Upper Clapton, N.E. John Henry Smith, 10, Radnor Street, Swindon. Kapibram H. Vakil, B.A., R.Sc.Tech., No. 5, Santa Cruz, Bombay, India. Harry James Vipond, B.R., Dept. of Agriculture, Pretoria, S. Africa. Ernest Walter Wright, C‘oniiaught Club, Seymour Street, W. Of the folloving papers, those marked * were read: *237. ‘‘ The alkaline condensations of nitrohydrazo-compounds.” By Arthur George Green and Ernest Arthur Bearder. The authors have studied the action of aqueous alkali hydroxides on 4 :4 -dinitrohydrazobenzene, and have ascertained that condens& tions occur analogous to those which give rise to the stilbene dyestuffs.A close parallelism is thus indicated between the nitroazo- and the nitrmtilbene series. The blue colour produced when 4:4 -dinitrohydrazobenzene is dissolved iii cold alkali hydroxides is apparently due to the formation qf the quinonoid salt: (M/O)NO:C,Ti, C,H,: NO(OM’) , since the original compound is reprecipitated unchanged when the 229 freshly prepared solution is acidified. When, however, the solution is kept at the ordinary temperature for several hours, a slow change of colour from pure blue to violet-blue occurs, with simultaneous precipitation of dinitroambenzene. The solution after removal of the latter then gives on acidification 4-nit7.oso-4/-nit7.o~~~~~uz~-benzene, I~O~C,€I,~hTI-I~NPI.C,H,*NO,,which crystallises from acetone in small, orange-red cubes having a violet reflex, and decom- poses without melting sharply at about 203O. Its alkali salts are violet-blue.It is rather unstable, and when boiled with neutral solvents or with aqueous alkali hydroxides undergoes further condensation according to the scheme: i H...................... .......................... q ;o H Hi ............................. .................. N! ),.CGH,;N*N~UGH,-~-+ t-N*CGH,*N*N*C,H,*N02 giving bisnitrobenzeneazo-azohene. The latt’er can also be obtaiiied without prior isolation of the intermediate, nitroso-deriv- ative by heating the alkaline solution of dinitrohydrazobenzene for some time at 100° until the disappearance of the blue colour.It forms small, orange-red needles, is very sparingly soluble in solvents, and nielts at 285-286O. +238. ‘I The characteristics and chemical composition of some early matches.” By Edwy Godwin Clayton. A description was given, and specimens were shown, of the Promethean match (date 1828), one of the numerous forms of (I chemical matches ” (ignited by the contact of sulphuric acid with a chlorate mixture) which preceded the non-phosphoric (( friction-ligbts,” invented in 1826-1827 by John Walker, and ignitable when drawn through folded sand paper. Some of the non-phosphoric ‘(lucifer matches,” which were soon afterwards manufactured in many quarters on the same principle as Walker’s matches, but were usually sulphur-coated (Walker’s were not, although the opposite is sometimes stated to be the case), were also described, and speci- mens were exhibited.The author has fixed the identity of the first user of the designation “Lucifers.” It was Samuel Jones, who, having previously introduced the, Prometheans, next manufactured friction matches closely resembling Walker’s, and called them Jones’s Lucifers,” or (‘chlorate matches.” Analyses of Prome-theans, and of two varieties of lucifer matches, British and foreign, are summarised in table I. Many inaccurate statements have been made about the Promethean matches, especially in reference to 230 the composition of tha igniting mixture, and the character of the glass vessel containing the acid. The last-name.d differs widely from that which most of the published descriptions would lead the reader to expect.TABLEI. CIasa : Chemical Matches. Class : Lucifer Matches. h --. * -I /-No. 2. No. 1. French Promethean Eng Zish Matches Matches. ' L'IccifEr (Lucifer$).Maker, Matches." Maker's S. Jones. The same, Maker, n ame Date, 1828. Liquid 3. Bell & Co unknown. Igniting in minute Date, Date,:omposition. glass tube. * 1832-33. 1832-33. Sulphur ................. 24.7 --Antimony sulphide .. --Lycopodium ............ 8.8 Potassium chlorate .. 34.9 -Ferric oxide ........... --Gnm........................ 31'6 -Sulphuric acid (H,SO,: -61'9 Wates ................... -38-1 Iudigo ..................... -(minute quantity: 100.0 100.0 100.0 * Tube about 7 nim.long and 1 mm. wide. Early in the 'thirties were introduced "Congreve " matches, which differed from lucifers in that they contained phosphorus, and were ignitable by being " struck upon the box." Congreves, which mere proljably so, named after the inventor of the war rocket, Sir W. Congreve, Bt., then recently deceased, were largely manufactured on the Continent, especially in Germany and Austria. They varied greatly in quality and appearance, although not much in composition. In table I1 are given the results of analyses of six kinds of Congreves. Some curious " Cigarren Ziinder " (phosphoric, and ignitable by friction), made about 1850 by a Viennese manu- facturer, aid Austrian matches of later date (included in table II), were also described.TABLE11. Class :Congreve Matches. KO. 5. No. 2.* No. 4. Germnn Gcrrnan German Matches. Matches . Matches. Labelled : ‘lass: On the label : No. 3. Labelled : ‘‘Superior lnss : Cigar ‘These matchch Qermnn ‘( Superior Congreve Uatcliea of Lighters. No. 1. invented and Matches. Congreves matches Enter date. Bermaii (2) improved by,, Chemische from one of from one of No. 9. Matches. Congreve ... S treich-;he greatest the greatest No. i. No. 8. A iutrian Labelled : Plso an illustra- feuerzeuge. ’’ and most and most Aiistriun Auslrian Cigar “Best tion of a hand Maker, famous famous Matches. Matches. London Con. striking n H. Link, German German Ini tialil, Maker and ‘Lighters.D’Bleaml’n ;reves.” No natch.Matches of manufac-manufrrc-No. 6. ( B.F. in S. date Cigarren maker’s packed in Dsrmstadt tories. ” torics.” Rubbing (Bernard unknoiv n . Ziinder. ” name. bran ... (Period, Maker’s Maker’s com-Fiirth of (Period B J aker, (Period, daker’s initials probably initials initials pnsition Schiit ten- probably , N. Pollak, between “J .C. K.” earlier “I.N.E.” *‘I.N.E.’’ on the hofen ?) later than Vienna. c.3 1838 and (Supposed date than (Period, (Period, boxes of (Period, any of the (Date, 03 1840.) c. 1835.) 1-840.) 1840-50.) 1840-50.) No. 5. 1845-50.) preceding.) c. 1850.) + Ordinary phosphoriis 10.5 20’5 13-0 6’9 7.7 5‘5 7.1 3.2 10.2Sulphur .................. 12’7 14.3 9.0 20’4 6-7 54.8 20’0Potassium chlorate ... 43-3 32 -1 60.7 39.0 38 ‘8 -----1 1‘4Potassium nitrate ......-Glass (pulverised) .... -----14 -9 -2.6 -Sand ..................... -----Chalk or whitening .. 12.5 8*o ---6.3 Ferric oxide .......... -----11.8 -Gum ..................... 21 --0 ----36 *5 -Dextrin, e tc. .......... 25.1 17-3 ---Starch .................... -(Wheat starch Much starch -present) Glue.. ...................... ---33.7 25.6 -35.9 -Dye ..................... (Traces) (Minute (Blue dye) -(Prussian ? quantity of a blue)blue dye) 1oo*o 100‘0 100-0 100.0 100.0 100.0 100-0 100.0 100’0 * These were probably among the phosphoric friction matches earliest sold in his country. 4' "239. 