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Proceedings of the Chemical Society, Vol. 28, No. 405 |
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Proceedings of the Chemical Society, London,
Volume 28,
Issue 405,
1912,
Page 213-280
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[Issued 16/11/12 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 28. No.405. The Council has ordered the following letter and report to be printed in the Journal and Proceedings of the Society: WHINFIELD, SALCOMBE, S. DEVON. Sept. 16th, 1912. GENTLEMEN, I have the honour to forward the Annual Report of the International Committee on Atomic Weights for 1913, together with a Table of Atomic Weights, which are submitted for publica- tion in the Society’s Transactions and Proceedings, as hitherto. The Report draws attention to all the atomic-weight determina- tions which have been published since the date of the preceding Report, but the only alteration suggested in the table which accom- panied last year’s Report is the inclusion of the element holmium, with Ho=163*5, as the result of the work of Holmberg.I am, Gentlemen, Your obedient Servant, T. E. THORPE. The Ron. Secretaries, The Chemical Society, Burlington Rouse, London, Wc b 214 Annual Report of the International Committee on Atomic Weights, 1913. SINCEthe annual report for 1912 was prepared, a number of important memoirs on atomic weights have appeared. There are also one or two earlier researches which were received too late to be noticed at the proper time. These investigations may be sum- marked as follows : Nitrogen.-Wourtzel (Compt. rend., 1912, 154, 115), by oxidis- ing NO to N,O,, has redetermined the ratio between nitrogen and oxygen. Five concordant measurements give, in mean, N =14.0068.Potassium and Chlorine.-Staehler and Meyer (Zeitsch. anorg. Chem., 1911, 71, 368) have made careful analyses of potassium chlorate, with special precautions against contamination by the chloride. Their final series gives KC1 =74.5551, whence E =39.097 and C1=35*458. For a discussion of their results, see also Guye (J.Chim. phys., 1912, 10, 145), who concludes that the impurity above mentioned was, if not completely, at least sufficiently elimin- ated to be practically negligible. Fluorine.-McAdam and Smith (J.Amer. Chem. SOC.,1912, 34, 592) have published two preliminary determinations of the atomic weight of fluorine. Sodium fluoride was converted into chloride by heating in dry, gaseous hydrochloric acid, and from the ratio between.the weights the atomic weight was calculated. The two values found are : F=19*0176 and 19.0133. Phosphorus.-From analyses of phosphorus tribromide, Baxter, Moore, and Boylston (Proc. Amer. 4cad., 47, 585; J. Amer. Chem. SOC.,1912, 34, 259) find, in mean of three series, P=31.027 when Ag=107.88. This agrees fairly well with the former work of Baxter and Jones on silver phosphate. Further work on phosphorus trichloride is promised. Mercury.-Easley and Brann (J. Amer. Chem. SOC.,1912, 34, 137), by analyses of mercuric bromide, find Hg=200-64. This confirms the previous work of Easley on the chloride. SeZenium.-Kuzma and Krehlik (Trans. Bohemian Acad of Emperor Francis Joseph, 19, No. 13, 1910. Data furnished to the committee by Professor B.Brauner) have redetermined the atomic weight of selenium by reduction of SeO, with SO,. The mean of ten determinations is Se=79.26. TeZZurium.-Harcourt and Baker (Trans., 1911, $9, 1311) have thrown doubt upon the work of Flint, who claimed to have split up the supposed element into two fractions of different atomic weight. They repeated his method of fractionation, and from the fourth fraction, found Te=127*54. This agrees with the figure 215 found by Baker and Bennett in 1907. Similar fractionations have been carried out also by Pellini (Atti R. Accad. Lincei, 1912, [v], 21, i, 218), who likewise failed to find any indication of a tellurium of low atomic weight. Radium.-Honigschmid (Momtsh., 1912, 33, 253), by careful analyses of relatively large quantities of radium chloride, finds Ra=225.95.On the other hand, Whytlaw-Gray and Ramsay (Proc. Roy. SOC.,1912, 86, A, 270), using very small quantities of material, and converting the bromide into the chloride, find Ra= 226.36, in agreement with previous work by Madame Curie and Thorpe. Until the discordance between Honigschmid’s low value snd the higher is explained, it is undesirable to change the figure given in the table. TantaZum.-The determinations of this atomic weight by Chapin and Smith (J. Amer. Chem. Soc., 1911, 33,1497) were made by the hydrolysis of TaBr,. The mean of eight determinations gave Ta=181.80, a figure somewhat higher than that found by Balke from similar analyses of the pentachloride.Iridium.-Eoyermann (Sitzungsber. phys. med. Soz. Erlangen, 42, 278), by five reductions of (NH4)&C16 in hydrogen, finds Ir =192.613. HoZmium.-Six determinations of the atomic weight of holmium by Holmberg (Zeitsch. anorg. Chem., 1911, 71, 226), gave Ho= 163‘45. The well known sulphate method was employed. There are also approximate determinations of the atomic weights of lead, zinc, and copper by Pecheux (Com,pt. rend. 1912, 154, 1419), and ef calcium by Oechsner de Coninck (Compt. rend., 1911, 153, 1579). The figures obtained are not conclusive enough to justify their use in the table, for the methods employed were not of great accuracy. Only one change is recommended in the table for 1913, namely, the insertion of holmium, for which, hitherto, no good atomic-weight determination has been available.Two or three other alterations of small importance might be made, but it seems undesirable to make changes too frequently. (Signed) F. W. CLARKE. T. E. THORPE. W. OSTWALD. G. UBBAIN. c 216 1913. International Aton~ic Weightt~ 0 =16. 0 =16. Aluminiuiii ................. A1 27 .1 Molybdeiiiuii ............... Mo 960 Antimony.................... St i 120.2 Neodymiimi ............... Nd 144.2 Argon .....................A 39.88 Neon .......................... Ne 20'2 Arsenic ..................... As 74.96 Nickel ........................ Xi 58'6> Barium ........................ Ba I hi$3; Niton (rarlium emanation) h't 262.* Bismuth .....................Ki 208'0 Ni trogeii .................... N 14-01 Roron ........................13 11.0 Osiniuiii ..................... 0s 190.9 Rroniine ....................Br $9'92 Oxygen .......................0 il6*0~1 Cadmium ..................... Ccl 112'40 Palladium .....................Yti lOti.7 Caesiuin ..................... C.i 132.81 l'hosphoriis .................1' 31'04 Calcium .....................Ca 40.07 Platinuiii ................... I't 1952 Carbon ........................ C 12.00 Potassium ................... I< 39 '10 Cerium ........................ Co 14025 ~'raseor3S-iiii:iiir............... l'r 140'6 Chlorine ..................... CI 35 '3(i Kadi11 11 I ......................ria 226 '4 Chromiuni ..................Cr 52 '0 Rhudiunl .................. I:h 102'9 Cobalt ....................... Co 5s.9; Riibidinm ....................Rb 85-45 Columbiuni ................. Cb 93'5 Rutlieiiiuni .................Ru 101.7 Copper ........................ Cii 63.57 Samarium ...............Sa 150'4 Erbium .....................ErDysprosium ................. DY 162.5 167.7 Scandium ................ Sc Selenium ................... Se 44'1 79.2 Europinni .....................Eu Fluorine .....................F Gadolinium ................. Gd 152.0 19.0 157.3 Silicon .................... Si ADnSilver ....................... Sodium ........................ Ka 28'3 107~ 23.00 Gallium ....................Ga 69.9 Strontium ..................Sr 87 '63 Germanium ..................Ge 72.5 Sull'hur ..................... S 52-07 Glucinum .....................G1 9.1 Tantalum .................Ta 181'5 Gold ........................... Au 197.2 Telluriuiii .................... Te 1275 Helium ........................ He 3.99 Terbium ..................... Tb 159.2 Holmium .....................Ho 163'5 Thallium .................... T1 204.0 Hydrogen ..................... H 1'008 Thorinm ..................... Th 232.4 Indium ...................... 111 114.8 Thulium .....................Trn 168% Iodine ........................I 124'92 Tin ........................... Sn 119'0 Iriclium.......................Ir 193.1 Titaiiiuiii .....................Ti 48'1 Iron ........................... Ye 55-84 Tungsten ..................... W 184.0 Krypton ..................... lir 82 92 Uraniiim ..................... U 238.5 Lantlianum ................La 139.0 Vannlliuni .................. V 51.0 Lead ......................... 1% 207.10 xc11011 ........................ Xe 130'2 Litiiiuiil ..................... Li 6'94 Ytterbiuiii (Neoytterbinm) Yb 1720 1,utwiuni ................... Lu 174.0 Yttrium ..................... Yt 89.0 MagiI esiimi .................. Mg 24-32 Zinc ........................... Zn 65 '37 nilangaiiese ..................Mn 54-03 Zirconium .....................Zr 90-6 Mercury .....................Hg 200.6 217 The following are abstracts of papers received during the vacation, and published, or passed for publication, in the Trcms-nctions : 189. The essential oil of the leaves of Atherosperma moschatum (I Australian sassafras ’).” By Margaret Emilie Scott. (Trans., 1912, 1616.) The essential oil of -4~heros~ier-irrc~nioscftatum, Labill., conhains the following compounds in approximately the proportions indi-cated : eugenol methyl ether, 50-60 per cent.; pinene, 15-20 psr cent. ;camphor, 15-20 per cent,. ;and safrole, 5--10 per cent. 190. “Harmine and harmaline. Part I.” By William Henry Perkin, jun., and Robert Robinson (Trans., 1912, 1i75.) A detailed descriptioii of work of which a preliminary acwu tI t, has already appeared (this vol., p.153). 191. “The chemistry of the glutaconic acids. Part V. The preparation of esters of the labile acids.” By Norman Bland and Jocelyn Field Thorpe. (Trans., 1912, 1557.) The esters of thme labile acids of the series which, by reason of the presence of a methyl group on the central carbon atom of the three-carbon system, possess considerable stability, can be pre-pared by the dissociation of their sodium compounds, provided that such a compound contains a potentially mobile hydrogen atom within its molecule. Thus the action of sodium ethoside on ethyl isodehydracetate (I) yields the sodium compound (11),and, by further action, ethyl acetate and the sodium compound (110: (1.1 * (11.) ---+CH;CO,Et + NaO.C(O~t):CH .CMe:CH*~OzEt.(111.) This sodium compound coiitains a potentially mobile hydrogen atom (*); it therefore reacts with water, yielding the pure labile ester (IV). The corresponding normal ester (V) can be prepared by the esterification of the normal acid: ICO,Et-C H :CMe*CH,*CO2Et C0,Et -CH CH M e-CI H* C0,E t (1 IT.) (V. 1 c2 218 The alkylation of the sodium compound (11) leads to the forma- tion of the labile esters of the dialkylated acids (VI): CO,Et*CR:CMe*CH,*CO,Et+CH,*CO,Et VI.) +NaI and by this means the labile forms of both aP-dimethylglutaconic acid and of B-methyl-a-ethylglutaconic acid can be isolated. 192. ‘‘The chemistry of the glutaconic acids. Part VI. Conditions which confer stability on the truns-forms of the labile acids.” By Norman Bland and Jocelyn Field Thorpe.(‘ham, 1912, 1739.) By increasing the weight of groups attached to the carbon atoms of the three-carbon system, sufficient stability is conferred on the labile state to render it capable of isolation in its cis-and tram-modifications ; thus a-benzyl-P-methylglutaconic acid has been obtained as the normal form (I) melting at 148O, the tmns-niodi- fication of the labile form (11)melting at 134O, and the unstable cis-modification of the labile form 011) which passes into the hydroxy-anhydride (IV) melting at 69O, when liberated from its salts : CII,Ph*$-CO,H CO,H *fl*CH,Ph CH,Ph*G*CO,H yH 1516 $?Me ?A1 e -CH*CO,H CH,*CO,H CH,*CO,H (1.1 (11.) (111.) 193.‘’4-Alkyl-1:4-thiazans.” By Hans Thacher Clarke. (Trans., 1912, 1583.) Alkyl derivatives of the cyclic compound thiazan, or thiomorph- oline, S< -2CH4>NH, in which the alkyl group is attached to the ‘/ZU4nitrogen atom, may be prepared by the interaction of BP’-dichloro-ethyl sulphide and primary amines : The methyl-, ethyl-, isoamyl-, and b enzyl-thiuzans, together with characteristic derivatives, are described. 219 194. “The triazo-group. Part XXI. Benzenoid azoimides con-taining multivalent iodine.” By Martin Onslow Forster and Johannes Heinrich Schaeppi. (Trans., 1912, 1359.) In order to ascertain whether any intramolecular action occurs between the azoimide nucleus and the iodoso- or iodoxy-group, the three iodophenylazoimides were prepared and converted into their respective triazophenyl iodochlorides, triazo-iodosobenzenes, triazo- iodoxybenzenes, and di-triazophenyliodinium iodides.195. ‘‘P-Hydroxy-up-dimethgladipic acid and p-hydr oxy-a@-tri-methyladipic acid.” By Victor John Harding. (Trans., 1912, 1590.) When ethyl lzvulate is condensed with ethyl a-bromopropionate by means of zinc in benzene solution, there is formed a mixture of diethyl fl-hydroxy-afl-dimethyladipate(I) and the ethyl ester of the lactone of fl-hydrosy-afl-dimethyladipicacid (11) : C0,Et*CH~le.CXiIe(OH).~~~2.~H2*~~2Et (1.1 A similar mixture of hydroxy-ester (111) and lactone (IV) is obtained by the condensation of ethyl lzvulate and ethyl a-bromo- isobutyrate : co---C0,Et -CMe,*CMe(OH)-CH,.CH,*C0,Et 4 O>CMe* C&Ie,*CO,EbOH,aH, (111.) (IV.) Acid hydrolysis results in the production of the lactonic acids.Attempts to prepare the unsaturated acids from the hydroxy-acids were without success. 196. “The migration of the para-halogen atom in phenols.” ByPhilip Wilfred Robertson and Henry Vincent Aird Briscoe. (Trans., 1912, 1964.) The observation that 6-bromothymol on nitration forms 2-bromo- 6-nitrothymol (Robertson, Trans., 1908, 93,793) has led the authors to investigate in more detail the cause of the migration of the halogen atom, and to extend the observations to other compounds. A similar migration takes place with 6-chlorothymol (I) on nitra- tion. It seemed probable that an intermediate hemiquinonoid compound (11) is first formed, and actually the dinitro-derivative of this substance (IV) has been isolated by the action of excess of nitrogen peroxide on 6-chlorothymol : Me e Me Me -~NO,(\Cl .NO,\/\\NO,CI/\ IOH -+NO,“I>/\\ I \/ \):O \,OH ’ NO,(\,:O PrP PrP P1‘3 PrP (1.) (1 I. 1 (JII.) (IV.) Not only is the nitro-group capable of causing a para-halogen atom to wander into the ortho-position, but also one halogen can cause another partly to migrate in the same manner, so that when 6-chlorothymol is brominated or 6-bromothymol is chlorinated a mixture of isomeric chlorobromothymols is obtained. These observations are easily explainable on the assumption of the inter- mediate formation of a hemiquinonoid compound, which yields two products, as indicated below : 3Te Me Me Similar changes have been observed in the case of certain deriv- atives of 2 :2'-diphenol ; thus, 5 :5’-dichloro-2 :2/-diphenol and 5 :5’-dibromo-2 :2’-diphenol both yield on nitration compounds containing the halogen in the 3 :3’-position.197. ‘‘ The resolution of sec.-butylamine into optically active components.” By William Jackson Pope and Charles Stanley Gibson. (Traits., 1912, 1702.) Externally compensated sec.-butylamine is readily resolved into its optically active components by crystallisation with d-and I-a-bromocamphor-.rr-sulphonic acids ; a number of derivatives of the active bases have been prepared and characterised. 198.‘‘The relation between residual affinity and chemical constitu- tion. Part 111. Some heterocyclic compounds.’’ By Hans Thacher Clarke. (Trltris., 191% 1788.) CH,*CH2\A series of compounds of the general formula X<CH,, cH2/Y, where X and Y are oxygen, nitrogen, or sulphur, has been examined. From a consideration of their chemical behaviour it is found that: (1) the atoms X and Y exert a mutual influence, wliich affects their reactive power ; 22 1 (2) when X and Y are atoms of the same element, the reactive power is abnormally great; (3) when X and Y are atoms of different elements, the reactivity is abnormally small. The refractive and dispersive powers, and tbe molecular volumes, of these and other compounds are recorded, but no definite conclu- sions could be drawn therefrom.199. ‘* The configuration of substituted ammonium cornp~unds.~’ By Humphrey Owen Jones and John Gunning Moore Dunlop. (Trans., 1912, 1748.) The paper describes the preparation and attempted resolutioii of a dicyclic quaternary ammonium compound, namely, 2-tri-lii e thylenetetrahydroisopuinolinium iodide, CH,-C I-CH/CH=C( %rr*cll 011the .‘ pyramid ” configuration for quinquevalent nitrogen compounds this substance should exist in enantiomorphous forms, but no evidence that it can exhibit optical activity was obtained. It is also to be expected that a-and &substituted pyridiniuni compounds and also quinolinium compounds would exhibit optical activity. A number of compounds belonging to these classes has been examined previously (7’rans., 1903, 83,1415; 1907, 91, 117), and more recently Miss M.B. Thomas has examined others, but no evidence of resolution has been obtained. It would therefore appear desirable to suggest some hypothesis to account for the apparent non-existence of enantiomorphous forms in these cases. It is suggested tentatively that a quaternary ammonium com-pound may be regarded as having the four alkyl groups arranged around a central nitrogen atom forming a group (Na4), which possesses enough residual valency to unite with an electronegative radicle, forming a salt, Na,X. 200. (6 Hydrolysis of acetic anhydride.” By Kennedy Joseph Previt6 Orton and Marian Jones. (Trans., 1912, 1708.) The hydrolysis of acetic anhydride in various media, acetic acids of various concentrations, and aqueous acetone, has been invmti- gated by the aid of the method of determining acetic anhydride previously described (Edwards and Orton, PTOC.,1911, 27, 121).The results show that the hydrolysis of acetic anhydride is quite 222 analogous to its reactions with hydroxy- and amino-compounds, and to the hydrolysis of esters, amides, etc. In anhydrous media, acids are very powerful catalysts of the hydrolysis, but in water they have but a feeble influence. In aqueous solutions, alkalis and alkaline salts are most effective. Nitric acid behaves exceptionally; in a medium containing 50 per cent. acetic acid or less, it has the normal catalytic effect. As the proportion of acetic acid is increased, its apparent activity decreases until in glacial acetic acid it is infinitesimal.201. (‘Acetic anhydride. The pure material, its physical properties, and its reaction with bromine.” By Kennedy Joseph Previt6 Orton and Marian Jones. (Trans., 1912, Itno.) The complete separation of acetic anhydride from acetic acid can be effected by fractional distillation with a Young’s “pear ” still-head. The boiling point of the pure anhydride is 139*55O/ 760 mm., the specific gravity 1.0876 at 15O/4O, and 1.0820 at 20°/40, and the refractive index for the line H” 1.39311 at 9-5O and 1.39069 at 15O. Landolt (Ann. Phys. Chem., 1864, [ii], 122, 556) is the only observer whose values for these constants are in close agreement with the authors’; the most delicate analysis of acetic anhydride, containing acetic acid, is given by the method of Orton and Edwards (Trans., 1911, 99, 1181).Pure acetic anhydride is stable to bromine and chlorine in ths dark, but rapid action occurs in the presence of traces of strong acids, ferric chloride, or iodine ;aluminium chloride and other ferric salts are without effect. It is remarkable that the disappearance of the bromine is independent of the initial concentration, and directly proportional to the time and to the concentration of the catalyst. Addition of small quantities of water diminishes the activity of the catalyst except in the case of iodine. L‘202. The action of sulphur on amines. Part I.o-Toluidine.” By Herbert Henry Hodgson. (Trans., 1912, 1693.) When o-toluidine is treated with sulphur in the presence of o-toluidine hydrochloride or free hydrochloric acid, the product appears to be entirely tm’thio-o-toluidine, which may be readily isolated by means of its sparingly soluble hydrochZo~-ide. The swlphate, oxalate, acetyl, and benzoyl derivatives have been pre- pared, and also the m-nitrobenzylidena and hisazo-P-nnphthol derivatives, 223 On reduction of the hydrochloride with zinc and hydrochloric acid, a mercaptan is produced which on oxidation furnishes dithio-o-toluidine, of which the hydrochlom’de, sulphate, oxalate, and acetyl, m-nitrobenzylidene, and bisazo-8-naphthol derivatives were prepared. The bisazo-dyestuffs produced from trithio-o-toluidine are of remarkable fastness towards ordinary agents, particularly towards soap and alkalis.203.“Acyl derivatives of the dihydroresorcins. Part I. The action of hydroxylamine and of phenylhydrazine on C-acetyl-dimethyl- and C-acetyltrimethyl-dihydroresorcins.” By Arthur William Crossley and Nora Renouf. (Trans., 1912, 1524.) The behitviour of C-acetyldimethyl-and C-acetyltrimethyl-di-hydroresorcin towards hydroxylamine and phenylhydrazine has been investigated with the object of gaining more definite informa- tion as to the constitution of these substances. C-Acetyldimethyldihydroresorcinbehaves as a monobasic acid, and may be represented by one or other of the following formula=, probably the latter : CMe, CMe, H2C/\CH, H,Cf\CH, HO*CI\/b0 oc+o c; 5CH;CO CH;C*OH When acted on by hydroxylamine it gives an acid oxime (I),an isooxazole (11),and an oxime of the isooxazole (III), and with phenylhydrazine it behaves in a similar manner, giving an acid phenylhydrazone, a phenylpyrazole, and a phenylhydrazone of the phenylpyrazole.C-Acetyltrimethyldihydroresorcin also gives an acid phenyl-hydrazone and a phenylpyrazole with phenylhydrazine, although all attempts to prepare a phenylhydrazone of the phenylpyrazole have so far failed. Reasons are given in the paper for assuming that these two C-acetyl derivatives are similarly constituted : Chile, CMe, CMe, H,C/\CK, ’\CH, H,C/\CH,OC{)C:N*OH Hd:(/c:N HO*N:UI IC:N IIG 1-71 ‘d I CH3*C*OH CH,*C--0 CH,*C--0 (1.) W.) (111.) d 224 204.‘‘The influence of so1vents:;on the rotation of optically active compounds. Part XVIII. The effect of inorganic salts on the rotation of ethyl tartrate in aqueous solution and in the homogeneous condition.” By Thomas Stewart Patterson and Duncan Geddes Anderson. (Trans., 1916, 1833.) 205. ‘‘ The action of aliphatic amines on s-dibromosuccinic acid. Part. 11. Allylamine.” By Edward Percy Frankland and Henry Edgar Smith. (Trans., 1912, 1724.) The authors have prepared a diallylaminosuccinic acid, C,H,* NH*CH(CO,H)*CH(CO,H)*NH CSH5, with properties similar to those of the dipropylamino- and dibutyl- amino-succinic acids previously obtained (Trans., 1912, 101, 57), and have prepared from it!a 7?ionol~yt~rochloride,and M ononitros2-and tetrabromo-derivatives.The latter substance : CH, Br*CHBr-CH,*NH*yH-CO,H CH,Br *CHEr*CH,*NH-CH*C0,H’ undergoes decomposition when heated with acids, water, or alcohol, afl-dibromopropylamine or its salts being liberated, and one molecule of carbon dioxide evolved. The authors propose to apply this reaction to other brominated alkylamino-compounds. 206. ‘(Studies on cyclic ketones. Part I.” By Siegfried Ruhemann. (Trans., 1912, 1729.) In connexion with the work on triketohydrindene hydrate and its methylenedioxy-derivative, the cyclic ketones have been sub-jected to a closer study with the object of transforming them into polycyclic systems. The action of ethyl oxalate on a number of cyclic ketones was examined, and ethyl a-hydrindoneoxalate, C,;H ,<~~~>CH*CO*CO,Et,which is produced by this reaction, was condensed with hydrazine and phenylhydrazine to ethyl 4 :5-indenopyrazoZe-3-curboxylat e, NH and its 1-phenyl derivative. It was further found that a-hydrindone reacts with ethyl phenyl- 225 propiolate in the presence of sodium ethoxide, like acetone or acetophenone, and yields 6-phenyl-2 :3-andeno-4-pyrone, CH, co /\/\ff‘gH \/-C\/CC,H,o 0 Attempts were also made to condense 1:3-dimethyl-A3-cycZohexen-5-one with y-nitrosodimethylaniline, with the result that an azomethine is not formed, but ths nitroso-compound is reduced to tetramethyldiaminoazoxybenzene,whereas the ketone is probably oxidised to m-5-xylenol.This view is supported by the formation of ethyl Al-cyclohexene-3 :6-dione-2 :5-dicarboxylate on treatment of ethyl succinosuccinate with sodium carbonate and nitroso-dimethylaniline. 207. ‘‘The bromination of phenol. 2 :4-and 2 : 6-Dibromophenol.” By Frank George Pope and Arthur Samuel Wood. (Trans., 1912, 1823.) 2 :4-Dibromophenol is most rapidly prepared by the bromination of phenol in the presence of hydrobromic acid (D 1.49). The puri- fied product melts at 40°, and has been characterised by conversion into its acetyl, benzoyl, and p-nitrobensoyl derivatives and its methyl and ethyl ethers. 2:6-Dibroinophemol can be obtained in good yields by +he elimination of carbon dioxide from 3 :5-dibromo-4-hydroxybenzoic acid.The acid may be obtained in about 90 per cent. yield by bromination of p-hydroxybenzoic acid in presence of sulphuric acid, and the carbon dioxide eliminated from the carboxyl group by heating the acid under pressure with dilute sulphuric acid, water, or bases. The authors are of the opinion that the reaction is ionic, since the rate of elimination of carbon dioxide is slower the greater the concentratioil of the mineral acid, and more rapid in the presence of bases. The resulting phenol was characterised by conversiou into its nitro-derivative and into its methyl and ethyl ethers. 208. The action of halogens on silver salts and on potassium cyanate in presence of water, with a note on the decomposition of cyanic acid in aqueous solution.” By Charles William Blyth Normand and Alexander Charles Cumming.(Trans., 1912, 1852.) The halogens react with silver salts to yield a silver halide, an wid, and one or more oxidation productx of either the acid or the d2 226 halide. The reactions, on account of secondary oxidations, are sometimes complex ; for example, silver thiocyanate and iodine interact according to the equation : 14AgCNS+ 71, + 10H20= 14AgI -I-12HCNS+2H,S04 + HCN +NH, + CO,. The oxidation reactions are much more marked with chlorine and bromine than with iodine. The main product obtained by treatment of silver cyanate with iodine is carbamide, formed probably by secondary decomposition of cyanic acid. Bromine and silver cyanate yield ammonium bromide, carbamide, cyanuric acid, and a little nitrogen. For comparison, the action of bromine on potassium cyanate was studied, and found to be in accord with the equation: 4KCNO +4H,O -t-3Br, =4KBr +2NH,Br +N2+ 4c’o,.It is suggested that the reactions are due to interactions between the silver salts and the products of the hydrolysis of the halogen by water; thus, a silver salt reacts with the chloridions formed by partial hydrolysis of chlorine : C1, +H20=H’ 4-C1’ +HClO. Further interaction may occur between the hypochlorous acid and one of the reaction products. The experimental results are in accord with this hypothesis. In connexion with the formation of carbamide, some experiments on the decomposition of aqueous cyanic acid were tried, and these in conjunction with previous work led to the conclusion that cyanic acid decomposes in three different ways according to the conditions of experiment.209. ‘(The refraction and dispersion of triazo-compounds. Part 11.” By James Charles Philip. (Trans., 1912, 1E66.) From the results of the earlier investigation (Tmns., 1908, 93, 918) and the data recorded in the present paper, the figure 8-91 is deduced as the most probable refraction value (D-line) for the N,-group in ordinary positions. The corresponding dispersion value (HY-H,) is 0.348. In the case of o-triazoiodoberizene and ay-bis- triazopropylene, two compounds in which the N,-group is attached to a doubly-linked carbon atom, there is distinct enhancement of bhe optical values.This observation is in harmony with what was found in the earlier work. An incidental refractometric investigation of the o-dihalogen derivatives of benzene shows the superiority of Eisenlohr’s newer values for atomic refraction as compared with the older figures for these constants. 210. The action of acyl chlorides on primary amides.” By Arthur Walsh Titherley and Thomas Halstead Holden. (Trans., 1912, 1871.) Whilst by long heating acetyl chloride acetylates benzamide, benzoyl chloride only gives very small yields of dibenzamide (decreasing with rising temperature) and large quantities of benzonitrile and benzoic acid at 140O. The action of benzoyl chloride on p-toluamide was studied in order to elucidate the mechanism of the reaction, which has been shown to follow two courses, ijivolving the normal and pseudo-amide forms, namely : Ph’COClA.Ar*CO*NH, -+ Ar*CO*NH*COPh Ph’COC1B. Ar*C(OH):NH --+ Ar*C(O*COPh):NH --t Ar*CN+Ph*CO,H. In addition to the above products, benzonitrile is also formed in quantities which are relatively great when equimolecular propor- tions of p-toluamide and benzoyl chloride are taken, but; small when an excess of amide is used. Its production has been traced to the decomposition of the secondary amide under the catalytic influence of hydrogen chloride, yielding a mixture of acids and a mixture of nitriles. This action is prevented by fixation of the hydrogen chloride when an excess of amide is used owing to the formation of amide hydrochloride.An important further secondary reaction is that between the amide hydrochloride and hydrogen chloride, yielding at 140° an acyl chloride and ammonium chloride, thus: In the reaction between benzoyl chloride and p-toluarnide, there- fore, p-toluamide hydrochloride, ammonium chloride, p-toluoyl chloride, benzoic and p-toluic acids, benzonitrile, p-toluonitrile, and benzo-p-toluamide (and probably di-p-toluamide) are formed. 211. “The action of benzotrichloride on primary amides.” By Arthur Walsh Titherley and Thomas Halstead Holden. (Trans., 1912, 1881.) Salicylamide on heating with benzotrichloride readily condenses, yielding o-benzoyloxybenzonitrile (75 per cent. of theory), together with small quantities of N-benzoylsalicylamide. The mechanism of this change has been elucidated by the study of the action of benzotrichloride on acetamide, benzamide, and p-toluamide.The first product of the change is the nitrile and benzoyl chloride, which in the latter cases enters into further action on the amide, yielding a secondary amide and benzoic acid, as shown by the authors (preceding abstract), Since with p-toluamide, benzo- trichloride may under certain conditions yield benzonitrile along with p-toluonitrile (which is the main constituent when an excess of ptoluamide is used), as well as p-toluoyl chloride, two distinct condensation reactions appear to be involved when benzo- trichloride acts on an aromatic amide, in which the normal and pseudo-forms participate, probably thus : PhCCl HCIA.Ar*CO*NH,-4 Ar*CO*NH*CCI,PhL+Ar*CO*N:CPhCl ---,split Ar*COCI+ Ph-CN PhCClB. Ar*C(OH):NH--2&Ar*C(O*CCI,Yh):NH --+ Ar*CN+ Ph-COC1 The first reaction is favoured by the presence of hydrogen chloride on account of the formation of the amide hydrochloride, Ar*CO*NH,,HCl, which tends to react as in ,4, whilst the free amids tends to react as in 13; and hence this reaction is favoured by an excess of p-toluamide. When three molecular proportions of the latter and one of benzotrichloride react at 140°, the chief products are ptoluamide hydrochloride, benzo-p-toluamide, p-toluo- nitrile, p-toluic acid, and benzoic acid. When equimolecular pro- portions are employed, the chief products are ptoluoyl chloride, benzoyl chloride, p-toluonitrile, and benzonitrile.212. isoQuinoline derivatives. Part VII. The preparation of hydrastinine from cotarnine.” By Frank Lee Pyman and Frederic Qeorge Percy Remfry. (Tinus., 1912, 15%) Hydrocotarnine (I) is converted into hydrohydrastinine (11) in a yield amounting to about 40 per cent. of the theoretical by the action of sodium and alcohol : Me0 CH, CH, o/\/\NM~ -+ CH,<O!O/\,”)NNeCH&I I I \\/\/cH2 GH2 CH, (I. 1 (11.1 Since hydrocotarnine is readily obtained by the reduction of cotarnine, and, on the other hand, hydrohydrastinine yields hydrastinine on oxidation, the latter alkaloid can now be prepared from cotarnine. Besides hydrohydrastinine, the following bases have been isolated from the products of the action of sodium and alcohol on hydrocotarnine : 6-l~ydroxy-3-nzethyltetrahydroisopuino-litLe, ’i-hydroxy-2-methyltet?.ahydroiisopzLinoline, 6-hydroxy-8-metZi-o.ry -2 -rnethylretrahydroisopuzlzoline, and 7-hydroxy-8-methoxy-2-methyl te trahydroisopuinoline.229 213. “The rate of reaction of alkyl haloids with certain tertiary bases.” By Richard William Dades Preston and Humphrey Owen Jones. (Trans., 1912, 1930.) The authors have studied the rate of combination of certain organic haloids (methyl, ethyl, n-propyl, and ally1 iodides, o-, m-, and pxylyl bromides, and p-bromobenzyl bromide) with two tertiary amines (dimethylaniline and triisoamylamine) in absolute alcohol solution at 40° and in two cases at 25O.The results show that the ratio of the velocity-constants for the haloids is (with one exception) practically independent of the nature of the tertiary amine, and that the relative reactivities of the xylyl bromides are in the order which would be expected from a consideration of the distribution of affinity in the molecule after the manner adopted by Fliirscheim. The rate of the reaction was measured by precipitating and weighing silver haloid. It has also been shown that change of conductivity of the solution can be used to measure the rate of the reaction. o-Chloroaniline ....... 