232 Experiments on the Walden inversion. Part VII. Action of phosphorus pentachloride and of thionyl chloride on optically active hydroxy-acids and esters." By Alex.McKenzie and Frtd Barrow. The authors bave examined the action of thionyl chloride on I-mandelic acid, methyl I-mandelate, ethyl I-mandelate, I-malic acid, ethyl I-malat e, ethyl d-t ar tr a te, I-a-h y droxy-8-phen y lprop ion ic acid and its ethyl ester, and d-and I-/3-hydroxy-P-phenylpropionic acids. The act'ion of phosphorus pentachloride has been examined in the case of d- and I-a-hydroxy-p-phenylpropionicacids and their ethyl esters, and also in the case of d-8-hydroxy-P-phenylpropionicacid. The behaviour of t>he latter acid and its I-isomeride towards hydrochloric acid has also been studied. DISCUSSION. The PRESIDENTasked Dr.McKenzie whether he had observed any differences in the amount of racemisation occurring according as phosphorus pentachloride or thionyl chloride respectiveIy were employed, and also according as the free acid or an ester respectively were acted on by these reagents. In reply to the President, Dr. MCKENZIEstated that a TValden inversion is accompanied in the great majority of cases by racemisa- tion, which is often very pronounced. 'When the action of phos-phorus pentachloride and of thionyl chloride towards any one hydroxy-acid (or its ester) is contrasted, it is found that the former has invariably a greater racemising influence than the latter ;thus, the crude dextrorota tory phenyIchIoroacetic acid obtained by the zction of phosphorus pentachloride on I-mandelic acid is optically active to a much less degree than the crude laevorotatory phenyl- chloroacetic acid obtained by the action of thionyl chloride on I-mandelic acid.A similar effect was noted in the behaviour of I-atrolactinic acid towards phosphorus pentachloride and thionyl chloride respectively (McKenzie and Clough), and there are numerous other instances of the same kind. In reply to Dr. Forster, it was stated that the method recently described by Darzens (Compt. rend., 1911, 152, 1601) of replacing the hydroxy-group by chlorine by the action of thionyl chloride on esters of hydroxy-acids in the presence of a tertiary base was not attempted by the authors. By the action of thionyl chloride on ethyl I-mslate studied by the authors, a satisfactory yield of ethyl d-chlorosuccinate with [a]: * +32-7O was readily obtained, whereas Darzens, carrying out the action in the presence of pyridine, found [a12 +31*Z0.233 *240. L4 Note on the preparation of the sp.-aldoximes.” By Albert Ernest Dunstan and Ferdinand Bernard Thole. The method for the preparation of benz-syn-aldoxime discovered by Beckmann (Ber., 1889, 22, 429, 1531) consists in saturating an ethereal solution of the anti-oxinie with dry hydrogen chloride and subsequently decomposing the precipitated hydrochloride with aqueous sodium carbonate. The authors have €ound that a much more simple and 2xpeditious preparation can be performed by suspending the finely powdered anti-oxime in cold concentrated hydrochloric acid, and leading in hydrogen chloride to saturation, when, in the case of benzaldoxime, ths hydrochloride passes into solution, and, in the case of piperon-aldoxime, tho salt is precipitated.On pouring the resulting solution or suspension into excess of aqueous sodium carbonate, a voluminous precipitate of the syn-modification appears, which can be collected, dried on porous earthenware, and crystallised f rclm benzene. Almost theoretical yields have been obtained in the cases of benzaldoxime, piperon- aldoxime, anisaldoxime, and m-nitrobenzaldoxime. “241. (‘The absorption spectra of the nitration products of dimethyl-p-toluidine.” By Gilbert T. Morgan and Arthur Clayton. 2-Nitrodimethyl-p-toluidine and 3-nitrodimethyl-p-toluidine ex-hibit absorption spectra quite comparable with those of the nitro- anilines and nit8rotoluidines, the absorption curves showing the broad, well-defined band which is characteristic of this series of bases.2 : 5-Dinitrociimethyl-p-toluidine, which contains its nitro-groups unsymmetrically arranged on either side of the dimethylamino-radicle, gives an absorption curve still showing the characteristic hand, but somewhat narrowed and modified. 2 : 6-Dinitrodimethyl-p-toluidine aad 3 : 5-dinitrodimethyl-pt~luidine,in each of which the two nitro-groups are in symmetrical positions with respect to the basic group, give absorption curva differing from the typical form, owing to the almost complete suppression of the absorption band.The substitution of a third nitro-group in the 2: 6-isomeride decreases the symmetry of the molecule, and the product, 2 :3 :6-tri-nitrodimethyl-pbluidine, again shows a well-defined absorption band. The least symmetrical base examined was 2 : 3-dinitromethyl-p-toluidine, which contains all its substituents in consecutive 234 positions. This substance gave tlie typical form of absorption curve with the most persistent band of the series. The observed difference between the absorption spectra of 3 : 6-and 3 : 5-dinitrotfimethyl-21-toluidinesand those of the other bases of this group is due, however, only in part to the symmetrical grouping of the nitro-groups; it is dependent, also, on t-he presence of the unsaturated basic radicle, for when the basicity is largely destroyed by the replacement of an N-methyl by a nitroso-group, similar spectra are exhibited, as, for example, with 3 : 5-dinitro-ptolylmethylnitrosoamine, 2 : 5 -dinitro-p-blylmethylnitrosoamine, and the corresponding 3-nitroarnine.242. “The action of Allium sativum or garlic-juice on lead and mercury.” By Manindranath Banerjee. When the juice of macerated garlic-crucifer= is triturated with highly impure mercury (containing lead) in a mortar for several hours, a pasty mass adheres to the sides of the mortar, and the mercury remains behind. On adding water tothe pasty mass, after removing the mercury, a greyish-black precipitate is formed, which, after being collected, dried in the air, and rendered free from minute particles of mercury, proves to be a mixture of lead sulphide (PbS) and a little mercuric sulphide (HgS).The mercury which has been removed, being partly free from lead and other impurities, is repeatedly subjected to the same treatment with garlic-juice, and after three or four hours’ rubbing, it is seen to be quite free from Isad, and shows all the qualities of pure mercury, when the garlic would no longer act on it. The sulphur present in the garlic acts on the lead to form lead sulphide (PUS). The higher sulphides present in the oil of garlic, such as diallyl disulphide, propyl dlyl disulphide, etc., are reduced to the lower ones, for example, diallyl disulphide is changed into diallyl sulphide or allyl sulphide; this oily liquid mixes with the lead sulphide to form a pasty mass.On adding water, the allyl sulphide and gummy matter present in garlic are dissolved, and lead sulphide is precipitated. The allyl sulphide is partly converted into allyl alcohol, hydrogen sulphide being evolved, which at once attacks the mercurous oxide always present in impure mercury, forming black mercurous sulphide (HgS+ Hg) and water, The lead and mercuric sulphides are separated from the mercury, which is thus obtained completely free from lead and mercurous oxide, and is found to be perfectly purified. It has been observed that garlic has no action on pure mercury, and its action on lead alone, even in the finest state of division, is extremely slow, whilst it readily attacks an amalgam of mercury and lead.In the case of diallyl disulphide the reaction may be represented thus : (C3H5)ZSz-+Pb =(C,H,),S -tYbS, (C3-HH,)2S+2H20 =2C3€E15*OH+H2S, H2S+Hg,O =Hg2S or (HgS +Hg) +H,O ; or, (C,H5),S2+Pb +Hg,O =2C3H5-OH+ (PbS +HgS) +H,O +Hg. 243. ‘‘Note on y-methoxysalicylaldehyde and its occurrence in the root of a species of Chlorocodon.” By Ernest Gonlding and Russell George Pelly. In a previous note (Proc., 1908, 24, 62) it was shown that the odorous constituent of the roots of Chlorocodorb sp., is the methyl ether of a dihydroxybenzaldehyde, ONeCGH3(OH)*C130, m. p. 41--42O, but that owing to the lack of sufficient material its configuration had not been established.A further quantity of the root was subsequently received at the Imperial Institute from Uganda, and was distilled with steam, the