199-200” p-Bromoaniline ............ 222-223” m-c3hloroaniline ......... 206-207 o-Nitroaniline ............ 216-217 y-Chloroaniline .........217-218 m-Nitroaniline ........... 231-233 o-Bromoaniliue ......... 206-208 .h p-Nitroaniline ........... 235 m-Brurnoaniline ........ 21 7-21 8 p-Benzoylsminophenol was found to melt at 216-21 7O, benzoyl-aminophenyl benzoate at 235O, these figures substantially agreeing with those given by Reverdin. The former compound gives benzeneazo- and p-nitrobenzeneazo-compounds, which melt at 201 O and 267-268O respectively. 230 216. 66 The absorption spectra of nitro-compounds.” By John Theodore Hewitt, Frank George Pope, and Winifred Isabel Willett (Trans., 1912, 1770.) The authors compare the absorption of benzoic acid and its p-bromo- and p-nitro-derivatives with their sodium salts. In each case salt-formation is accompanied by only slight diminution of the oscillation frequency, and the same holds good for phenylacetic acid and its nitrile.In all these cases the possibility of quinonoid change is precluded, but when alkali is added to p-nitrophenyl- acetonitrile a deep purple colour is produced and a radical change in absorption spectrum occurs. Similar, although less marked, changes are observed in the case of ethyl p-nitrophenylacetate and p-nitrophenylacetic acid. Attention is drawn to the possibility of quinonoid rearrangement taking place according to the scheme : NOa*C6H4=CH,*CN -+NaNO,: C,H, ICH-CN I 216. Lc A study of some dicyclic quaternary ammonium compounds.” By John Gunning Moore Dunlop. (Trans., 1912, 1998.) 1:l-Trimethylenepiperidinium hydroxide, obtained by the action of silver oxide on 1:l-trimethylenepiperidinium bromide, yields on distillation y-hydroxypropylpiperidine, C,H,,N*CH,*CH,=CH,*OH, together with traces of piperidine.Marckwald and Frobenius (Ber., 1902, 34, 3557) stated that the product of the action of heat on P-chloroethylpiperidine, C,H,,N-CH,*CH,Cl, is 1:l-ethylenepiperidinium chloride, This is shown to be incorrect, the product being really diethylene- dipiperidin e dichloride, 217. ‘‘3-Aminocoumarin.” By Frank William Linch. (Trans.1912, 1678.) 3-Acetylaminocoumarin was prepared by the condensation of salicylaldehyde with glycine, or more advantageously from the 333 oxime of 3-acetylcoumarin by means of the Beckmann transforma- tion : CH It crystallises in white, silky needles, melting at 201°, and on hydrolysis gives 3-aminocoumarin, whioh forms cream-coloured tieedles melting at 130O.This compound behaves as if it possessed the imino-structure ;for example, nitrous acid gives an isonitroso- compound, and on hydrolysis 3-ketocoumarin is produced, with the liberation of ammonia. 7-Bromo-3-acetylccumarin, prepared by the condensation of 5-bromosalicylaldehyde with ethyl acetoacetate, forms pale yellow needles melting at 217O; the oxime decomposes at 220O. 7-Bromo-3-acetylomi1iocoumari.r~,prepared from the above oxime by means of the Beckmann reaction, crystallises from most organic solvents in needlsa melting at 266O. On acid hydrolysis it gives 7-br orno-3-aminocoumarin, which forms pale cream-coloured needles melting at 205O.218. ck Studies in the azine series. Part 11.” By Kathleen Balls, John Theodore Kewitt, and Sidney Herbert Newman (Trans., 19!2, 1840.) The question of the ortho-or para-quinonoid nature of the safranines has been examined, and several reactions lead to the detection of on!y one amino-group at a time in the phenosafranine molecule (monacid salts); thus not only can one amino-group alone be diazotised in solutions of medium acid concentration, but pheno- safranine condenses with one molecule of benzaldehyde ; whilst tetramethylsafrp nine unites with one molecule of methyl iodide. The absorption spectra of several derivatives of phenylphen-azonium have besn measured.219. Properties of mixtures of allyl alcohol, water, and benzene. Part 11.’’ By Thomas Arthur Wallace and William Ringrose Qelston Atkins. (Trans., 1912, 1958.) Pure allyl alcohol has D: 0.86911 and boils at 97.06O. It forms the following mixtures of constant boiling point: Alc oh01, per cent. Benzene, per cent. Water, per cent. Boiling point. 72.00 - 28-00 88‘00” 17.36 82.64 - 76.75 9’16 82.26 8-58 68-21 e The alcohol when mixed with water shows a large, and with n-propyl alcohol a slight, contraction in volume ; with benzene, however, there is a small expansion. The above data show that by distillation of the aqueous alcohol, and subsequent addition of benzene to the alcohol-water binary mixture, a pure anhydrous ally1 alcohol may be obtained in quantity.220. '' Some new diazoamino-and o-aminoazo-compounds.'' By George Marshall Norman. (TILLS.,1912, 1913.) Aminoazo-compounds have been obtained from 4 :4l-dibromo- and 4 :4~-dichloro-diazoaminobenzene by heating these compounds at 65O with excess of the corresponding amine and one molecule of its hydrochloride. 4 :4/-Dibromo-%-aminoazohenzene, C6E[,Br*N,*C6H3Br*NH,, forms red needles, m. p. 146-147'. 4:4~-Dichloro-2-ami~ioazo~enzene forms bright red plates with a green reflex, m. p. 140O. 3 :3~-Dibromodiazoarnino-p-tol.uene, CH3*CGH3Br*N3H*C6H3Br.CH,, crystallising in yellow needles, m. p. 11l0,could not be transformed into an azo-compound by heating with 3-bromo-p-toluidine and its hydrochloride.P -Naphthalenediasoamino-p-chlorobenzene, CGH,C1*N,H-C,,H7, crystallises in dark yellow needles, m. p. 156O. P-Naphthalenediazoamino-p-toluene, when heated with p-toluidine and its hydrochloride, gave a good yield of p-tolueneazo-;6-naphthyl-amine. o-Tolueneazo-&naphthylanzine, CH,*C6H,*Nz*C,,HB*NH,,forms long, dark red needles, m. p. 122O. It iS produced either by the action of o-toluenediazonium chloride on P-naphthylamine, or by the action of /3-naphthalenediazonium chloride on o-toluidine. m-Tolueneaso-P-naphthylamineis produced by the action of m-toluenediazonium chloride on P-naphthylamine. It crystallises in small, orange-red needles, m. p. 102O. By the action of P-naphthalenediazonium chloride on m-toluidine there is produced in small quantity P-naphthalenediazoamino-m-toluene, CH3*C,H,*N,H=C,,H,,which crystallises in thin, yellow plates, m.p. 183O. The action of nitrous acid on the azo-compounds, and of B-naphthol on some of the diazoamino-compounds mentioned, has also been studied. 233 221. '' The alkaline condensations of nitrohydrazo-compounds. Part 11." By Arthur George Green and Frederick Maurice Rowe. (TEUIS.,1912, 2003.) When bisnitrobenzeneazo-azobenzene (dinitrotrisazobenzene), NO2*C'6H4'N2'C6H,*N2'C6H4'N,oC6H,.N02, is reduced with phenylhydrazine and sodium hydroxide, it is con- ver ted into te t rak isazobenzene, *C6H,'N2*C6H,'# N*C,H,-N,*C,H;N . This is a red, granular substance of high melting point, which is the nitrogen analogue of Mikado-orange, and like this dyestuff it dissolves in concentrated sulphuric acid with a pure blue colour.The analogy between the condensations which give rise to bisnitro- benzeneazo-azobenzene and those by which the stilbene dyestuffs are formed, is thus confirmed. As a by-product in the reduction there is also produced the bisaminobenzeneazo-azobenzene, NH,~C6H4*~2~C6H,*N2*C6H,*h',.c6~,~NH,, recently described by Witt and Kopetschni (Ber., 1912, 45, 1147). This crystaliises from xylene in garnet-red crystals, which melt at 294O. 222. '(The absorption spectra of simple aliphatic substances in solutions, vapours, and thin films. Part I. Saturated aldehydes and ketones." By John Edward Purvis and Nial Patrick McCleland.(Trans., 1912, 1810.) A comparative study of the absorption spectra of various simple aliphatic aldehydes and ketones has been made in order to deter-mine in what direction, and how far, the absorption of light is affected when they are in different physical conditions. The pheno- mena are discussed from a consideration of the vibrations having their primary oscillations originating in definite oscillation centres. 223. '(The influence of certain salts on the dynamic isomerism of ammonium thiocyanate and thiocarbamide." By William Ringrose Gelston Atkins and Emil Alphonse Werner. (Trans., 1912, 1982.) In continuation of the work already published (Trans., 1912, 101, 1167), experiments have been made in the hope of obtaining evidence likely to throw further light on the reversible isomerism e2 234 of the above two conipounds.The action of heat on the com-pounds (CsN,H1),,KI, 111. p. 189O, (CsN,H,),,CsI, In. p. 19l0, and (CsN,H,),RbI, m. p. 302O, has been studied; in each case the equilibrium percentage of thiocarbamide was lowered, as compared with the normal 25 per cent. It was found to be about 14 per cent. in the case of the potassium iodide compound, and about 16 per cent. with the other two. The iniluence of the chlorides, bromides, and iodides of potassium, sodium, and ammonium on the reversion of t liiocarbamide and ammonium thiocyanate at 170° has been studied; sodium iodide differs from the other salts by effecting an almost complete reversion of thiocarbamide.The action of heat on the compound (CsN,H,),,KSCN has also been examined; in this case the normal equilibrium was not disturbed. Several new additive compounds of thiocarbamide with saline iodides have been prepared for comparative study. Whilst tetra- iriethylammoniurn iodide does not form a compound with thio-carbamide, ihe additive compound (CsN,H,),,NMe,EtI, m. p. 141°, was readily obtained. 224. 6i The molecular condition of some organic ammonium salts in bromoform.” By William Ernest Stephen Turner. (Trans., 1912, 1923.) In continuation of the author’s investigation (T~mzs.,1911, 99, 880), the molecular complexities of twelve salts of organic ammonium bases have been determined in bromoform. The results confirm bhe author’s previous conclusions based on the use of chloro-form as a solvent, and indicate that these salts are strongly associated, the extent depending on the character of the salt, on the concentration of the solution, and on the solvent employed, Associztion in bromoform is even more pronounced than in chloroform, and the conclusion is drawn that the probable cause is to be traced to the lower dielectric constant of bromoform.The effect of the solvent on the molecular weight differs, however, from salt to salt. 225. ‘‘The action of sodium methoxide on 2 :3 :4 :B-tetrachloro-pyridine. Part 11.” By William James Sell. (Trans., 1912, 1945. ) The action of sodium methoxide on 2 :3 :4 :5-tetrachloropyridine has been studied on a fairly large scale at) the ordinary pressure 235 in a flask heated by immersion in a water-bath, the experiments being conducted in two series, namely, (1) in which the sodium methoxide solution was of moderate strength, the main product being 3 :5-dichloro-2 :4-dimethoxypyridine ; no methyl ether was produced.(2) In which the sodium methoxide was of such strength 5s to solidify on cooling, and the only products were 3 :5-dichloro-4-hydroxy-2-methoxypyridineand methyl ether. The methyl ether is believed to be the product of the further action of sodium methoxide on the pyridine methoxide first produced, thus : (a) RC1t CH,-ON&= NaCl +RO-CH,. (b’) RO*CH3+ CH,*ONa=RONa +(C“H,),O. Some evidence is adduced as to the constitution of the chief products of this reaction, and it is indicated that at a temperature below the boiling point of water the 4-methoxy-group in the 3 :5-dichloro-2:4-dimethoxy-compound is converted into the hydroxy-group, but that it requires a considerably higher tempera- ture to effect the conversion of the methoxy-group in the 2-position.226. (( The preparation of glycogen and yeast-gum from yeast.” By Arthur Harden and William John Young, (Trails., 1912, 1928.) The method previously described for the preparation of pure glycogen from yeast (Trans., 1902, 81,1224) has been simplified by adopting the procedure of Pfliiger for the preliminary extraction and purification. By the process described, glycogen is obtained which contains no nitrogen and only 0.02 per cent.of ash. From the filtrate, after removal of the glycogen, yeast-gum is obtained as a white powder dissolving in water to a clear solution, which gives 110 red colour with iodine, produces a bulky, flocculent pre- cipitate when warmed with Fehling’s solution, and yields mannose when hydrolysed by boiling with acid. 227. Studies of Chinese wood oil. P-Elzeostearic acid.” By Robert Selby lorrell. (Tran~.,191.7, 2082 ) Further investigation of the glyceride produced when Chines6 wood oil is exposed to light seemed advisable in view of the diversity of opinion hs to the structure of elzostearic acid. The results obtained confirm many of the statements of previous investigators. P-Ekostcaric acid (m.p. 72O) and its glyceride (m. p. 61-62O) are stereoisomerides of a-elzostearic acid (m. p. 48O) and its liquid glyceride. With the exception of the potassium salt., the deriv- atives of the acid ahsork, oxygen with great rapidity, and in several 236 cases it was impossible to prevent oxidation before analysis. Oxida-tion of the potassium salt by alkaline perrnanganate gave n-valeric and azelaic acids, together with substances showing t,he pyrrole reaction. Tartaric and succinic acids could not be detected among the oxidation products. Ethyl &elzostearate (b. p. 232O/ 14 mm.) undoubtedly contains only two doubly-linked carbon atoms. The reactions of elaxstearic acid are best expressed by the constitutional formula proposed by Majima (Ber., 1909, 42, 674), namely, CH,*[CH,J,*CH:CH*[CH2]2*C’H:CH*[CH,],*C0,H, Preiiniinary investigations of the action of oxygen and air on the salts of 0-elzostearic acid have shown that the gain in weight depends on the nature of the salt.During the oxidation of the glyceride a change from crystalline to spongy character occurs without alteratian in colour. If the temperature is raised to looo there is a sudden change in colour and oxidation products (aldehydes and acids) are expelled. 228. “The constitution of camphene. Part I. The structure of camphenic acid.” By Walter Norman Haworth and Albert Theodore King. (Trans., 1912, 1975.) Aschan (Aimaleti, 1910, 375, 336) ascribes to camphenic acid the constitution (I); to dehydrocamphenic acid (11); and to the product of the oxidation of this with nitric acid, the lactonic acid formula (111): CH,*yH*CMe;CO,H CH,.~H-CMe,*CO,H QO2H I EH CH,*C*CMe,*CO,HYH2C:H,*CH*CO,H --+CH,*C*CO,H -+I >o UH2*C0 (1.1 (11.) (111.) By the aid of a Reforinatsky condensation between ethyl a-keto- glutarate and ethyl a-bromoisobutyrate, the authors have syn-thesised a lactonic acid having the constitution represented by (111), which, however, is not identical with the lactonic acid obtained by Aschan by the oxidation of dehydrocamphenic acid.Consequently, some modification of the above accepted structure (I) for camphenic acid must be adopted. ‘(229. Studies in phototropy and thermotropy. Part 111. Argl-ideneamines.” By Alfred Senier, Frederick George Shepheard, and Rosalind Clarke.(Ttanq., 1912, 1950.) The effect of light on the Schiff’s bases, which are phototropic at the ordinary temperature, has been studied at temperatures up 237 to their melting points, and some bases which are not phototropic at the ordinary temperature have been submitted to the action of light at lower temperatures in order to find out if they might not exhibit phototropy under such conditions. In the first case it has been found that whilst some Schiff’s bases are phototropic at tem- peratures up to their melting points, others have a limiting tem-perature, above which they are not phototropic; secondly, of the compounds examined at lower temperatures, two, namely, salicylidene -p -anisidine and 2-hydroxy-3-methoxybenzylidene-p-xylidine, were found to be phototropic.The colour changes which take place in salicylidene-b-naphthyl-amine (Senier and Shepheard, Trans., 1909, 96, 1950) have been further investigated, and it has been found that this compound is phototropic at the ordinary temperature, but that the darkm phototrope only changes very slowly into the lighter one. Salicyli-dene-fl-naphthylamine, similar to some other anils of this series, can be obtained in two forms, yellow and red, by varying the method of preparation, and it is now shown that these modifications are identical with the light and dark phototropes. To the list of phototropic Schiff’s bases already known, the follow- ing compounds have been added : salicyZiderLe-o-anisidine, disalicyli-dene-m-phenylenediamine, and 2-h~droxy-3-methoxybenzyZidene-p-zylidine, which have not hitherto been described, and salicylidene- aniline, salicylidene-o-bromoaniline, salicylidene-p-bromoaniline,and salicylidene-p-anisidine, already described, but with no mention hitherto of their phototropic properties. 230.“Studies of the constitution of soap in solution: sodium myristate and sodium laurate.” BY James William McBain, Elfreida Constance Victoria Cornish, and Richard Charles Bowden. (Trans., 1912, 2048.) The anomalous conductivity curve for sodium palmitate at 90° is closely paralleled by that of the very much more mobile sodium myristate solutions. The curve for sodium laurate is much less anomalous in that the maximum and minimum are obliterated. Only the degree, and not the position, of the abnormality in the curves is altered in passing down the homologous series from stearate to laurate. The conductivity curves of sodium myristate at a number of temperatures between 90° and 40° reveal a very high temperature-coefficient, which, however, is nearly uniform for a11 concentrations, so that the position and degree of development of maximum and minimum is largely unaffected.Finally, a number of qualitative observations closely bearing on the colloid theory of 238 soap solutions and ‘‘ supersaturation ” of gelatinisation are dis-cussed. The coagulation of a suspensoid or gelatinisation of an emulsoid does not appear to be connected with change in the degree of dispersion of the colloid in certain cases.231. (( The condensation of a-keto-p-anilino-up-diphenylethaneand its homologues with ethyl chlorocarbonate and thionyl chloride.” By Hamilton McCombie and John Wilfred Parkes. (Trans., 1912, 1991.) Some of the acyl derivatives of a-keto-P-anilino-up-diphenylethane were found by Everest and McCombie (T/.aizs., 1911, 99, 1746) to undergo condensation with ammonia to yield glyoxalines. In con- tinuation of this work, the authors have prepared the carbethoxy- derivatives of a-keto-P-anilinc&?-diphenylethane (I) and its homo- lopes. The carbethoxy-compound (I), when heated with ammonia in a sealed tube, was found to yield 2-keto-3:4 :5-triphenyl-2 :3-dihydro-oxazole (11), the ammonia merely acting as a hydrolysing agent. It was found that this oxazole could be prepared more conveniently from the carbethoxy-compound by the action of alcoholic potassium hydroxide, or directly from a-keto-P-anilino-a@ diphenylethane by the action of carbonyl chloride in presence of pyridine : gPh.8 €‘h>>ci., gPh*NPh>soCOPh*COPh*NPh*COPEt CPh--0 CPh---0 (1.1 (11.) (111.) The dihydro-oxazoles, which have been prepared, are found to be very stable towards acids and alkalis, they resist the action of reducing agents, and are not sufficiently basic to form salts.The reaction between thionyl chloride and a-keto-P-anilino-a& diphenylethane and its homologues was also investigated.In this case, the compounds obtained (111) were analogous to the oxazoles described above, having the CO-group replaced by the SO-group. The authors suggest the name oxasulphinazole for this new hetero- cyclic ring, so that compound (111) would be 3 :4:5-triphenyloxa-sulphinazole. Like the oxazoles, the oxasulphinazoles were found to be extremely unreactive. Attempts were also made to substitute sulphuryl chloride for thionyl chloride in this reaction, but no ring compounds were obtained, only chloro-derivatives of the original a-keto-B-anilino- afi-diphenylethane being produced. 239 ((232, Carbon disulphide as solvent for the determination of the ‘refraction constant.’” By Fri5dBric Schwers. (Trans., 1912, 1889.) Some new experiments have been made on the density and refrac- Live index of binary mixtures, and the results calculated according to the formula which was theoretically explained in previous papers.Measurements were made with mixtures of carbon disulphide with aliphatic acids (acetic, isobutyric, isovaleric) and alcohols (ethyl and isobutyl), and the refraction constant ‘‘ A ” was calcu- lated and compared with the value for the corresponding solutions in water. Some differences are to be noted between the two kinds of solutions, namely, (1) there occurs a dilatation of both density and refractive index in the case of carbon disulphide mixtures, and not a contraction as in the case of aqueous solutions; (2) the absolute values of “ A ” are much smaller than for the correspond- ing solutions in water; moreover, there does not exist an absolute proportionality between these A-values in carbon disulphide and aqueous solutions.On the other hand, solutions in carbon disulphide have important points in common with those in water, namely, (1) by comparing solutions of carbon disulphide with‘ the different terms of a series, it appears that “A” diminishes with the increase of the molecular weight ; (2) increase of temperature produces increase of “A ”; (3) the refraction constant diminishes from the red to the violet end of the spectrum. bi233. The electrochemistry of solutions in acetone. Part 11. The silver nitrate concentration cell.” By Alexander Roshdest- wensky and William Cudmore McCullagh Lewis.Employing a more sensitive form of capillary electrometer, further measurements have been carried out on the E.M.F. of concentra-tion cells coritaining silver nitrate in acetone. The E.M.F. values were found net to be affected by the interposition of a silver nitrate solution of a,ibitrary concentration ;and taking this into account along with results previously obtained, the conclusion is drawn that the Nernst formulz are applicable. On this basis the transport numbers of the ions of silver nitrate in acetone have been calcu- lated. Measurements have also been carried out with saturated ammonium acetate as the middle liquid. 240 234. “The influence of neutral solvents on velocity of reaction. Part 11.Transformation of anissynaldoxime in various solvents.” By Thomas Stewart Patterson and Harvey Hugh Montgomerie. The influence of neutral solvents on the velocity of transform* tion of anissynaldoxime into anisantialdoxime has been studied, the transformation being rendered apparent by a corresponding alteration in the rotation of ethyl tartrate used as an indicator. 235. “ The condensation of pentaerythritol with aldehydes.” By John Read (Trans., 1912, 2090.) The condensation products of pentaerythritol with a number of aldehydes have been made and investigated with a view to their resolution into enantiomorphously related isomerides. 236. ‘‘ The interaction of iodine and thiocarbamide. The properties of formamidine disulphide and its salts.” By Emil Alphonse Werner.Iodine and thiocarbamide interact in presence of an ionising solvent in accordance with the equation: 2CSN,H, +I, T-NH,*C(:NH)*S;C(:NH)*NH2,2H1 Formamidine disulphide hydriodide. The amount of the hydriodide of the base produced is inversely proportional to the concentration of the products when equilibrium is established, and directly proportional to the ionising power of the solvent. In presence of nitric acid a quantitative yield of the dinitrate, C2S2N,H6,2HN03, is obtained. Three final results can be realised under different conditions, namely, (1) quantitative formation of f ormamidine disulphide, (a) with concentrated solutions of the components, (b) in a high degree of dilution, and (2) a condition of equilibrium in which the base and thiocarbamide are present in equivalent proportions, c2s,N,H6 : 2CsN2H,.An additive compound, (CsN,H,),I,, is formed only when iodine and thiocarbamide are allowed to interact in presence of benzene or chloroform. It melts at 87O, and when brought in contact with water, or other ionising solvent, is converted into formamidine disulphide hydriodide (m. p. 81O). Claus’ compound, (CSN,H,),Cl, (Annalen, 1875, 179, 139), is the hydrochloride of the base. 241 The picrate (m. p. 154O), platinichloritle, and the compound C2S2N4H,,2€II,12are described. The action of potassium iodide in increasing the dissociation of the hydriodide, with generation of thiocarbamide and iodine, has been examined, and its influence on the estimation of thiocarbamide by N/lO-iodine solution is pointed out.The production of form-amidine disulphide by oxidising agents, such as potassium perman- ganate, nitrous acid, and hydrogen peroxide on thiocarbamide, only takes place in presence of strong acids, whilst with iodine the base is produced just as readily in neutral solution. An explanation of the probable mechanism of the interaction is given, which accounts for the formation of the base by the action of iodine under condi- tions different from those necessary with the oxidising agents menticned. 237. “The action of nitrous acid on thiocarbamide and on formamidine disulphide. A new structural formula of thio-carbamide.” By Emil Alphonse Werner. When nitrous acid and thiocarbamide interact., the change proceeds in two different directions according as a weak or a strong acid is present.In the presence of a weak acid the interaction is expressed by the equation CSN2H4+ HONO =HSCN + N, + 2H,O, as proposed by A. E. Dixon (Trans., 1892, 61, 526), with a strong acid present, formamidine disulphide, C2S,N,H, (Storch, Monufslz., 1890, 11, 452), is first produced thus: 2CSN2H4+2€ION01= C2S,N,H6 + 2NO + 2H20, and this is decomposed by further action of nitrous acid with production of thiocyanic acid and evolution of nitrogen. The changes have been studied quantitatively, and the secondary reactions, which takes place to a small extent in both cases, have been explained. Thiocarbamide can be used for the rapid and accurate assay of nitrites.To account for the different phenomena described, neither the symmetrical nor the unsymmetrical formula of thiocarbamide is sufficient, but a new formula, HN:C<yH3, is proposed, as5 probably representing the true structure of thiocarbamide in a neutral solution, or in presence of a weak acid. This formula shows a much closer connexion between thiocarb-amide and ammonium thiocyanate than the other two, and readily explains how the compound may give rise to derivatives of the symmetrical or unsymmetrical structure, under different conditions, f2 242 by the migration of an atJomof hydrogen in either of the dire~t~ions shown below : li Syniriietrical. Normal strncture.Unsymmetrical. (8.1 (cc. ) (c.) The change from (a) to (c) is determined by the presence of a strong acid or other strong negative reagent. 238. (‘The oxidation of some benzyl compounds of sulphur. Part I.” By John Armstrong Smythe. (Trans., 1912, 2076.) The comparative study of a number of benzyl compounds of sulphur has been undertaken. Oxidation is carried out with hydrogen peroxide in solution of glacial acetic acid. The simple monosulphidic compounds are converted quantitatively into higher oxy-derivatives, but the polysulphidic compounds suffer rupture. Benzy! disulphide yields benzyl disulphoxide, benzylsulphonic acid, benzaldehyde, and sulphuric acid, and the last three are among tho products of reaction of benzyl disulphoxide, benzyl mercaptan, and benzoyl benzyl sulphide.An explanation of this peculiarity is sought in the hydrolysis of the disulphoxide and subsequent reaction of the hydrolytic products. 239. (( The synthetical production of derivatives of dinaphth-anthracene.” By William Hobson Mills and Mildred Mills. Under the influence of aluminium chloride, pyromellitic anhydride condenses with benzene, forming a mixture of 2 :5-dibenzoyltere-phthalic acid and 4:6-diben~oylisop~~.thalicacid, as shown by the following equations : The constitution of these acids has been established by fusion with potassium hydroxide,, which decomposes them into benzoic acid, on the one hand, and terephthalic and isophthalic acids respectively on the other. When warmed with concentrated sulphuric acid, both of these acids lose two molecules of water and give rise to 243 This diquinone when reduced with zinc dust and alkali is con- verted into dihydrodinnphthanthracene (I); when heated with hydriodic acid and phosphorus it gives rise to two isomeric a-and 6-tetrahydrodinaphthanthracenes. CH, CO ,A/\/\/\/\ /\/’\/\/\AI1 I Ill I’ ’ \/\/’\/\/\/ \/\A/\/\CH, GO (1.1 (11.) a-Tetrahydrodinaphthanthraceneon oxidation is converted suc-cessively into dihydrodinaphthanthracene (I), dinaph thantl/ir.o?zr, C,,H6<~~2>C,,H,.and dinaphth.nnthrapuino?~~(11). The con-st,itution of dinaphthanthraquinone is established by the fact that, it is decomposed by sodium hydroxide into a mixture of benzoic and 0-naphthoic acids. 240.The preparation of durylic and pyromellitic acids.” By William Hobson Mills. The conditions are specified under which acetyl-$-cumene, which can readily be obtained in any quantity from $-cumene by the Friedel-Crafts reaction, can be converted easily and with a satisfac- tory yield into pyromellitic acid. The process consists in the trans- formation of the ketone by sodium hypobromite into durylic acid, and the subsequent oxidation of the latter with potassium perman- ganate. ‘6241. Organic derivatives of silicon. Part XV. The nomenclature of organic silicon compounds.” By Frederic Stanley Kipping. Some suggestions are made for systematising the nomenclature of different types of silicon compounds, more especially those described in the following papers.242. (‘Organic derivatives of silicon. Part XVI. The preparation I’and properties of diphenylsilicanediol By Frederic Stanley Kip ping. The hydrolysis of pure dichlorodiphenylsilicane under various conditions has been studied, and it has been found that the isolation of diphenylsil:canediol, SiPh,(OH),, from the product is an excep- tionally difficult task, partly owing to the readiness with which 244 the diol undergoes condensation, giving compounds which it adsorbs from solutions. Pure dipheiiylsilicallediol usually decomposes with effervescence at about 128--132O, but it is dimorphous, and in the neighbour- hood of its decomposition point it may pass into a more stable, crystalline modification, which does not decompose and effervesce until about 150-160O; this change seems to occiir always when the crxstals of the diol contain relatively small quantities of some of its condensation products, but seldom takes place when the compound is pure, so that impure specimens appear to have a much higher decomposition point than the pure substance.The isomeric ‘‘ diphenylsilicols ” described by Martin (Rer., 1912, 45, 403) as melting at about 140° and 160° respectively were prob- ably impure specimens of diphenylsilicanediol, and the methods which he gave for the conversion of these supposed isomerides into one another do not bring about any isomeric change. 