yield of the aldehyde amounting in this case to little more than 0.25 per cent., as compared with 0.5 per cent. from the earlier sample. When the compound was fused with potassium hydroxide it furnishcd either B-resorcylic acid or resorcinol, depending on the temperature at which the experiment was carried out, thus proving that the substance is pmethoxysalicylaldehyde, OM@*C6~3(OH)*CH’O[4:2 :11. This conclusion has already been reached by Friedlander (Momt~h.,1910, 30, 879j, who obtained the compound by the action of sodium hydroxide on 4-methoxybenzene-Z-indoleindigo (formed by the condensation of isatin chloride with resorcinol methyl ether).Friedliinder’s substance melted at 41°, and was identified with the compound from ChZorocodon roots by means of the oxime and phenylhydrszone described in the earlier paper (loc. cit.). When an alcoholic solution of the aldehyde (1 mol.) is warmed xith aniline (1 mol.), condensation readily takes place, with forma- tion of p-methoqsaZicylid eneaniline, 0Me* C6H3(OH) CH:NP h, which separates in long, narrow, Iustrous, yellow plates, and, after recrystallisation from alcohol, melts at 67-68O : 0.4410 gave 23.5 C.C. N, (moist) at 12’5O and 750 mm. N= 6.22. C,,H,302N requires N =6-17’ per cent. 236 244. “8. simple apparatus for sublimation in a vacuum.” By Harold Christopher, In the course of some recent researches on thioxanthones it was desired to purify these substances by sublimation in a vacuum.It was found, however, that, o*ing to the great density of the vapours, diffusion to the cold part of the sublimation tube was an exceedingly slow process. To overcome this difficulty the idea was conceived of drawing a current of air over the substance, and for this purpose the apparatus illustrated by the accompanying figure W;LS designed. Essentially it consists of a glass tube ABCD, of which the region ab contains the substance to be sublimed, and is heated in an oil-or metal-hahh, whilst the limb C, into which the vapours of the substance are carried by a current of air, serves as the cooling chamber. In order to prevent the sublimate which collects in the region de from falling back on the unsublimed substance, the tube 237 is constricted and bent, as shown at FHM, and to avoid condensa tion and consequent blocking at this part, the apparatus is immersed in the bath up to the level L.The current of air, which is regulated by means of a screw-dip compressing the indiarubber tube p, enters the a,pparatus through the glass tube mm,from which it issues by ths orifice n, and passes down the cylindrical space between the outer wall of the sealed and exhausted tube TS and the inner wall of the limb A of the sublimation tube. From here it passes over the substance to the condensing limb C, and thence through a filter, shorn in section at I, to the pump.This filter, which is of great importance, the outlet tubes invariably becoming choked if it is omitted, consists of a, piece of filter-paper held against the under- surface of a perforated porcelain disk. It rests on the end of the condensing limb, and is held in place by the hea.d D and the thick rubber band t. Should the tube rs be omitted, vortices are formed, and some of the vapour of the substance is carried to the cool part of the limb 4, where it condenses. It is not essential that this tube should be sealed at the junction with my but it is perhaps preferable, as any contamination of the inside would be very troublesome to remove. If it is sealed it is safer to exhaust it, at least as completely as is possible, with a water-jet pump, since, when in use, it is surrounded by an atmosphere at low pressure and high temperature.Some idea of the amount of air passing may be obtained by inserting a mercury bubbler between the apparatus and the pump. The substance to be sublimed is, of course, intre duced through the limb A, and the sublimate scraped out of the limb C, th3 head and filter being removed for the purpose. This device has proved of great utility in the researches alluded to above. The external diameter of the tube employed was five-eighths of an inch, and the total height about 7 inches. The working pressure was usually about 40 min. (internal), at which a quite suffi- ciently rapid stream of air wa drawn through by the water-jet pump used, whilst the temperature waa in the neighbourhood of 200O.245. (‘Note on the dehydration of crystals.’’ By James Brierley Firth. The removal of water of crystdlisation from various salts by means of calcium carbide has been described by Irvine Masson (Trms., 1910, 97, %l), wlio finds that in most cases complete dehydration call he obtained, the rapidity of dehydration depending on the vapour pressure of the hydrate. In the case of copper, zine, and ma.gnesium sulphates, the final stage is that of the monohydrate. The author has conducted a series of similar experiments, using phosphoric oxide, and it was found that the above sulphates could be rendered completely anhydrous. The extent of the dehydration was determined by taking the monohydrate, and in all three cases it was further dehydrated by phosphoric oxide.* It would appear, therefore, that the apparent stability of the monohydrate, when calcium carbide is used, must be due to the conditions under which the dehydration is carried out.The decomposition of calcium carbide results in the production of calcium hydroxide. Now it would appear that, if during dehydration any hydrate was formed which had a vapour pressure equal to, or lower than, that of calcium hydroxide, further dehydra- tion would not be possible. From the following t.able it will be seen that this is the case with copper, zinc, and magnesium sulphates. Vapour pressures at 25*.* CuSO,, 5-3H20 ...... 7 -0 rnm. MgS04,6-7H,0 ...... 11-5 inni. CuSO,,1-3H,O ......4.7 .. MgS04,5--6H,O ...... 9.8 !,CUSO~,O-~H,O ...... 0.8 .. (0.5) t. MgS04,4-5H,0 ...... 8.8 .. Z1lSO4,6-7H2O ...... 13.6 .. MgSO,,1-4H,O ...... 4'9 91 ZnS04,1-6H,0 ..... 12% ,, MgSO,,O-lH,O ...... 1.0 .. (0.5) t ZnS04,0-lH,0 ...... 1.0 .. (0.5) 1-CaO, H,O ............... 0.8 .. * Foote and Scholes, J. Amr. Chem. Sue., 1911, 33,1324. Muller-Erzbach, BET.,1881, 14, 1093, and Zeitsch. phy.7ik.d. CJLem., 1888, 2, 113. The vapour pressures of all three monohydrates are very low, and not known very accurately, but they are probably near to that of calcium hydroxide. In all other cases where the dehydration is complete, using calcium carbide, the vapour pressure of the lowest hydrate is higher than that of calcium hydroxide. The bse of phosphoric oxide involves the production of phosphoric acid, and hence secondary reactions frequently occur. In the case of barium cbloride the acid reacts with the anhydrous salt, giving a regular stream of hydrogen chloride.This seems to furnish a simple method of preparing fairly pure dry hydrogen chloride. It ma,y be easily done by mixing powdered crystals of barium chloride with phosphoric oxide in a test-tube. In a few minutes hydrogen chloride is evolved, the rate depending on the intimacy of the mixture. * It is well known that copper sulphate can be completely dehydrated at 50" by concentrated snlphuric acoid. 246. ‘‘The dip henylcarbamyloximes.” (Preliminary note.) By Frederick Percy Dnnn. The diphenylcarbamyloximes of benzaldehyde and the three nitrobenzaldehydes have been prepared by heating equivalent quantities of diphenylcarbamyl chloride and the sodium salts of the ‘‘anti ”-oximes in dry chloroform or ether.It was found that the sitme compound was obtained by condensing diphenylcarbamyl chloride with the sodium salt of benzontialdoxime as with that of benzsynaldoxime, either by heating or more slowly at the ordinary temperature. Treatment with alcoholic potassium hydroxide gave diphenylamine and benzonitrile, this result showing that the diphenylcarbamyloxime is a I‘syn ” derivative (compare Hantzsch, Uer., 1891, 24, 17): C,H,*CH C,H,-Ch-o~o~~-~(~,~5)2-+ N+CO, + HN(C,H&. The syn-~~~hen?/Zcarbcm~lox~~~eof benzaldehyde crystallises in colourlees, flat needles, decomposing at 163O (Maquenne block).The three diphenylcarbamyloximes of t.he nitrobenzaldehydes decompose about the same temperature, and all become yellow on exposure to light. *4s it was found. that the sodium salt prepared from o-nitro- benzsynaldoxime was mainly an (‘anti”-salt, the further investiga- tion of the diphenylcarbamyloximes has been postponed in order to study the metallic salts of the oximes. The author also hopes to prepare the carbamyloximes and the phenylcarbamyloximes. 247. (‘Some reactions of phenyl isopropyl ketone.” By Arthur Lapworth and Victor Steele. As isobutyryl chloride is difficult to obt’ain quite free from propionyl chloride, phenyl isopropyl ketone, prepared by the Friedel-Crafts’ reaction, is liable to be contaminated with phenyl ethyl ketone, which may be detected by the formation of @-ketonic esters when the ketone is treated with oxalic, formic, phthalic, and other esters in presence of sodium or sodium ethoxide; the pure ketone does not react at all with these esters.Phenyl iyopropyl ketoxime, which may be used in purifying the kctone, melts at 94O, and appears to exist in one form only, although previous observers have recorded 58O and G1° respectively as the melting pint of the compound. Whilst inert towards carboxylic esters, phenyl .isopropyl ketone is acted on by ainyl nitrite in the presence of alcoholic sodium ethoxide, yielding acetoxime, ethyl benzmte, and sodium benzoate, the latter doubtless being formed as the result of the presence of water in the alcohol used.248. ‘‘A new stereoisomeride of cyanodihydrocarvone.” By Arthur Lapworth and Victor Steele. d-Carvone unites with hydrogen cyanide in hot alcoholio solution and in the presence of potassium cyanide, yielding a product isomeric with the nitrils obtained at the ordinary temperature (Trans., 1906, 89,945 and 1819). It melts at 84O, and has [a]:: -42’1O in absolute alcohol; it shows mutarotation in presence of bases, but the equili- brium point attained corresponds with a rotatory power quite different from that reached by the cyanodihydrocarvone first discovered. As both compounds yield pure d-carvone on removal of hydroger cyanide, the existence of four isomeric nitriles derived from d-carvone is indicated by these facts, this number correspond- ing with that theoretically possible.249. ‘‘ The action of hydrogen cyanide on carvone hydrosulphide.” By Victor Steele. Many ketones which contain an ethylenic linking in the a/3-position do not form simple cyanohydrins, but first yield saturated 8-cy ano ketone s, which may subsequently be converted , by union with hydrogen cyanide, into hydroxydicyano-compounds. It was thought possible that in certain cases a cyanohydrin of the aP-hydrochloride might be prepared, from which, by hydrolysis and subsequent removal of the elements of hydrogen chloride, the required unsaturated hydroxy-acid might be obtained. As these operations were not found possible, an analogous series of reactions, involving the 1.180 of hydrogen sulphide instead of hydrogen chloride, was examined.The additive compound of hydrogen sulphide with carvone (Varrentrap, Handworterbuch d. Chemie, 4, 688 ; KekulB and Fleischer, Bw.,1873, 6, 1088) was mixed with one and a-half times its weight of alcohol and two molecular proportions of potassium cyanide dissolved in water, glacial acetic acid being subsequently added until the whole remained but slightly alkaline. To facilitate interaction, 30 C.C.of ether were then added, and the whole left in ;t corked flask four days at room temperature, when an equal bull^ of water was added, and the ethereal solution separated, washed, dried, and evaporated. The residue formed a mass of needles, and was purified by crystallisation from alcohol : 241 0.1972 gaveU.5422 C'O, aud 0.1414 H,O.G=75*0; H=8+0. 0.1704 ,, 11.7 C.C. N, (moist) at 14O and 760 mm. N=8-08. 0.2505 ,, 0.1657 BaSO,. S=9*1. C,,H,,N,S requires C =;75.0 ;H The compound has therefore been produced by the elimination of the elements of water from the cyanohydrin first formed, and the following formula may therefore be assigned to it : CH3-$X CH, CH,:Y*CH, CK CH I I CH3 CH3 The compound dissolves fairly readily in the usual solvent media, with the exception of light petroleum, carbon disulphide, and water ; it crystallises from alcohol in flat needles, which melt sharply at 94@. It at once discharges the cdour of a solution of bromine in chloroform or of potassium permanganate in acetone : 0.4062, made up to 25 C.C.with absolute alcohol, gave, in a 2-dcm. tube, a + Oa160, whence [a]g+4092~. In accordance with the absence of hydroxyl groups, the compound is not altered by acetic anhydride or chloride. It readily loses both hydrogen cyanide and hydrogen sulphide when heated with ferrous hydroxide and alkali, but is stable in the cold. When titrated with a standard solution of bromine in acetic acid in presence of sodium acetate, 0.5 gram used up 0.465 gram of bromine instantaneously, corresponding with 4 atomic proportions of bromine; an additional 0.465 gram was absorbed in the course of thirty minutes, corresponding with a total quantity of 8 atomic proportions of bromine.The new dinitrile is partly hydrolysed when heated for three hours with saturated hydrobromic acid, and an acid product, apparently a mixture, is obtained, contaminated with a neutral oil. The acidic portion of the product finally yielded a small quantity of an apparently pure compound, which melted sharply at 125O : 0.1940 gave 0.4770 CO, and 0.1443 H,O. C=67.1; H=8*2. (C,,H,,*CO,'H),S requires C =67.7 ;H= 7.7 per cent. 0.1438 gram required 7.4 C.C. NI10-NaOH for complete neutral- isation with phenolphthalein as indicator, whence the equivalent is 194; the value calculated for it dibmic acid, (C,oH,,*CO,H),S, is 195. The acid is readily soluble in most of the usual media, with the per cent. 9-09S=;7.95 =: W;8.0= exception of water, carbon disulphide, and light petroleum.It decomposes if heated for a considerable time at looo, giving 8 neutral, dark-coloured oil. 250. “Preparation of the nitrites of the primary, secondary, and tertiary ammonium bases.” (Preliminary note.) By Paiichlnan Neogi. Small quantities of benzylammonium nitrite (R&y a.nd Datta, Trans., 1911,99, 1475), piperidinium nitrite (Neogi, ibid., p. 1599), and triethylammonium nitrite (Neogi, ibid., p. 1253) have been obtained by the distillation and sublimation in a vacuum of a concentrated solution of the hydrochlorides of the bases and the alkali nitrites. The actual isolation of these nitrites from the mixtures leads the author to believe that the reaction between nitrous acid and the primary, secondary, and tertiary amines proceeds through the intermediate stage of a nitrite, which decom- poses, in the case of a primary aniine to alcohol, in the cae of a secondaxy amine to a nitroso-compound, and in the case of a tertiary amiiie to the original amine.251. “Studies of ammonium solutions. Part I. An ammonium electrode.” By Roland Edgar Slade. When hydrogen containing ammonia is passed over platinised platinum in a solution containing ammonium ions, the platinum behaves as an ammonium electrode. The potential of this electrode at 25‘ depends on the partial pressures of hydrogen and ammonia and on the concentxation of ammonium ions in the solution in the following way : where e = eelectmdaeaolution,-and the potential of the normal hydrogen electrode is taken as zero.Complexes of the form (NH&EI.