243. (‘Organic derivatives of silicon. Part XVII. Some condensa-tion products of diphenylsilicanediol.” By Frederic Stanley Hipping.Diphenylsilicanediol very readily undergoes condensation in presence of acids or alkalis, and in the preparation of the diol from dichlorodiphenylsilicane by different methods, various oily or glue-like products are obtained in considerable quantities. These products are usually mixtures of three or more compounds, which are formed from the diol by a process of condensation, and of which the following four have so far been isolated: HO*SiPh,*O* SiPh,*OH HO*SiPh,*O *SiPh,*O*SiPh,*OH (1.)Anfiyclrobisdipheriplsilicanediol. (11.)Dinnhydrotrisdiphenylsilicanediol. o<SiPSiPb,-Oh, 0>SiPh (111.) Trianhydrotrisdiphenylsilicanediol. W.)Tetra-anhydrotctrakisdiphenylsilicanediol. The conditions under which these four condensation products are obtained from the diol have been studied, and also methods for the conversion of the two hydroxy-compounds (I and 11) into their respective anhydro-derivatives (IV and 111).The results of these and of further experiments which are in progress may throw some light on the constitutions of the complex mineral silicates. 245 244. ‘(Organic derivatives of silicon. Part XVIII. Dibenzyl-silicanediol and its anhydro-derivative.’’ By Robert Robison and Frederic Stanley Kipping. The further study Gf the compounds described as a-dibenzyl-silicol and @-dibenzylsilicol (Trans., 1908, 93,441) has shown that the former is a dibenzylsilicanediol of the constitution si(CH2*C6H,),( OH),, whereas the latter is an anhydrob isdibenzylsilicanediol of the con- stitution HO*Si(CH2*C,H5)2*O~Si(CH2~C6H5)2~OH,crystallised with one molecule of water; although, therefore, the two compounds have the same composition they are not isomeric.Dibenzylsilicanediol is the primary product of the hydrolysis of dichlorodibenzylsilicane, and methods for the preparation of the pure diol are described. When heated, or when treated with various reagents, dibenzylsilicanediol undergoes condensation, yielding products from which anhydrobisdibenzylsilicanediol and trianhydro- trisdibenzylsilicanediol may be isolated, the former in hydrated crystals. These hydrated crystals lose their water at looo, and give anhydrobisdibenzylsilicanediol as a viscid oil, which is so very hygroscopic that it passes into the hydrated crystals on exposure to moist air.245. ‘‘ Organic derivatives of silicon. Part XIX. The preparation and properties of some silicanediols of the type SiR,(OH),.” By Robert Robison and Frederic Stanley Hipping. Phenyte th ylsilicanediol, SiPhEt(OH),, benzylethytsilicanediot, SiEt(CH2*C6H5)(OH),, and phenylb enzylsilicanediol, SiPh(CH2*C6H5)(OH),, may be obtained by carefully hydrolysing the corresponding disub- stituted dichlorosilicanes with an aqueous solution of ammonium hydroxide. These three crystalline compounds, like diphenyl-silicanediol and dibenzylsilicanediol, give soluble derivatives with solutions of the alkali hydroxides; they are all very easily changed by heat and also by various reagents, giving oils which are doubtless mixtures of their condensation products.formed when purified phenylethylsilicanediol is kept at the ordinary temperature, and also when an aqueous solution of the last-named compound is treated with a very little dilute hydrochloric acid. 246 246. The purification, density, and expansion of ethyl acetate.” By John Wade and Richard William Merriman. Defects in the methods of preparing dry esters, used by previous workers, are pointed out and overcome. The density at Oo compared with water at 4O was found to be 0-92454, which is higher than the values obtained by Perkin (Tram., 1884, 45, 492), and by Young and Thomas (Tmics., 1893, 63, 1216).Reasons for this difference are given. Taking the specific volume at Oo to be unity, the specific volumes at loo, 20°, and 30° were found to be 1.01301, 1.02663, and 1.04080 respectively. A method of using a Dewar vacuum vessel as a constant-temperature bath is described. 247. ‘‘ The vapour pressure of ethyl acetate from 0” to loo”.” By John Wade and Richard William Merriman. For temperatures above 15O the boiling point of ethyl acetate was determined at constant pressure in the manner previously described by the authors (Trans., 1911, 99, 989). At each pressurc a complete fractionation of 100 grams of pure ester was made, the temperature recorded being that at which A per cent. was a maxi- mum (Wade, Trans., 1905, 87, 1656).At looo the pressure found was 1536 mm., as compared with 1515 mm. obtained by Young and Thomas (Trans., 1893, 63, 1216). Reasons are advanced for regarding the new value as correct. Below a pressure of 900 mm. the agreement with Young and Thomas is almost perfect. A new method was used for finding the vapour pressures below 15O. 248. L‘Halogen derivatives and ‘refraction constant.’ ” By Fr6dBric Schwers. The anomalies with regard to the “ refraction constant ” shown by mixtfires containing a halogen derivative have been sub-mitted to a closer investigation. It appears that the irregular behaviour (a compared with other mixtures) of the Cv and C, curves is related to the number of halogen atoms, and affects the density much more than the refractive index, which shows more regularity.Particularly curious are the mixtures alcohol-chlorof orm and acetone-chloroform ; their density varia- tions are positive for certain concentrations and negative for others, whereas the refraction changes in quite a different manner and in the most regular way. Interesting is the fact that mixtures of halogen derivatives with fatty acids do not show the same pheno- mena. For the explanation of the observed phenomena, the hypo- thesis of an atom nucleus with variable volume (Richards) seem? more necessary than ever. The following communication has been received during the vacation : 6i249. Bimolecular glycollaldehyde. A correction.” By Nial Patrick McCleland. The author regrets that a mistake was allowed to pass unnoticed in the akove paper (Trum., 1911, 99, 1827): Af -60-.On p.1829, line 17, for C-6o should be read C = hO ‘W/2 \Vitli this alteration the values of X: become (i) 0.00140 not 0*00210. (ii) 0.00196 ,, 0.00303. (iii) 0.00381 ,, 0.00561. the variatioii front tlie mean value in only one instance exceeding 4 per cent. This alteration in no way affects tlie conclusions arrived at in tlie paper. At an Extra Meeting of the Chemical Society, held in the Large Theatre of Burlington House (by the kind permission of His Majesty’s Office of Works) on Thursday, October 17th, 1912, at 8.30 p.m., Professor Percy F. Frankland, LL.D., F.R.S.,President, in the Chair, Sir Oliver Lodge, D.Sc., F.R.S., delivered the Becquerel Memorial Lecture.A vote of thanks to Sir Oliver Lodge, proposed by Sir William Crookes, O.M., F.R.S., and seconded by Professor H. E. Armstrong, F.R.S., was supported by the President and carried with acclama- tion. Thursday, November 7th, 1912, 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 : 248 On August 7th, 1912, of Mr. Robert Holford MacDowall Bosan- quet, F.R.S. (who was elected a Fellow on February 2nd, 1865); On August 15th, 1912, of Dr. H. 0. Jones, F.R.S.; and of Dr. John Wade. The PRESIDENTread the following Address, which had been presented to the Royal Society on the celebration of the 250th Anniversary of its Foundation in July, 1912 : THE CHEMICAL SOCIETY TO THEPRESIDENT, COUNCIL, -4ND FELLOWSOF THE ROYALSOCIETY.GREETING, Amongst the many Learned Bodies represented here to-day there is certainly none which can wish to offer you more sincere and heartfelt congratulations than the Chemical Society. The Officers, Council, and Fellows of our Society desire to asso-ciate themselves with you in celebrating the Two-hundred-and- fiftieth Anniversary of the birth of a scientific corporation which in the distinction of its history is assuredly second to no similar body in the World. The great army of diligent and determined workers who are united by the solemn covenant to extend Man’s knowledge of Nature look with reverence and gratitude on the Society which, during two and a-half centuries, has kept alive in these Islands the sacred fire of Research, and has included within its Fellowship men whose names and achievements are amongst the most imperishable glories of the human race.We desire to take this opportunity of expressing, however imper- fectly, our indebtedness to the Society of Boyle, of Cauendish, of Priestley, of Dulton, and of Dovy, and we are proud to remember that these early masters of our Science, by the stimulus which their investigations gave to the growth of Chemical Knowledge, led to the origin of our Society by a natural process of gemmation from your body. It.is, therefore, in the capacity of children, and as an act of filial piety, that we desire to offer to you, our parents, dutiful felicitations to-day.We would take this opportunity again of gladly and freely acknowledging before all men that whatever success our own Society may have achieved, whatever may be the dignity to which we have attained, and whatever service to Science and to Mankind we may have been privileged to perform, we largely owe to the 249 inspiration which our founders drew from the magnificent tradi- tions of the Royal Society. This quickening influence has been, and, we trust, may long be, maintained by a close association with you, by the community of Fellowship which exists between your Society and ours, and by the kindred ideals and aspirations which animate us both.Signed on behalf of the Chemical Society, PERCY President.F. FRANHLAND, ALEXANDERSCOTT,Treasurer. ARTHURW. CROSSLEY,) Secretaries.SAMUELSMILES, HORACE Foreign Secretary. T. BROWN, Sealed in Council this Twentieth Day of June, One Thousand Nine Hundred and Twelve. It was announced that, during the vacation, the rooms of the Society had been redecorated throughout, and that a fan had been installed with the object of securing more efficient ventilation in the Meeting Room. Messrs. T. V. Barker and W. E. Hawkins were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : James Henry Young Baker, 86, Chestnut Avenue, Hamilton, Ontario. Douglas Anderson Bowack, 15, Belsize Square, Hampstead, N.W.Richard Westman Challinor, Quidington, Emmerick Street, Leichardt, Sydney, N.S.W. Frank Andrew Coombs, Sydney Technical College, Sydney, N.S.W. Walter Henry Dixon, 51, High Street, East Grinstead. H. H. Dodds, M.Sc., Explosives Works,. Umbogintwini, Natal. George Davidson Elsdon, B.Sc., City Analysts’ Laboratory, Birmingham. Harold Heath Gray, B.Sc., University Hall, More’s Gardens, Cheyne Walk, Chelsea, S.W. Ardesir Naserwanji Peston Jamas, M.A., B.Sc., Karrim Build- ing, Grant Road, Bombay. Edgar Jobling, B.Sc., H.M. Patent Office, Southampton Build- ings, W.C. Frederick Russell Lankshear, B.A., M.Sc., Dalton Hall, Victoria Park, Manchester. Stanley Isaac Levy, B.A., B.Sc., St.John’s College, Cambridge. Ernest Lawson Lomax, &I,Sc., Mowbreck, Parington, Preston. 250 George Francis Morrell, Ph.D., B.Sc., 7, Claylands Road, Ken- nington Gate, S.W. Ernest Moore Mumford, B.Sc., 75, High Street, Chorlton-on- Medlock, Manchester. Leslie Frank Newman, B.A., Downing College, Cambridge. William Moore Nichols, 17, Ferrybridge Road, Castleford. Maximilian Nierenstein, Ph.D., 30, Cavendish Road, Henleaze, Bristol. Lionel Orange, B.Sc., 148, Barkworth Road, N. Camberwell, S.E. John William Patterson, 88, Park Road, West Dulwich, S.E. Charles Etty Potter, B.Sc., 9, Church View, Church Lane, Heckmondwike. Jitendra Nath Rakshit, 11/1, Bahar Urijapur Road, Calcutta. Martin Remers, L.R.C.P., L.R.C.S., 24, Chorley Old Road, Bolton.Albert Sasson, Department of Agriculture, Alexandria, Egypt. Harold Archibald Scarborough, B.Sc., 60, Highbury Terrace, Hill Street, Coventry. Walter Scott, 2, Wordswortli Avenue, Cardiff. Kunjo Behary Seal, 5, Nilmony Dutt Lane, Calcutta. Cyril Edgar Sladden, B.A., 12, Charleville Circus, Sydenham, S.N. Thomas Alfred Smith, B.Sc., 3, Colegrave Street, Lincoln. William Charles Smith, Church Lane, Lowton, Newton-le-Willows. Victor Steele, 438, New Cross Road, New Cross, S.E. Alfred Ernest Stephen, Bank of New South Wales, Sydney, N.S.W. William Compton Till, M.Sc., Barnacle House, Coventry. Paul Jenner Ure, c/o Dr. Ure, George Street, Brisbane, Queens- land. Of the following papers, those marked * were read: *250. Aniline-black and allied compounds.Part 111,” By Arthur George Green and Salomon Wolff. The authors have studied the action of various primary amines on nigraniline. They find that this base, when in a finely-divided state, reacts readily in the cold with neutral or weakly acid solutions of amine salts, giving compounds in which one molecule of amine has entered into combination with one molecule of nigraniline. The products obtained are represented as monoaryl- azonium compounds of the constitution : N--NR NH NH NH/v\/\/\/\//\ /)A/\ /‘\/\AII II 251 In their formation a portion of the quinonoid groups has under- gone reduction, and the product resembles protoemeraldine in char- acter, although considerably blacker in colour.By treatment with hydrogen percxide or chromic acid, by which the compound is reoxidised to a higher (probably tri-) quinonoid stage, it is enabled to react again with a further quantity of a primary amine; and on several repetitions of these alternate treatments three molecules of amine can eventually be introduced. At this stage the product (when aniline is the amine employed) has all the properties charac- teristic of "ungreenable aniline-black " produced on the fibre in the usual way. The analyses and properties agree with the con- stitution : N----NPh N---NPh N--Nl'h NH /'\/\/'\~\/\/\/',~\,/\/\/\/\/\/\/\I 11 IIIII \/ \/\/\/ \Ad\/ \/>/\/ dNH2 By employing p-bromoaniline in place of aniline, the correspond- ing tribrominated aniline-black, of very similar properties to the above, was obtained, the analysis of which substantiated the above formula.Monoarylazonium compounds were also prepared and analysed, in which the reacting amines were o-toluidine, p-toluidine, m-bromo- aniline, 8-naphthylamine, tolidine, and diaminodiphenylmethane. 1\11 these products are very similar to the aniline condensation product. *251. '* The alkaline condensation of nitrohydrazo-compounds. Part 111. Influence of ortho-groupson their formation and condensa- tion." By Arthur George Green and Frederick Xorris Rowe. The presence of sulpho- or nitro-groups in the ortho-position with respect to basic nitrogen prevents or impedes the normal reactions; thus 2 :4dinitroaniline and p-nitroanilinesulphonic acid cannot under ordinary conditions be oxidised to the azo-compounds, nor can their corresponding hydrazines be condensed with chloronitro- compounds to give hydrazo-compounds, except with the extremely reactive picryl chloride. A search for the cause of this impeding action, which is the exact reverse of that observed in the derivatives of pnitrotoluene, pointed to its being due to the occurrence of condensation between the basic nitrogen group and the o-nitro- or o-sulphonic group.This was confirmed by the observation that when o-nitroaniline is oxidised with hypochlorites in alkaline solution it is converted entirely into benzisooxadiazole (benzfurazan) 252 oxide (“ dinitrosobenzene ”) (see following abstract), whilst the normal oxidation to 2 :2/-dinitroazobenzene only occurs when strictly neutral conditions are maintained, that is, when isomerisation of the nitroamine into its quinonoid form is prevented.A similar condensation appears to occur when the hydrazo-com- pounds containing o-nitro-groups are treated with alkalis, and con- sequently the blue quinonoid salts of these compounds are very unstable. The conditions of formation and reaction were studied for the following azo- and hydrazo-compounds : The 2 :2’-dinitro-, 2 :4 :21 :41-tetranitro- and 2 :2/-dichloro-4 :4/-dinitro-azobenzenes; the 2 :2/-dinitro-, 2 :4 :4/-trinitro-, 2 :4 :2/ :4’-tetranitro-, 2 :4 :6 :4/-tetra-nitro-, 2 :4 :6 :2’ :4’-pentanitro-, 2:4 :6 :2’ :4/:6/-hexanitro-, and 2 :2/-dichloro-4:4/-dinitro-hydrazobenzenes. *252.