*, where z is greater than one, do not exist to any appreciable extent in dilute aqueous ammonia or ammoniacal ammonium chloride solutions, although there is some evidencm of their existence at higher concentrations. 252. ‘‘ The absorption speotra of triketohydrindene hydrate and certain derivatives.” By John Edward Purvis. The results of an investigation of the absorption spectra of triketohydrindene hydrate and its derivatives showed that (1) the 248 colour of the compounds is intimately connected with the presence of ketonic groups; (2) the shade of colour is modified according to the nature of the substituting groups; (3) where another ring is established, there is no selective absorption, and the colour is produced by an extension of the general absorpt’ion within the regions of the visible spectrum.253. “The action of chlorine on alkalis and of carbon dioxide on bleaching powder.’’ By Robert Llewellyn Taylor. In reply to Higgins’ suggestion (Tram., 1911, 99, $58) that the increaved bleaching efficiency of a solution of bleaching powder on the removal of free lime or the addition of chlorides (Taylor, Trans., 1910, 97, 2641) is not due to the reversal of the action and consequent liberation of chlorine, but, in the first case, to the further action of the carbon dioxide of the air, and, in the second case, to the iucreased attraction of such solutions for the carbon dioxide of the air, the author pointed out that most of his experi- ments were performed either in absence of air or with air from which the carbon dioxide had been removed, and described further experiments performed in closed vessels, in which he obt%a;ined similar results.Higgins further stated that other neutral salts of sodium had a similar stimulating effect on the bleaching action of a solution of sodium hypochlorite to the chloride. Further experiments by the author show that if a solution of sodium hypochlorite contains considerable excess of free alkali, its bleaching action is very slow, and it is not much stimulated by the addition of any sodium salts, but if there is not much free alkali present the stimulating action of sodium chloride is much greater thav.that of other neutral sodium salts. The author further pointed out that Riggins’ suggested e’xplana- tion of the action of carbon dioxide on bleaching powder is not really very diiferent from his own. Higgins represents the action by two equations, and the author by three, the second and third of the latter being merely a simplification of Higgins’ second. 254. ‘I The relation between residual affinity and chemical constitution. Part 11. Certain compounds of nitrogen.” By Hans Thacher Clarke. An account was given of a study of the reactivity towards alcoholic benzyl chloride under standard conditions, and the refrat- tive power of a series of open-chain and cyclic tertiary amines 244 containing one and two nitrogen atoms in the molecule.The conclusion was put forward that derivatives of piperazine display abnormal reactivity and refractive power when compared with the corresponding open-chain compounds. In a series of derivatives of piperidine, it, was shown that the reactivity increased similarly when the nitrogen atoms were present in the 1 :5-psition in a normal chain. 255. (( Theory of dyeing : colour and molecular state of picric acid.” By William Porter Drecper. Picric acid in the anhydrous state is probably colourless. In the presence of moisture it is yellow: and pwibly then has a quinonoid structure. In continuation of a previous investigation into the relative inhibiting action of fibre colloids on this colour change (Dreiaper and Stokes, J.SOC.Dyers, 1909, 25, lo), the action of toluene on picric acid when present within the fibre area has been examined. The experimental results indicab that even in the case of cotton, although the change to the colourlw type takes place readily in the presence of dehydrating agenb, yet the presence of toluene will not bring about this change, in spite o€ the known fact that picric acid has little affinity for vegetable fibres in the presence of water; also, that under certain conditions picric acid in the yellow state will be adsorbed by cotton from a colourless toluene solution. 256. “Electromotive forces in alcohol. Part 11. The hydrogen electrode in alcohol and the influence of water on its electro- motive force.” By Robert Taylor Hardman and Arthur Lapworth.Concentration cdls reversible to hydrogen ions with solutions of hydrogen chloride in absolute alcohol gave potentials which were constant and reproducible within a fraction of a millivolt. Results with solutions not weaker than X/20 were in fairly good agreement with those calculated by employing the transport numbers deduced in Part I (Trans., 1911, 99, 1420); with lower concentrations, discrepancies of several millivolts were found. Water depresses the potential of the hydrogen electrode in alco- holic hydrogen chloride, and when the acid is dilute the results indi- cate it fall in the concentration of the “ free” hydrogen ions which is very close to that anticipated on the assumption that the avail- ability of the acid is a measure of this concentration as well as of 245 the catalytic activity of the cations of the acid in a given solvent (Trans., 1908, 93,2168, 2i90 et seq.; 1910, 97, 23).With fir/ 100-hydrochloric acid in both compartments of such a concentration cell, the potentials observed when water is added to cne compartment indicated a “ water value ” for absolute alcohol = 0-132 at 25O; with N/500-hydrochloric acid and N/lO-lithium chloride to minimise potential difierences at the liquid boundary, the “water value ” indicated was 0.122 at 25O. These numbers are intermediate between those previously deduced from (i) measure-msnts of the catalytic and (ii) the salt-forming activity of hydrogen chloride in absolute alcohol by Goldschmidt and Udby (0.15) and by Lapworth and Partington (0.10) respectlvely. 257.(( Notes on new coumarin derivatives.” By Arthur Clayton. In view of the characteristic odour of the 5-nitresubstituted coumarins (Clayton, Trans., 1910, 97, 1388), the author attempted to prepar;, 5-nitrocoumarin, since its odour might reasonably be supposed to be stronger than that of the foregoing compounds. A study of the action of nitric acid on the homologues of coumarin indicated a tendency for the nitregroup to enter position 5 when position 6 is already occupied by a substituent, whence it was hoped that 6-aminocoumsrin would yield 5-nitre6-amine coumarin when nitrated, and that the amino-group could be subsequently removed by the diazo-reaction.PreIiminary experiments showed that 6-aminocoumarin yielded an unworkable tar when treaked with nitric acid, either alone or in solution in acetic or sulphuric mid, but 6-acetylaminocoumarin, when dissolved in nitric acid (D 1.5) cooled to loo, yielded a solution which, on dilution with water, furnished an abundant and almost white solid. The 1zitro-6-acetylaminocoumarinso obtained crystallised from glacial acetic acid in pale yellow needles, melting at 222-223O: 0.1452 gave 0.2828 GO, and 0.0590 H,O. C=53*10; H =4.52. 0.1438 ,, 15.1 C.C. N, at 21° and 742 mm. N=11.67. C,lH,O,N, requires C =53-23 ;H =3.23 ;N =11-29 per cent. Nitro-6-acetylaminocoumarin proved to be easily hydrolysed by boiling with sulphuric acid diluted with three times its volume of water for thirty minutes.The product, 1zitro-6-aminocoumarin, was obtained by further dilution with water, and was then crys- tallised from glacial acetic acid, when orange needles, melting at 238--240°, were obtained : 246 0.1182 gave 0.2266 CO, and 0.0354 H,O. C=52.31; H= 3-36. 0.1432 ,, 17.5 C.C. N, at 21° and 742 mm. N=13.58. C,H,O,N, requires C=52.43; H=2.91; N=13*59 per cent. All attempts to eliminate the amino-group from the foregoing compound proved unsuccessful, owing to the extreme ease with which coumari~6-diazo-5-oxide is formed. The latter compound is prduced in greatest quantity when nitro-6-aminocoumarin (1gram) is mixed with absolute alcohol (10 c.c.), and concentrated sulphuric acid (4 to six drops) and an excess of amyl nitrite are consecutively added.On warming, the mixture becomes less pasty, and then, rather suddenly, a mass of crystals is deposited. This product was separated and crystallised from very dilute alcohol, when yellow needles ware obtained, melting with abrupt decomposition at l55-16Oo. It yields no definite product when boiled with acids or alkalis : 0.1468 gave 0.3076 CO, and 0.0307 H,O. C=57.14; H=2*32. 0.1203 ,, 15.0 C.C. N2 at 18O and 770 mm. N=14.60. CgH403N2requires C=57.45; H=2*13; N=14.89 per cent. During experiments performed in other directions with the hope of obtaining odorous nitrocoumarins, the following compounds were also obtained. &Met hylcoztmarin was prepared by heating together 2-hydroxy- m-tolualdehgde (3 grams), anhydrous sodium acetate (3 grams), and acetic anhydride (5 grams) in an oil-bath at 180° for four hours.The product solidified to a brown cake on cooling. This was boiled with water to r0move the sodium acetate, and the residue from the cold liquid ground up with methyl alcohol (2 to 3 c.c.). The filtered product was then crystallised, first from dilute methyl alcohol and then from petroleum, after which it formed white needles, melting at 75O. These crystals are somewhat soluble in water, and possess an odour of coumarin : 0.1083 gave 0.2983 CO, and 0-0520 H,O. C=75II ;H=5*34. ClO’H8O2requires C=75.00 ;H=5.00per cent. Nitro-6-methylcoumarin was obtained by dissolving 6-methyl-coumarin in concentrated sulphuric acid (20 parts), and adding nitric acid (1 molecule).After twenty minutes, the liquid was poured on ice, and the precipitated solid crystallised from alcohol, when white, inodorous needles, melting at 147-148O, separated : 0.1576 gave 9.6 C.C.N, at 23O and 766 mm. N= 6.92. CloR70,N requires N=6*83 per cent. 4 : 8-~~methyZ-6-tert.-butylcouma1~irt.--Thiscompound resulted from tho condensation of equimollecular quantities of p-t ert.-butyl-0-cresol znd ethyl acetoacetate in the presence of concentrated 247 sulphuric acid. White, inodorous needles were obtained, melting at 159-16OO: 0.1980 gave 0.5664 CO, and 0.1422 H,O. C=78.03; H=7.98. C,,H,,O, requirm C =78-26;H =7-83 per cent. The substance appmrs to behave abnormally toward nitric acid, owing probably to the presence of the tert.-butyl group.The nitration product forms white needles, melting at 240-241°, and possesses a pleasant but not very marked odour. 258. (( The temperature-coefficientof the electrical conductivity of hydrogen chloride in alcoholic solution.” By James Riddick Par tingt on. The experiments proposed in a former communication (Lapworth and Partington, Trms., 1911, 99, 1426) are now completed, and the conductivities of alcoholic hydrogen chloride at Oo, 18O, and 25O have been determined. The values at infinite dilution are found to be: A, at 0°=46*50, A, at 18O= 60.00, A, at 25O= 66.50. From these the mean value of the temperature-coefficient, a,, is found to be 0.0178 units of A, at Oo per lo, and is therefore normal. 259.(( The constituents of the oil of Pinus longifolia.” By Henry Haliburton Robinson. By fractional distillation, the oil of Pinus longifolia was found to be divisible into two portions; one portion, ?mounting to about one-third of the whole, was of a much lower boiling point than the other, and was found to be I-pinene. The remaining tw+thirds was mainly composed of an oil boiling at 173O, having D:X 0.867 and a, about +13O. From this, by treatment with dry hydrogen chloride, sylvestrene dihydrochloride was obtained, from which sylvestrene was regenerated. From the mother liquors left after removing as far as pmsible the sylvestrene dihydrochloride, dipentene was obtained.It is thought very possible that the sylvestrene is not present as such in the original oiI, but that a terpene is there contained, which unites with hydrogen chloride to form sylvestrene dihydrochloride, just as pinene yields a hydrs chloride from which camphene is obtained when the hydrogen chloride is removed. 260. (6 The active constituents of the Indian solanaceous plants : Datura Stramonium, D. fastuosa, and D. Metel.” By Albert Edward Andrews. It was found that in the Indian Datura Stramonium plants the percentage of total alkaloid in the stems was 0.25; in the leaves, 0.41 to 0.45; and in the fruits, 0.46 per cent.; with one exception this alkaloid consisted of hyoscyamine either alone or associated with a small proportion of scopolamine.The results icdicate that the Indian plant bears f avourable comparison with the European and Egyptian plants as regards the amount of total alkaloid, but the presence of scopolamine in some of the Indian samples appears to be a point of difference. In the Indian Datura fastuosa samples, the total alkaloid varied from 0.1 in the rootsto 0.2 in the fruit8, and scopolamine was found tc be the predominant alkaloid. In these respects the Indian plant closely resembles the European plant. Tn the Indian Datura Metel samples the seeds and the leaves contained 0.25, and the capsules 0.12 per cent., of total alkaloid. On comparing the results with those recorded for the European species it appears that in the Indian plant the amount of total alkaloid in the seeds and in the leaves is only about one-half what it is in khe European plant, but with one exception the samples resemble the latter in so far that scopolamine is almost unaccom- panied by other mydriatic alkaloids.261. Contributions to the chemistry of the terpenes. Part X. The action of chromyl ohloride, nitrous acid, and nitric acid on bornylene.” By Oeorge Oerald Henderson and Isidor Morris Heilbron. On treatment with chromyl chloride dissolved in carbon disulphide, bornylene is converted into a solid additive prodwct, C1,H1,,2Cr0,(;4, which is decomposed by water, giving a chloro-ketone, CloHl5QC1, and an aldehyde, CgHIS-CHO. The ketone, a crystalline solid, m. p. 165O, gives a semicarbazone, melting at 234--235O, and yields camphoric acid when oxidised with potassium permanganate, and camphor when heated with alcoholic potassium hydroxide under pressure.It therefore appears to be a new chloro-camphor. The aldehyde was proved to be camphenilanaldehyde, a derivative of camphene, which has been prepared in several different ways from that hydrocarbon. The direct formation of this camphene derivative from bornylene indicates close similarity in the molecular structure of these terpenes. 