‘‘The existence of quinonoid salts of o-nitroamines and their conversion into oxadiazole oxides.” By Arthur George Green and Frederick Morris Rowe. In the course of the previous investigation it was observed that when o-nitroaniline is oxidised with hypochlorites in strongly alkaline solution it is quantitatively converted into the compound hitherto known as “ dinitrosobenzene ” or o-benzoquinonedioximeI‘ peroxide.” This reaction, together with several other considerations, has led the authors to believe that the compound and its analogues are more correctly represented as benzisooxadiazole (benzfurazan) oxides, and that the change takes place thus: .. .. ..0 0 0 This formula for the product involves no migration of an oxygen atom, either here or in Zincke and Schwartz’s method of formation from o-nitrotrisazobenzene.If its correctness is admitted, the reaction affords strong support for the existence of mi-quinonoid salts of o-nitroamines, and this conclusion is still further strengthened by the observation that o-nitroaniline dissolves in alcoholic potassium hydroxide with an orange-red colour, and that the oxidation in neutral solution takes an entirely different and more normal course, giving 2 :2/-dinitroazobenzene : The formation of benzisooxadiazole (benzfurazan) oxides by alkaline oxidation of o-nitroamines appears to be a general one, and affords a convenient method of preparing these compounds.253 “253. “The essential oil of cocoa.” By James Scott Bainbridge and Samuel Henry Davies. The authors find that the aromatic principle of the cocoa bean is an essential oil. Two thousand kilos. of cocoa nibs were subjected to distillation with steam. From the distillate 24 C.C. of a purified oil were isolated, which proved to be a mixture of esters formed during the fermentation of the cocoa bean with the true essen€.ial oil. The latter consists chiefly of a d-linalool. Octoic acid and other fatty acids probably derived from cocoa-buther were present, and a small proportion of a stable nitrogenous compound, which was not identified. *254. (‘Studies in chemical crystallography. Part I. Co-ordination, isomorphism, and valency.” By Thomas Vipond Barker.Some new cases of isomorphism of unusual types were described, the bearing of which on chemical and crystallographic theory was discussed. The conclusion was drawn that the ordinarily accepted theory of valency structure is incapable of offering any useful information concerning the structure of the compounds in question. Ceordination structures, on the other hand, bring out pronounced chemical analogies, from which it is inferred that such structures are not only supported by the crystallographic evidence, but also are more gmeral in inorganic compounds tha,n was formerly sus-pected. The theories of Sollas and of Barlow and Pope were criti- cised from the point of view of isomorphism, and the conclusion was drawn that Barlow and Pope’s theory in its present form is certainly incapable of general application to inorganic compounds.The view is entertained that the true volume unit in crystalline structures is the atomic rather than the valency volume. *255. “ The oxidation of aconitine.” By Francis Howard Carr. It was shown that a neutral substance, oxonitin, C,,H,O,N, together with acetaldehyde, results from the oxidation of aconitine with potassium permanganate in acid solution. Oxonitin crystal- lises in white, prismatic crystals, m. p. 276-277O; it is sparingly soluble in all solvents, neutral in reaction, and does not combine with acids or alkalis, nor does it give a precipitate with the common alkaloidal reagents. Methyl iodide, hydroxylamine, and acetic anhydride fail to act upon it.It contains three methoxyl groups, and since it gives, like aconitine, acetic and benzoic acids on hydrolysis, it coiitains also an acetyl and beiizoyl group. It, tnay he presumed that the N*CH,-group contained in monitine is unchanged ;its constitution may therefore be represented thus : C,~,€190,NMe(OBz)(OA4c)(OMe),. Oxonitin yields different products according as the hydrolysis is brought about by alkali or by hydrocliloric acid; in the former case a neutral substance, and in the latter an alkaloid, is produced; in both instances acetic and benzoic acids are formed. The investiga- tion is being continued with a view to the elucidation of the consti- tution of the hydrolytic substances and of the hypothetical base, C,,HI,OIN.DISCUSSION. Rlr. BEADYsaid that he had been working 011 the compound described for some time, but had not been able to establish the presence of the acetyl group, and inquired how the author had identified it. 256. (( Some time-reactions suitable for lecture experiments.” By William Gerald Glendinning and Alfred Walter Stewart. In concentrated solution, potassium iodide, potassium persulphate, and starch react practically instantaneously, producing starch-iodine blue. When sodium thiosulphate is also present, the appear- ance of the colour takes a longer or shorter time according to the amount of thiosulphate added. When carried out in the way described below, the reaction forms a simple demonstration of induction periods.The solutions required are M/5-potassium iodide, ,V I 10-thio-sulphate, a saturated solution of potassium persulphate, and some starch solution. A burette is filled with the thiosulphate solution and fixed over a vessel into which are placed 10 C.C. of the iodide solution, 5 C.C. of the persulphate solution, and 5 C.C.of the starch solution. The starch-iodine blue is formed immediately, and is exactly removed by the thiosulphate. If three extra drops of the thiosulphate are added, the blue colour will not return until a lapse of sixty-three seconds; and if six or nine drops be used, the period is correspondingly prolonged. In more dilute solutions, of course, much longer intervals are obtained. In order to avoid error in timing, due to adding the thiosulphate drop by drop, the following device may be employed.A T-piece is passed through a loosely-bored cork, which is clamped above the vessel used for the reaction in such a way that the T-piece lies liorizontally. A second cork with a flat side cut on it is fixed 255 firmly on the straight end of theT-piece. The requisite number of drops of thiosulphate solution are then dropped on to a microscope cover glass, which rests on the flat cork; and when it is necessary to add this to the solution, the T-piece is turned round in the bore of the cork so that the cover glass drops off the flat side into the reaction vessel, In this way the whole of the thiosulphate can be added at once.An ordinary square cover glass will retain ten drops easily if care is taken. The quantities given above are sufficient to allow of the succes- sive addition of three, six, and nine drops of thiosulphate solution without exhausting the other reagents to an undue extent. Two modifications of the above reaction are as follows: A solution of hydrogen peroxide may be substituted for the persulphate solu- tion, the rest of the reagents remaining the same. In this case, if several titrations have to be carried out with the same solution, it is advisable to add some fresh starch each time the solution is rendered colourless, as otherwise a good tint is not obtained. Using 2 C.C. of potassium iodide solution, 10 C.C. of hydrogen peroxide solutioii (approximately 20 volumes), 8 C.C.of starch solution, and 50 C.C. of water, when three drops of thiosulphate solution are added the colour appears after about half a minute, the reaction being much more rapid than when potassium persulphate is used. Instead of using hydrogen peroxide itself, a saturated solution of barium peroxide may be employed; but in this case certain modifications are necessary. The method of working is as follows: The barium peroxide solution is placed in the reaction vessel, and to it some phenolphthalein is added. Sufficient hydrochloric acid to decolorise the phenolphthalein is poured in; and then the starch and potassium iodide are added. The starch-iodine blue is decolor- ised with thiosulphate as before, and a small excess of thiosulphate added. Should the liquid show any signs of becoming alkaline, as can be seen from the phenolphthalein tint reappearing, a few drops of hydrochloric acid are added.It is inadvisable to have a large excess of acid owing to its effect on the thiosulphate solution. 257. '' The problem of strong electrolytes. (Preliminary note.) " By James Kendall. The dissociation formula m2/(1 -m)v=k+c. (1-m)/m has been recently shown by the author from experimental results (Trans., 1912, 101, 1275) to hold for all acids. The above formula may be arrived at theoretically by the assumption of the presence of complex ions of the type (Re)'' or (X2)//in the aqueous solution of 256 an electrolyte RX. This is already known to be the case for mercurous chloride, which ionises as (Hg2)*o(Cl’)2.The equations for equilibrium, under the assumption of one complex ion, are of the form: fzX Rj’+X’ (1) 21:X (R2)”+ 2X‘ (2) Let the undissociated ratio at dilution v be 1 -m ; of the total dissociated part m I& m, in the case of one ion, be complex. Then, applying the law of mass action ‘to the balanced equations (1) and (2) above, we obtain: (m/v). [(m--n)/v]=k.(1-m)/v (3)(n/Zv).(m2/2’2)=(c/2).(1 -m)?/.Z (4)9 where Ic and c/2 are constants. From equation (4) we have n,=cv(1-m)2/m2; substituting for n in (3) we finally arrive at the equation: m2/(1-rn)v=k+c. (l-m)/m (5), already found by experiment to hold in the case of all acids. By the assumption that the ions form complexes of the above type in aqueous solution, the above dissociation formula, first obtained experimentally for acids only, may be extended to cover all uni-univalent elactrolytes.258. ‘(Action of semicarbazide hydrochloride on the p-quinones. (Preliminary note.) ” By Isidor Morris Heilbron and James Alexander Russell Henderson. Thiele and Barlorn (Annalen, 1898, 302, 315) and Borsche (ibid., 1904, 334, 143) have already examined the action of semicarbazide hydrochloride on p-benzoquinone and on sonie of its deriva.tives, and found that the compounds formed gave phenols on treatment with sodium hydroxide. They suggest that the condensation products exist in tautomeric forms as seinicarbazones (I) and p-hydroxyazoformamides (11): O:/=\N*NH-CO-P~’H, HO/’-\N:N-CO*NH,\=/ \-/(1.1 (11.) It seemed, however, to the authors that further evidence was necessary to decide the true constitution of the free condensation products.A spectrographic investigation has been made of the substances obtained by the act)ion of semicnrbazide hydrochloride on various pquinones, as well as of the salts and esters of these products. The absorption curves of all the products are very similar, and practically identical in shape and position to those obtained by Tuck (Trans., 1907, 91, 449) for the p-hydroxyazo- compounds. The p-quinone condensation products with semicarbazide hydro- chloride are theref ore true hydroxyazo-compounds of the type (11). The investigation is at present being extended to other similar types of compounds. 259.L'The interaction of azoimide and nitrous acid. (Preliminary note.)'' By Emil Alphonse Werner. Whilst the decomposition of hydrazine by nitrous acid constitutes one of the numerous methods by which azoimide may be obtained, the further action of nitrous acid on azoimide does not appear to have been hitherto examined. When a solution containing sodium azide and sodium nitrite is treated with dilute sulphuric or acetic acid, interaction immediately takes place with brisk evolution of gas, consisting of nitrogen and nitrous oxide. The change takes place in accordance witb the equation: N3H+ =NO2 =N, +N20+H20, and even with very dilute solutions the reaction is completed in a few minutes.This interaction may be made the basis of a simple and rapid method for the analysis of azides, either by carrying out the decom- position in a nitrometer and measuring the volume of evolved gas, or by titration of a dilute solution of the azide, previously acidu- lated with dilute sulphuric acid, with a iT/10-solution of sodium nitrite. The following results were obtained with a sample of commercial sodium azide (Schuchardt) in a preliminary trial. I. 0.05 gram of the azide and 0.06 gram of sodium nitrite (95 per cent.) dissolved in 1.5 C.C. of water were introduced irto a nitrometer, and 0.5 C.C. of dilute sulphuric acid was added, Gas evolved=33.55 C.C. (dry) at Oo and 760 mm. 0.05 Gram of pure sodium azide requires 34.46 C.C.Hence, 97.35 per cent. of pure sodium azide was present in the sample. 11. A solution was prepared by dissolving 1 gram of the sodium azide in 100 C.C. of water. Ten C.C. diluted with 70 C.C. of water, and 2 C.C.of dilute sulphuric acid (1 :7) added, were titrated with a NjlO-solution of sodium nitrite (1 c.c.=O*OO65 N3Na) until a drop of the solution after being well stirred gave an immediate blue colour with starch and 258 potassium iodide solution: 15 C.C. of the sodium nitrite solution were required. Hence, 97.5 per cent. of pure sodium azide was present in the sample. The latter result is very probably the more accurate, as a small quantaity of nitrous oxide is likely to remain in solution in the nitrclmeter method. It is intended to test the method more fully with some pure azides.260. ‘‘Benzylmethyl-, benzylethyl-, and allyl-ammonium nitrites. ” By Prafulla Chandra Riy and Rasik La1 Datta. Benzylmethylammonium nitrite has been obtained in solution only by the double decomposition between silver nitrite and the amine hydrochloride. During the process, minute drops of an oily liquid make their appearance and float on the surface. After the end-point is carefully attained, the solution is left to remain, when within a short time the oil increases considerably, and settles down in globules at the bottom of the vessel. The oil was found to be a iiitroso-compound, and analysis proved it to be henzylmethylnitroso-amane. Found : C =-63.54 ;H =6-79;N =18.36.C,H,,ON, requires C =64.00 ;H =6-66;N =18.66 per cent. The supernatant liquid was examined from time to time, and found to respond to the nitrite reaction. Evidently after the con- version of t,he greater portion of the nitrite into the nitroso-com- pound a process of equilibrium sets in, thus: CiH,.NHMe,HNO, Z? C,H7*NMe*N0+H,O. Ilurlzyl~tl~ylanzronizlrnnitrite has been obtained by the usual method as a pale yellow, crystalline substance. Found : C =59.02 ;H =7-83;N =15.45. C,H,,O,N, requires C= 59-34;IT,=7-69;N =15-38 per cent. The salt sublimes at 50--55O with simultaneous decomposition, althouah it begins to decompose slowly at the ordinary temperature (24O) ?n a vacuum. The sublimate consists of white, glistening crystals.The products of decomposition are nitrogen, a nitrow compound, and alcohols, according to the equations : CgH,,O,N,,= C,H,*OH +C2H,*OH+N,. CgHl,02N, =CiH,.NEt*NO +H,O. Allylammoriiunt nitrite prepared similarly is a brown, viscid liquid, having the characteristic odour of alkylammonium nitrites. Found : C= 34-82;H =8-05;N =27.15. C3H80,N, requires C= 34.62 ;H =7.69 ;N =26.92 per cent. The salt decomposes in a vacuum into nitrogen and ally1 alcohol. 261. ‘‘Note on the action of ethylene oxide on hydrazine hydrate.” By Edward de Barry Barnett. R7hen ethylene oxide is added to a large excess of well-cooled hydrazine hydrate, a brisk reaction takes place with evolution of heat. After distilling off th‘e excess of hydrazine, an oily residue remains, from which two substances can be separated by repeated fractionatioa in a vacuum. P-H?/droxyet~ylhydr~~~r~e, is the inah pro- HO*C,H4*NH*KH2, duct of the reaction, and forms a colourless, very viscous oil, which boils at 119--120°/9 mm.: 0.2628 gave 0.3034 CO, and 0.2560 H20. C=31.5 ;H= 10.8. 0.1378 ,, 44.0 C.C. N2 at 18O and 756 mm. N=36.7. C2H,0N, requires C =31.6 ;H =10.5 ; N =36.9 per cent. It at once combines with formaldehyde with evolution of heat to form a (*ompuu/[d,C,H,ON,, which crystalliscs from alcohol in colourless needles melting at 224O : 0.2058 gave 0.3610 GO, and 0.1556 €&O. C -=47.8 ;H =8.4. 0.1010 ,, 23.8 C.C. N, at 15O and 762 nim. N=27.7. C’,H,ON, requires C =48.0 ;H r= 8.0 ;N =28.0 per cent.Di-j3-hydroxyethylhydrazine, [HO*C,H,.NH*], or (H0 C, H4) N NH, (Found, C=39*7 ; H =10-1. Calc., C=40*0; H=10.0 per cent.), forms a colourless, very viscous syrup, which boils at 171°/10 mm. It is probably identical with the as-di-P-hydroxyethylhydrazine described by Knorr and Brownsdon (Bey., 1902, 35, 4474) as boiling at 188-190°/25 mm. 262. “Note on the hydrolysis of acetic anhydride.” By James Charles Philip. In coiinexion with Orton and Jones’s paper on this subject (7’mns., 1912, 101, 1708), the results of some preliminary experi- ments made a few years ago in the author’s laboratory were described. The coursp, of the reaction between acetic anhydride and water in glacial aceti:: acid solution was followed by determining thG freezing point from time to time. As the anhydride and water progressively combine, the freezing point rises steadily until, when one or other of the two substances has disappeared, it reaches a constant value.If the acetic anhydride and water were taken in equivalent proportion, this final constant value would be the freezing point of absolute acetic acid. In reality, the depressions recorded at successive intervals am not strictly comparable, for as the reaction proceeds the quantity 260 of solvent increases-by about 3 per cent. from beginning to end in the actual experiments. It would be quite possible to allow for this in evaluating the velocity-coefficient, but, in view of the preliminary character of the work, no correction was applied.When a mixture of acetic acid, acetic anhydride, and water had been prepared, portions were transferred to tubes of special resist- ance glass, which were then sealed up and immersed for different periods in a water-bath kept at a constant temperature. Each tube, on being taken out of the bath, was rapidly cooled, and the freezing point of the contents was determined immediately. The acetic acid used was obtained by repeatedly freezing out the pure commercial acid, and had a freezing point of 16.42O (corr.). It still contained a trace of water, the amount of which was deter- mined by adding a slight excess of acetic anhydride, and heating samples of the mixture in sealed tubes until no further change in freezing point was observed; thus, in one estimation, 0.939 gram of pure anhydride was added to 68.154 grams of the acetic acid with freezing point 16'42O; a sample of this mixture, heated at looo for fifteen hours, showed a rise of 0-39O in freezing point; another sample, heated for thirty-two hours at looo, showed a rise of 0'40O.Half the rise was due to the water, the amount of which was therefore 0.1 per cent. The following table shows the results obtained in one case for the velocity of the reaction at 70'1O. The mixture made up con- tained 267.02 grams of acetic acid, 6-23 grams of anhydride, and 1.123 grams of water. In calculating the velocity-coefficient by the formula 0.4343k=----log--,h(a -T) allowance has been made for (a-b)t u(b -x) the water present in the acetic acid.t min. 0 F. -p. depression. 1-550" k. - 30 1'415 0.0033 60 1*290 0-0035 90 1-170 0.0037 160 0.970 0.0037 250 0.784 0-0038 360 0.653 0 -0036 500 0'520 0.0037 600 0.446 0.0037 co 0'115 - In the experiment just recorded, water was in excess. Another similar experiment, carried out at the same temperature but with acetic anhydride' in excess, gave the following values of k at some- what similar intervals : 0.0032, 0*0034,0.0034, 0.0035, 0.0035, 0*0036, 0.0037, 0.0037, 0.0037, 0-0036. The mean value of k at 70*1°may therefore be taken as approxi- mately 0.0036. From an experiment made at 80-5O a mean value of 0.0063 was obtained for k. 263. "Condensation of bromoacyl haloids with glucosamine (Pre-liminary note.)" By Arthur Hopwood and Charles Weizmann.Bromoacyl haloids condense with glucosamine in cold alkaline solution, yielding bromoacylglucosamines. a-Bromopopionplylucosamine, C~,*CHBr*~O*NH*CH(CHO)*[C'H(O€€)],*CH,*OH, is prepared by adding a-bromopropionyl bromide (1 rnol.) and N-sodium hydroxide (1 mol.) gradually, and alternately with frequent shaking to a cold solution of glucosamine hydrochloride (1 mol.) in N-sodium hydroxide (1 mol.). A colourless precipitate separates out, which, after addition of hydrochloric acid in slight excess, is collected, washed with a little cold water, and dried in air on a porous plate. The product crystallises from hot absolute alcohol in prismatic needles, melting and decomposing at 200-201" when gently heated, and at 210-211° when quickly heated.The crystals are readily soluble in water or dilute alcohol, but are only sparingly soluble in absolute alcohol. They dissolve instantly in cold ammonia or alkali hydroxides. a-Bromoiaohexoylyl?ccosnmine, CHMe,*CH2*CHBr*CO*NH*CH(CNO)*[CH(OH)],-CH,*OH, is prepared by the condensation of a-bromoisohexoyl bromide (1 rnol.) and glucosainine hydrochloride (1 mol.) in alkaline solution. It crystallises from absolute alcohol as a mixture of rhombic plates and prismatic needles, which melts when heated quickly at l78--18l0 with much decomposition. The crystals are moderately soluble in cold, and readily so in hot, water. They are sparingly soluble in cold, but readily so in hot, absolute alcohol.They dissolve slowly in cold ammonia or alkali hydroxides. a-BromolnuTylglwmsarnine, C,lH2,Br*CO~NH*CI~(CHO)~[CH(OH)]3~CH2~OH, is prepared by condensing a-bromolauryl chloride (1 mol.) aild glucosamine hydrochloride (1 mol.) in a slightly alkaline solution. It crystalliaes from absolute alcohol in rhombic plates, which melt and decompose at 183-1SG0. The crystals are insoluble in hot or cold water, and moderately soluble in hot absolute alcohol. They do not dissolve in dilute hydrochloric acid, which shows that the amino-group, and not the hydroxy-groups in glucosamine, has been attacked during the condensation. The crystals are also almost insoluble in cold ammonia or alkali hydroxides.The bromoacylglucosa mines reduce alkaline copper solutions, yieiding I ed cuproas oxide, or ammonio-silver nitrate solution giving ;t silver mirror. On treatinelit with cold ammonium hydroxide and subsequent evaporation to dryness under diminished pressure, they yield colourless, crystalline solids, probably aminoacylglucosamines. 264. " Note on the formation of tetrachlorophthalyl chloride by chlorination of tetrachlorophthalide," By William Kobson Mills and Walter Henry Watson, In view of the paper '' On Symmetrical and Asymmetrical Dicarb- oxylic Acid Chlorides," by E. Ott, which appears in the current number of the Artizulen (1912, 392, 245), the authors communi- cated this note on some experiments on the chlorination of tetra-chlorophthalide, undertaken 011 account of their possible bearing on the constitutioii of the chlorides of the 1:2-dicarboxylic acids.Tetrachlorophthalide, as would be expected, is very resistant to chlorination, but the displacenient of the two atoms of hydrogen was effected by heating the phthaJide (5 grams) with excess of iodine trichloride (10 grams) in a sealed tube for five hours to 150O. Iodine and iodine chlorides were then removed by warming under diminished pressure, and the product was purified as far as possible by crystallising first irom carbon tetrachloride and then repeatedly from light petroleum, when it melted at 132-134O. That it had been formed from the phthalide by the displacement of the two hydrogen atoms by two atoms of chlorine was shown by the fact that on warming with sodium carbonate solution it was hydrolysed with the formation of tetrachlorophthalic acid, as well as by the analysis.(Found : reactive Cl =20.3 ; C,O,Cl,(Cl,) requires reactive C1= 20.8 per cent.) This product was identical with that obtained by the action of phosphorus penta.chloride on tetrachlorophthalic anhydride, agree- ing exactly in melting point," general characters, and analysis. In particular, the mixed melting point showed no depression, and although a similar difficulty to that experienced by Ott (Zoc. cit., p. 274) and by Bruhl (A4nnn7en,1886, 235, 13) was met with in obtaining either product quite free from acid anhydride, there was no doubt as to their identity.In the light of Ott's discoveries, it is clear that the obvious conclusion that tetrachlorophthalyl chloride possesses the asym-* The melting point 118" given by GraeLt! (14nnnlc??r,188i, 238,328) is accord-ingly too low if the compout~dis not dimorphic. 253 metrical structure (11) (hexachlorophthalide) would not be legiti-mate : C,CI,<g-~O 3c,cl,<~c,:>ci (I.1 (11.) -------+ COCl c,c1,<g>o 4C6C’4<co c1 (111.) It must rather be assumed that at the temperature at which the chlorination takes place, hexachlorophthalide undergoes transforma- tion, and that the product obtained in both reactions is the symmetrical acid chloride (111). 265. “Note on the preparation and properties of sulphonic esters.” By John Ferns and Arthur Lapworth.In a recent paper (Trans.,1912, 101, 273) the authors described experiments showing that the reactions of sulphonic esters almost wholly depend on the nature of the alcohol from which the esters are derived. The behaviour of ethyl and methyl esters towards bases, and also towards sodium P-naphthoxide had been previously described, however (compare Gllmann and Werner, Bnnalen, 1903, 327,120, and D.R.-P. 112177), a fact which the authors regret they had overlooked. The list of available methods for preparing sulphonic esters given in that paper was intended to be complete, but did not include one by Ullmann (Annulen, 1903, 327, 117), who showed that certain aromatic sulphonic acids may be converted into esters by treatment of their sodium salts with methyl sulphate.In extension of the work described in the former paper, the authors have found that p-toluenesulphonyl chloride, dissolved in pyridine, converts many alcohols directly and smoothly into the corrcsponding unsaturated hydrocarbons, sulphonic esters being doubtless intermediate products ;by the same process glycerol may partly be converted into acrolein. It is hoped to extend the observations to other hydroxy-compounds. 266. “ Electromotive forces in alcohol. Part 111. Further experi- ments with the hydrogen electrode in dry and moist alcoholic hydrogen chloride.” By Robert Taylor Hardman and Arthur Lapworth. The electromotive forces of a series of concentration cells revers- ible to hydriong have been measured ah 25O, and the corresponding values for the transport number of chloridion in absolute alcoholic hydrogen chloride were calculated with the aid of Nernst’s equation. These values vary between 0.20 and 0.35, according to the concen- tration of hydrogen chloride, a result perhaps attributable to the inadequacy of the expression when applied to such electrolytes.A re-examination of the influence of water on the potential of the hydrogen electrode in dilute alcoholic hydrogen chloride at 25O has been carried out with results similar to those recorded in Part 11. (Tram., 1911, 99, 2250). The temperature-coefficients of the cells were also determined, and shown to be in fairly satis- factory agrsement with the requirements of the solvate theory and with previous numerical data obtained from measurements on catalytic activity and availability. 267.“The properties of a-bromonaphthalene,” By John Ickeringill Crabtree and Arthur Lapworth. The autliors have prepared a-bromonaphthalene in a fairly high state of purity. It appears to be dimorphous, the ordinary modi- fication melting at 6*20° and tlie second between 0’2O and 0’7O, although it is uncertain whether the latter has been obtained quite free from the former. Several of ths more import ant physical constants of the substancra have been redetermined. 268. Absorption spectra of the cobalto-derivatives of primary aliphatic nitroamines.” By Antoine Paul Nicolas Franchimont and Hilmar Johannes Backer.The cobalto-derivatives of primary aliphatic nitroamines, Co(NR*NO,),, have, both in aqueous solution and in the anhydrous state, an intensely purple-violet colour, differing from that of solutions of ordinary cobalt salts. The cobalt derivatives of ethylnitroamine and propylnitroamine combine with two molecules of water, forming respectively yellowish- brown and bronze-green crystals ;from methylnitroamine such a compound has not been obtained. In order to gain objective data, the absorptive power for visible rays of the dissolved cobalt, salts of methyl-, ethyl-, and propyl- nitroamine has been studied and compared with that of a cobalt nitrate solution. The chief absorption band is found to be almost the same for the three cobaltonitroamines, but different from that shown by cobalt 265 nitrate.In addition, cobaltomethylnitroamine shows an absorption for smaller wave-lengths. The conclusion is drawn that in cobaltonitroamines the metal is attached to the nitrogen atom. 269. The constituents of Cluytia similis.” By Frank Tutin and Hubert William Bentley Clewer. Cluytia sirnilis, Muell. Arg., which is identical with the plant referred to by Smith ((‘A Contribution to South African Materia Medica,” Cape Town, 1895, p. 57) as a smaller variety of Cluytio hirsuta, is reputed in South Africa to be of value as an antidote for anthrax and for the disinfection of ‘r milt-ziek,” or anthrax-infected meat. The root of this plant is also stated to be eaten by natives as an antidote for snakebite poisoning.The entire above- ground portions, and also the root, of C. sirnilis have therefore been submitted to chemical examination, when, in addition to chryso- phanol, fatty acids, and other known compounds, the following new substances were isolated : (i) Cluytyl alcohol, C28H580(m. p. 82’5O) ; (ii) cluytinic acid, C‘,,H,,O, (m. p. 69O) ; (iii) cluytyl cluytinafe, C,,H,,O, (m. p. 76.5O); (iv) cluytiasterol, C,,H,,O (m. p. 159O); (v) a new acid, C,oH,,O, (m. p. 159O); (vi) cluytianol, C23H370(OR), (m. p. 300--305O). Cluytiaiiol is isomeric with the dihydric alcohol, ipuranol, which it, resembles in its general properties. Triacetyl-cluytianol melts at 160°, and the tribensoyl compound at 192O.The rook also contained a quantity of inorganic matter, in which skrontium was present. 270. 6L The constitution and reactions of thiocarbamides.” By Augustus Edward Dixon and John Taylor. A consideration of the synthetic methods for producing “thio-carbamide,” or its substitution derivatives containing univalent radicles, and of the properties displayed by these substances, leads the authors to conclude that, when in the static condition, they are all constituted on the type NH,*CS*NH,. By reaction with halogen compounds, RX (X =haloid), thiocarb- amides generally yield products containing the nucleus of imino-thiocarbamic acid, NH,*C(:NH)*SH, or “thiourea ” ; it does not follow, however, that the parent substances have the configuration of the latter, or acquire it through tautomeric change of a thio-carbamide, prior to interaction. In the authors’ view, such pheno- mena are better explained as follows: The primary product is an NH:>C:S<g; when from this theadditive compound of the type NN - 266 elements of HX are withdrawn, the sulphur again becomes bivalent, the radicle, R, if alkpl, retaining its place, with formation of NH,-C(:NH)*SR, but if acyl, moving to the unsaturated nitrogen atom, to give a substituted thiocarbamide, RNH*CS*NH,.When tho radicle, R, itself contains halogen or hydroxyl, the secondary product may undergo further change, with loss Gf halogen acid, or of water; in the former case, if the thiocarbamide contains an acyl radicle, this is eliminated preferentially to hydrogen.s -Dibenzoyldiphenylthiocarbamide yields with chloroacetyl chloride, diphenylisothiohydantoin, PhN:C<,--NPb*(?o ,and benzoyl CH, chloride, the explanation, on the above lines, being as-follows : N PhBz> :s< C1 Y’’Bz>C~S*CH2*COC1-+NPhBz CH,*COC1 PhX--+ 271. “The effect of heat on a mixture of benzaldehydecyanohydrin with m-chloroaniline and with m-toluidine.” By Clement William Bailey and Hamilton McCombie. The authors have extended the work described by Everest and NcCombie (Trans., 1911, 99, 1752) by studying the effect of replacing aniline by substituted anilines. When benzaldehydecyanohydrin and o-chloroaniline are heated together, even for several days, no condensation product could be obtained.In the case of m-chloroaniline, the products obtained were exactly analogous to those described by Everest and McCombie in the case of aniline itself, namely, (I) m-chloroanilinophenyI-ace tonitrile, C,H,Cl*NH*CHPh*C“; (2) dibenzoyldi-m-chloro-anilinostilb ene, C6H,Cl*NBz*CPh:CPh*NBz*C,H,C1; (3) 1:5-di-phenyl-3-m-chtoropher~yZglyoxa~ine,C2,H,,N2C1, and (4) a-keto-p-m-clz Zoroani7ino-ap-dipheIzylefhane. When p-chloroaniline was employed, the reaction took a different course. The product which was obtained gave figures in agreement with the formula C3,€12,03N,Cl,. The constitution to be assigned to this compound has not been determined, but it is hoped to return to this work later. When the reaction was extended to the toluidines, results similar to those obtained in the case of the chloroanilines were obtained; thus, o-toluidine did not react with benzaldehydecyanohydrin, m-toluidine yielded products exactly analogous to those obtained 267 in the case of aniline and m-chloroaniline, whilst p-toluidine gave a substance of the formula CB,H,,O,N,.272. ('Pilosine : a new alkaloid from Pilocarpus microphyllus." By Frank Lee Pyman. From the mother liquors remaining after the separation of pilo-carpine and isopilocarpine from t.he total alkaloids of Pilocarpus rnicrophyllus, a new alkaloid, pilosine, has been isolated in a yield amounting to 0.007 per cent. of the leaves. Pilosine has the empirical formula C,,H,,O,N,, and is a monacid base.It melts at 187O (corr.), and has [a], +39*9O. It contains an N-methyl, but no methoxy-group. It also contains a lactonic grouping. On treat-ment with acetic anhydride it yields a new unsaturated base, anhydropilosine, C,,H,,O,N,, which melts at 133-134O (corr.), and has [a], + 66.2O. Pilosine is decomposed on distillation with 20 per cent. aqueous potassium hydroxide, benzaldehyde and a new base, pilosinine, C,H,,O,N,, being formed. The chemical and physiologi- cal properties, as well as the solubilities of the latter base, are very similar to those of pilocarpine and isopilocarpine, and it seems probable that this base is a lower homologue of these alkaloids. Its formation from pilosine may then be represented as follows: C, H,.CH(OH) YH-yH *CH,*E*NMe>CH --+CO CH, CH-N \/0 Pilosine.H,-yH*CH,*g*NMe>CH.C,H,*CHO +(?CO CH, CH--N \/0 Pilosinine. and anhydropilosine would then have the formula : The physiological action o€ the three alkaloids is similar to, but very much weaker than that of pilocarpine. 