249 It has been observed that camphenilanic acid, C9H15*C92H,can be converted into isocamphenilanic wid by repeated crystallisation from water, alcohol, or light petroleum, and also that the semi- carbazones obtained from camphenilanaldehyde and isocamphenilan- aldehyde respectively are identical, and that each yields the igo-aldehyde when decomposed with dilute acids.Bromoisoca.rnp~enilun~cacid,a crystalline solid, m. p. 204-205°, was prepared by converting isocamphenilanic acid into its chloride, C,H,,*C?OCl, a dense liquid, b. p. 118O/25 mm., heating this with bromine under pressure, and decomposing the ch2om’de of the tcromo-acid, CSHl,Br*COC1, which is also a heavy, viscous liquid, with water. When warmed with aqueous sodium carbonate, the bromo-acid does not give a corresponding hydroxy-acid, but is converted into an unsaturated acid, C,H,,*CO,H, a colourleas, crystalline solid, m. p. 147O. Bornylene shows a generd resemblance to camphene in ita behaviour towards nitrous acid, but different produch are obtained on attacking these tarpenes with nitric acid.On trmtment with nitrous acid, bornylene yields (I) a nitrosite, (C10H1s-N203)2,which crystallises in silky needles, m. p. 163O, and yields camphoric acid on oxidation; (2) an oily, green liquid, Rhich decomposa when heated, dissolves in solutions of alkalis, and is probably an ismitrosite; (3) some cmphorquinone; and (4) a very small quantity of a colourless, crystalline compound, m. p. 84--85O, which is possibly a nitrite. When heated with nitric acid, bornylene is, for the most part, oxidised to camphoric acid, but some of it is converted into a yellow, crystalline compound, m. p. 137O, which has the formula C,,H,6(N02)2,and appears to be dinitrocamphane.On reduction with alcoholic ammonium sulphide, this substance yields a compoztnd which cryst.alIises in yellow needles, M. p. 196-198O, and which apparently is not an aminderivative. A trace of a colourless, crystalline cornvnd, m. p. about 174O, was also found among the oxidation products. 262. The constitution of camphene.”By George Gerald Henderaon and Isidor Horris Heilbron. Arguments were adduced in support of the view that the constitution of camphene is best represented by the formula: 250 263. “Candelilla wax.” By James lKcConnell Sanders. A sample of Candelilla wax, prepared in the month of January from plants collected in Coahuila, had the appearance of a greenish- white mas3 with a granular fracture.It contained a considerable proportion of water, and when freed from this, was dark brown, and gave the following values: Melting point .................. 67.5” Density........................... 0 -9850 Acid value ..................... 14’39 Saponification value ......... 46 *76 Iodine value (Hubl) ......... 16’60 per cent. Unsaponifiable matter ...... 77 *OO ,,Hydrocarbons ................. 48’60 ,, The wax contained hentriacontane and myricyl alcohol. 264. “A convenient method for determining the density of heavy petroleums.” By James McConnell Sanders. Heavy crude petroleum and derived products of similar charac- ter, such as the more viscous lubricants, “black oils,” etc., present difficulties in manipulation when the determination of their density at the standard temperature is attempted by the usual procedure.In the absence of a knowledge of the coefficient of expansion of a particular sample, it is always desirable to determine the density at a temperature as close to the normal air temperature as possible, this being the more desirable when the data to be obtained are subsequently to be utilised for calculation with large volumes of the commercial article. Crude petroleums are often so dense and viscous that a deter-mination of the density with the pyknomebr is very troublesome, and a very appreciable error is introduced by the presence of suspended water, which cannot be removed easily without employing means which are liable materially to modify the density of the oil.Filtering through hot anhydrous sodium sulphate, or dry salt, usually results in the loss of the more volatile components of the oil, and the use of the filter pump to facilitate filtration in the cold often gives rise to the same source of error. With increasing density and viscosity of an oil, there is increased difficulty of manipulation and simultaneously increased error from included water. In the simple method about to be described, the error from suspended water is considerably decreamd, although not entirely 251 removed; at the same time, the method possesses the advantage of rapidity and economy in the amount of sample employed. The necessary apparatus consists of a curved glass tube of the form shown, provided with a small rubber bulb or a rubber tube with a pinchcock, wording to the density of the oil to be examined.In addition, two graduated burettes of 100 C.C. capacity, a cylinder capable of containing 100 c.c., a thermometer, and a rubber-tipped glass rod. Two solutions of almhol and water are required, one containing 0.5 per cent. of alcohol, the other 75 per cent., both by volume. These solutions should be prepared beforehand, and preserved in stoppered stock bottles. The alcohol used should be pure, and the water free from air. The following method of procedure is to bO followed. A well-mixed and representative sample of the oil is poured into the curved glass tube so as nearly to fill it; if the oil is very viscous the small, rubber, pear-shaped cap is used to close the upper orifice of the tube, otherwise the tube and pinchcock are employed.The burettes are then filled each with one of the alcoholic mixtures, the level of the liquids being brought to the zero point on the burettes, and these are then supported one on each side of the glass cylinder. The thermometer is then fastened to the filled glass tube in such a manner that its bulb will occupy the central zone of the cylinder when the tube is placed within it so as to rest on the bottom. About 75 C.C. of the more dilute alcohol axe then run into the cylinder from the burette, and the glass tube is immersed in the cylinder. By means of the pinchcock or rubber bulb, a single small drop of the oil is expelled from the lower orifice of the tube, when, if the density of the liquid is greater than that of the oil drop, it will imme- diately rise to the surface, and can be “fished out” by touch- ing it with the rubber-tipped glass rod.A little of the stronger alcohol is then run in from the other burette, and another trial drop of oil expelled; these operations are repeated until the trial drops begin to rise more slowly and assume a spherical form, showing that the density of the alcohol mixture is approaching that of the oil. When this point is reached, the oil drops should be allowed to exude more slowly, so to allow any suspended water 252 to be dissolved out by the alcohol, and also to allow the temperature of the alcoholic mixture to coincide with thaqt of the oil in the tube. With a little practice, it is possible to procure a number of oil drops floating in various zones of the alcoholic mixture, when the latter should be well stirred, using the tube and attached thermometer for the purpose.As soon as the densities of the mixture and the oil drops are identical, the volumes of the two alcohols used to form the mixture are read off from the burettes, and the density of the mixture is calculated from the amounts used. Instead‘of calculating the density of the mixture (which assumes a previous determination of the density of each dilute alcohol), the mixture may be filtered quickly through moistened cotton wool to separate the oil drops, and the density taken with the hydrometer or the Westphal balance.A convenient practice oonsists in preserving the alcoholic mix- tures obtained in a series of experiments in closely stoppered bottles, labelled with the corresponding densities and temperatures. These empirical solutions can then be used for approximate determinations of fresh samplw of oil. 265. 1c The probable cause of the elimination of a carbethoxyl group as ethyl carbonate by the action of sodium ethoxide.” By Ferdinand Bernard Thole and Jocelyn Field Thorpe. The cause of the elimination of a carbethoxy-group during the passage of an open-chain nitrile carboxylic ester into a five-ring imino-compound is not due to any condition of strain consequent on the presence of more than one carbethoxy-group on any one carbon atom of the ring, but must be ascribed to a tendency which exists for the compound to acquire the hydrogen atom necessary to enable it to react in its tautomeric form.266. “The chemistry of the glutaconic acids. Part 11. The reactions of the alkglglutaconic acids having one mobile hydrogen atom.” By Ferdinand Bernard Thole and Jocelyn Field Thorpe. The experiments which have been carried out lead to the follow- ing conclusions : (1 ) The a-monosulostituted derivatives of glutaconic acid are stable in their trans-forms, but can be isolated as unstable cis-mdificatlons. (2) The stability of the cis-modifications increases with the weight of the group occupying the a-position. 253 (3) The tendency for the mobile hydrogen atom to pass outside the threecarbon system is manifested as soon as ring formation is produced from the cis-modification.Thus, the normal anhydride (I) is converted into the hydroxy-anhydride (11) on distillation, and this is transformed into the chloro-anhydride (111) by acetyl chloride: CH,<(-lH.COCR*CO>o --t cH<g;gHp -+ CH<;;;:9>0 (1.1 (11.1 (111.) (4) The anilic acids of the &-modifications pass into the anilic acids of the trans-forms when heated. (5) The di- and tri-substituted derivatives are stable as their cis-f orms, and cannot be isolated as tmns-modifications. (6) The tefidency for the mobile hydrogen atom to pass outside the three-carbon system diminishes with the increase of alkyl groups in the molecule.(‘7) The presence of the mobile hydrogen is indicated, not only by the formation of hydroxy-anhydrides and chloro-anhydrides, but also by the behaviour of the anilic acids (IV), which are converted into anilino-lactones (V) when heated : (IT.) (V.1 (Sj The stability of the form which has the hydrogen atom outside the threecarbon system is shown by the fact that the more stable hydroxy-anhydrides behave on titration as monobasic acids, and can be recovered from the solution on acidifying. Analysis of the salts shows them to possess the constitution (VI). It is only when the neutral solution is warmed that the hydrogen passes back into the threecarbon system, yielding the dkali salt of the cis-modification : ADDITIONS TO THE LIBRARY.I. Donations. Avogadro, Arnsdeo. Opere scelte. Pubblicate dalla R. Academia delle Scienze di Torino. pp. cxl + 491. Portrait. Torino 1911. (Referents.) From the Academy. 254 Backer, Hilmr Johalznes. De Nitraminen en hunne electro-chemische reductie tot Hydrazinen. pp. xv + 242. Leiden 1911. (Recd. 6/7/11.) From the Author. Cross, Charles Frederick, Bevan, Edward John, Sindall, Robert Walter, and Bacon, William N. Wood pulp and its uses. pp. xi + 270. ill. London 2911. (Recd. 19/7/11.) From the Authors. Friend, Joh Albert Newton. The corrosion of iron and steel. pp. xiv + 300. London 1911. (Recd. 27/7/ 11,) From the Publishers : Messrs. Longmans, Green and Co. Graebe, Carl.Untersuchungen iiber Chinone. Edited by Herman Decker. pp. viii + 672. Portraits. Leipzig 191 1. (Reference.) From the Author. Jago,William,and Jago, William C. The technology of bread-making. Including the chemistry and analytical and practical testing of wheat, flour, and other materials employed in breadmaking and confectionery. pp. viii + 908. ill. London 191 1. (Recd. 28/9/11.) Frorn the Authors. Knecht, Ednzund, Rawson, Christopher, and Loewenthal, Richard. A manual of dyeing, 2nd edition. 2 vols. pp. xii+902. ill. London 19 10. (Becd. 6/7/11 .) From Professor E. Knecht. Lunge, George. [Editor.] Technical methods of chemical analysis. English translation from the latest German edition, adapted to English conditions of manufacture, edited by Chudes Alexander Keane.Vol. 11, in two parts. pp. xvvii+ 1253. ill. London 1911. (Recd. 14/10/11.> From Dr. Charles A. Keane. Mastin, John, The chemistry, properties and tests of precious stones. pp. vi+ 114. London 1911. (Recd. 14/lO/ll.) From the Author. Mennicke, Hans. Die Metallurgie des Wolframs mit besonderer Beriicksichtigung der Elektrometallurgie sowie der Verbindungen und Legierungen des Wolframs samt seinen Verwendungen. pp. ii + 416. ill. Berlin 1911. (Recd. ll/lO/ll.) From the Publisher : &I.Krayn. Henachutkin, Boris N. Life and work of N. A. Menschutkin. pp. viii+ 376. ill. 1908. [In Russian.] (Recd. 21/7/11.) From Sir William Tilden, F.R.S. Paxthgton, J. Riddick. Higher mathematics for chemical students.pp. iv+272. London 1911. (Recd. 27/7/11.) From the Publishers : Messrs. Methuen & Co. Roscoe, The Right Honouruble Sir Henry E@eEd, and Schorlemmer, Cud. A treatise on chemistry. Vol. I. The non-metallic elements. New edition completely revised by Sir H. 3.Roscoe, assisted by J. C. Cain. pp. xii + 955. ill. London 191 1, (Reference.) From the Right Honourable Sir H. E. Roscoe, F.R.S. 255 Simmons, William Herbert, and Mitchell, CJLarles Aimworth. Edible fats and oils. Their composition, manufacture and analysis. pp. viii+150. London 1911. (Recd. 28/9/11.) From the Authors. Spencer, James Frederick. An experimen tal course of physical chemistry. Part I. Statical experiments. pp. xiv + 228. ill. London 1911. (Recd. 29/9/11.) From the Author.Zacharias, Johannes. Elektrochemische Umformer [Galvanische Elemente]. pp. xii+ 262. ill, Wien 1911. (Recd. 12/10/11.) From the Publisher : A. Hartleben. 11. By Pwchccse. Allen, Aljred Henry. Commercial organic analysis. Vol. V. 4th edition. Edited by William Alfred Davis and Scmuel S. Sadtler. pp. ix + 704. London 1911. (Recd. 16/10/11.) Chalon, Paul F. Les explosifs modernes. 3rd edition. pp. vi + 789. Paris 1911. (Recd. 19/7/11.) Higgins, William. An essay on the theory and practice of bleaching, wherein the sulphuret of lime is recommended as a substitute for pot-ash. pp. xxxii + 71. London 1799. (Recd. 16/6/11.) Scheithaner, W. Die Schwelteere, ihre Gewinnung und Verrtr- beitung. pp. viii+ 192. Leipzig 1911. (Recd. 25/7/11.) RESEARCH 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 4th, 1911. All persons who received grants in December, 1910, or in December of any previous year, whom accounts have not been declared closed by the Councii, are reminded that reports must be in the hands of the Hon. Secretaries not later than Friday, December lat. 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 encourage- ment of research in inorganic and metallurgical chemistry. Furthermore, that the income due to the sum accruing from the Perkin Memorial Fund is to be applied to investigations relating to problems connected with the coal-tar and allied industries.256 MARCELIN BERTHELOT MEMORIAL LECTURE. An Extra Meeting will be held on Thursday, November 23rd7 1911, at 8.30 p.m., when the Berthelot Memorial Lecture will be delivered by Professor Harold B. Dixon, M.A., Ph.D., F.R.S. ERRATA. Page 184 191 Line 10 8" PROCEEDINGS,19 11. af&r "many '' insert "other." for ''j3-5 -hydroxy-3-methoxyphenylethylaminc " mad ''8-5 -hydr-oxy-3-methoxyphenylpropionicacid." * From below. At the next Ordinary Scientific Meeting on Thursday, November 2nd, 1911, at 8.30 p.m., the following papers will be communicated : “The constituents of the seeds of C’asimiroa Edutis.” By F.B. Power and T. Callan. “Preparation of the betaine of tryptophan,and its identity with the alkaloid hypaphorine.” By P. von Romburgh and G. Barger. “B-2-Methoxynaphthylpropionic acid and methoxy-peg-naphth-indanone.” By G. Barger and W. W. Starling.‘‘Dihydroxydihydrindylamine and its rmlution into optically active components.’’ By W. J. Pope and J. Read. ‘‘Studia in phototropy and thermotropy. Part 11. Naphthyl-ideneamines.” By A. Senier and R. Clarke. ‘‘Some derivatives of 4-(or5)-methylglyoxdine.” By A. J. Ewias. “The stability of the double oxalates of sodium and nickel, and sodium and ccrbait.” By J. W.Dodgson. “The lower limit of inflammation of mixtures of the paraffin hydrocarbons with air.” By M. J. Burgess and R.V. Wheeler. R. CLAY AKD SONS, LTD., BRUNSWICK ST., STAMFORD ST., S.E., AND BUNOAY, SUFFOLK;.
ISSN:0369-8718
DOI:10.1039/PL9112700201
出版商:RSC
年代:1911
数据来源: RSC
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