268 273. ‘‘Note on the alkaloids of Pilocarpus racernosus.” By Hooper Albert Dickinson Jowett and Frank Lee Pyman. The statements in the literature with regard to the amount and nature of the alkaloid contained in the leaves of Pilocarpus ?*acerrzosus (Guadeloupe jaborandi) are conflicting. Holmes (Pharm. J., 1903, [iv], 17, 713) quoted the statement of G. Rocher, who examined the leaves in 1898-1899, that these contained 1 per cent, of total alkaloids, of which two-thirds was pilocarpine, but mentioned that another sample examined in the laboratories of Messrs.Wright, Layman, and Umney, Ltd., contained only 0.34 per cent. of total alkaloids. Later, Holmes stated (ibid.,1904, 18, 54) on the authority of A. J. Cownley, that the leaves of P. rucemosus contained 0.6 per cent,. of total alkaloids, which gave about 50 per cent. of a crystalline nitrate melting at 155O. Since pilocarpine nitrate melts at 178O arid isopilocarpine nitrate at 159O, he considered that this nitrate probably consisted largely of isopilocarpine nitrate, or possibly of some other alkaloid. Some time ago the authors examined a qLiantity of leaves of Y. race?7zosus at the request of the Director of the Royal Gardens at Kew; on extracting the alkaioids and purifying them in the usual way, they obtained pure pilocarpine nitrate melting at 178O (corr.) in a yield amounting to 0.12 per cent.of the leaves, but no other crystalline products. This result confirms Rocher’s statement that the leaves contain pilocarpine. The mother liquors after the removal of pilocarpine gave a red coloration with sodium diazobenzene-p-sulphonate, indicating the presence of a base containing a free imino-group, and contained a small amount of bases sparingly soluble in water. The latter did not yield pilosine (compare the preceding abstract) when seeded with this alkaloid, and the quantity was insufficient to admit of further purification. 274. “The ignition of electrolytic gas by the electric discharge.” By Hubert Frank Coward, Charles Cooper, and Christopher Henry Warburton.By suitable modifications in the usual apparatus for passing an electric discharge through a gaseous mixture, it has been found possible to ignite electrolytic gas (2H, +0,) at pressures much lower than any previously recorded. A flame which filled a globe of 570 C.C. capacity has been produced at 5 mni. pressure, and onc which travelled the whole length of a cylinder 2 metres long at 8 mm. In each case a small amount of gas remained uncombined. In two globes this residue varied in amount inversely as the original pressure of the gas, up to 70 mm. pressure. 275. “ The relation between viscosity and chemical constitution. Part V.The viscosity of homologous series.” By Albert Ernest Dunstan and Ferdinand Bernard Thole. Having had two long homologous series placed at their disposal 1)y Dr. Plckard, the authors have examined the viscosities of the different members therein. They have compared the various physical properties which have been measured for these series, namely, rotatory power, density, refractive power, and viscosity, and find that the strongly constitutive properties of optical rotatory power and viscosity give similar curves when plotted against molecular weight. Linear relationships are afforded by density, boiling point, refractive index, and log 7. The rotatory powers and viscosities rise to the third or fourth member, and then proceed iiormally. 276.bb The relation between viscosity and chemical constitution. Part VI. Viscosity an additive function. By Albert Ernest Dunstan and Ferdinand Bernard Thole. *4ttention was drawn to the linear relationship afforded by log viscosity in any homologous series. Using the data of Garten-meister and Thorpe and Rodger, it was shown that group constants of log 11 may be obtained, from which molecular values may be calculated in good agreement with those observed. Using this met’hod €or ethyl acetoacehte, it is found that 6.7 per cent. of the eriolic form is present in the equilibrium mixture. 277. ‘(The relation between viscosity and chemical constitution, Part VII. The effect of the relative position of two unsaturated groups on viscosity.” By Albert Ernest Dunstan, Thomas Percy Hilditch, and Ferdinand Bernard Thole. The authors have examined the viscosities of a number of homo-logous series of compounds of the respective types R*[CH21n*Rand Ph-[CH,],*R, where R is a varying unsaturated radicle.In both series the general order of the molecular viscosity rises when R is varied in the order GI, CO,Et, NH,, and CN, and in adciitior; tbhe iuitial ilienilxx, coiit:tining two cheniically adjacent 270 unsaturated groups, has been found to possess an exalted molecular x 106viscosity, as calculated from the expression -3----__Mol. Vol.’ In the symmetrical series R*[CH2];R, the members represented by R*CH2-CH2-Rpossess an enhanced value for this expression, but this is not the case in the phenyl group of compounds.In the latter group the anomaly of the initial member is in general very pronounced, and is followed by an equally well-marked depression in the case of the second member, the values therea’fter rising somewhat rapidly ; the relative positions of the curves connecting the molecular viscosities of the members of each homo- logous series, the relative slopes of these curves, and the extent of the depression at the second term are in the ascending order R=H, C1, CO,Et, NH2, CN, and OH. The series examined afford undoubted evidence of the strong mutual influence of two unsaturated groups on viscosity, not only when the radicles concerned are adjacent in the molecule, but also when they may be supposed from common steric considerations to approach one another in space.In addition, indications have been obtained of the varied influ- ences exerted by combinations of two similar, and on the other hand of two dissimilar, radicles, the effects in the latter case depend- ing to all appearance on the relative degree of unsaturation of the component radicles. 278. “Contributions to the chemistry of the terpenes. Part XIV. The oxidation of pinene with hydrogen peroxide.” By George Gerald Henderson and Maggie Xillen Jeffs Sutherland. When pinene is oxidised with 30 per cent. aqueous hydrogen peroxide in presence of acetic acid, the chief product is a-terpineol, C,,H,,*OH, partly free and partly as the acetate. The other. neutral products of the reaction include borneol (as the acetate), a small quantity of dipentene, a trace of the aldehyde, C,,€I,,O, formerly obtained by the oxidation of pinene with chromyl chloride, and some menthane-1 :4 :8-trio1 (1 :4 :8-trioxyterpan), CloHl,(O€I)3. The last compound has been obtained by oxidising A4(a)-menthenol-l with dilute permanganate, but has not hitherto been directly produced fram pinene.Neither pinene glycol, pinol, nor any ketone was detected among the oxidation products, and only a trace of an oily acid, or mixture of acids, was obtained. It is obvious that the behaviour of pinene towards hydrogen peroxide differs very considerably from that of camphene under sirnilar conditions (Henderson and Sutherland, Trans., 1911, 99, 27 1 1539), and trhat in t<his case, as in many others, the action of t,he reagent leads to disruption of the dimethylcyclobutane ring in pinene, and to the formatmion of derivatives of isomeric terpenes.279. ‘‘ Baly and Krulla’s hypothesis of fluorescence.” By Alexander Killen Macbeth. To be of ordinary utility and find general acceptance, a theory of fluorescegce must necessarily differentiate between absorbing substances which fluoresce and those which do not. It must also lay stress on the variation in wave-length and the increase in duration of the emission when the substance is in the solid state. The recent hypothesis of fluorescence put forward by Baly and Krulla (Truns., 1912, 101, 1469) offers no explanation of these points.The basis on which their hypothesis is built is the assumption of different degrees of binding up of the secondary valencies of the constituent atoms of the molecule; thus a substance is capable of existing, first, in a state 1, in which maximum condensation of the force field has occurred; after that in states 2, 3, 4, . . . etc., repre- senting various stages of ‘‘ opening up.” The change 1-32 is brought about by the selective absorption of light of wave-length he. By the influence of light of, say, wave-length A, and a suitable solvent, the substance may be opened up into 3. Hence the reverse reaction 3-2 must be accompanied by an emission of light of wave-length A,. If the substances 1, 2, 3, . . . are present, the change 2 -+1 must invdve disturbance of the system 3-+ 2 ; that is, in the bringing about again of the state 1, which has been disturbed by the absorption of light A?, we must get the process 3 -+2, or emission of A, also.Baly and Krulla further state that because of this, when 1 passes into 2 by the absorption of light of wavelength A,, the change 3-+- 2 is produced with the emission of light of wave-length A,, the latter constituting the fluorescence. It does not seem reasonable to suppose such to be the case. If the substance can exist in the forms 1, 2, 3, . . ., it is justifiable, in the light of chemical theory, to assume that these forms are in the state of chemical equilibrium; thus, 1, 2, 3, . . . being intimately connected, the system can be represented as follows: 1z213.On Baly and Krulla’s assumptions, the change 1--+2 is accom-panied by the absorption of light of wave-length A~;and the reverse change, 2 -+l, by an emission of the same light. Similarly, the changes 2 -+ 3 and 3 -+Z are accompanied respectively by absorp- tion and emission of light of wave-length A~. It is thus evident 27 2 that ir, e,quilibrium in solution there is a complete balance of light, as is seen on separating the two systems: 1 +------. 2 +----Emissicn of A2 2.J Eniission of As. If, now, the whole system is supposed to be disturbed by an exciting light of wave-length A,, effecting the change I-+ 2, accord-ing to the hypothesis, the equilibrium position will then be disturbed, and some of the process 2 +3 will result.Later, equilibrium may be supposed to be again attained. The changes in this cass are, first, an absorption of A,, and secondly, an absorp- tion of h3; and if equilibrium is then attained, there is a balance of light with, in addition, the preceding absorption effect. That is, the hypothesis leads to a further absorption of light, without any emission; thus, when the exciting light, A,, is cast on the substance, the changes may be represented as shown below : and the effect outstanding is clearly an absorption of A, plus h3. Further, if the exciting light is withdrawn, it is most reason- able to suppose that under suitable conditions the reverse reaction will commence, and there will be an emission of the original wave- lengths which were absorbed, in agreement with Kirchhoff’s law.This change may be represented thus: First, the system 3, 2 is involved, giving the process 3--+ 2, with its attendant emission of x~. This necessarily involves the process 2 -+ 1, giving emission of A,, and, later, equilibrium is established between 1, 2, and 3. . . . The effect, may be summarised thus: 3 -+ 2 Emission of A, 2 --3-1 Emission of A, 1 2 ZI 3 Balance Thus the application of the hypothesis would not explain fluorescence; and it seems more capable of explaining phosphor- escence, since, whilst the light was acting, the reaction would be driven in the direction 1--+ 2 -+ 3, the reverse change taking place under suitable conditions when the source of free energy is with- drawn.The system, in closing, would emit free energy in the form of light, and from the above considerations this light would be of a similar nature to that absorbed when the exciting source was in action, Examples in support of this are found in the cases of luminous paints and other phosphorescing substances. Moreover, it would appear f roin the behaviour of ammonium platinocyanide 27 3 that the later stages may be isolated, as on cooling a crystal of this substance to the temperature of liquid hydrogen and exposing it to a strong light, no phosphorescence is noticed on removal to a dark room. On withdrawing the crystal from the chilled tube and allowing it to become warm, it presently emits light of great intensity.Fluorescence in this case is not shown until additional free energy enters the system in t,he form of heat, disturbing the molecular compound 3, 4, . . . n,and resulting in the re-formation of 1. A real difficulty, however, is met when one considers the case of substances which show no fluorescence at the ordinary tempera- ture, and yet give strong emissions at low temperatures. At -180”, acetophenone, benzophenone, asparagine, hippuric, salicylic, ancl uric acids give brilliant fluorescence which they do not exhibit at the ordinary temperature. Here there are substances, at the ordinary temperature, containing free energy, and showing 110 fluorescence, which at low temperatures, when much of the free energy has been withdrawn, fluoresce strongly.This cannot be brought into agreement with the hypothesis of Baly and Krulla. An analogy may be drawn between the hypothetical states 1, 2, 3 . . . n, and a spring fixed at one end. The first state 1 is denoted at (a), this being the state under ordinary conditions. When free energy is supplied to the spring (as light is applied to the sub-stance 11, there is absorption, and the spring is compressed to position (b), corresponding with the state 2. Further free energy will compress it to (c), corresponding with h3, giving 2-+3. Now the Baly-Krulla hypothesis states that 1--+2, with absorption of A,, involves the change 3 -+2 with the emission of x3; yet there is no apparent reason why compression from (a) to (b) should necessitate the change from (c) to (b), the more so since the state (c) has not been reached.Similarly, on the basis of the hypothesis, if 2 is praduced solely by the absorption of hZ, then 3 cannot exist until 2 is passed, that is, until further absorption has taken place. On these grounds it cannot be affirmed that an absorption of A, develops an emission of A,. An idea of phosphorescence in such cases can, however, be formed by this means. At any degree of compression of the spring, withdrawal of the free energy supply 27 4 (that is, premure) is followed by an emission of the energy stored by the spring; and in the, analogous case of light, this represents phosphorescence; but it cannot he taken as giving an account of the cases of acetophenone, etc., mentioned above.Again, Nichols and Merritt (Phys. Eev., 1904, June and July) have verified that the wave-length of the exciting light may vary over a very wide range, and still produce the same fluorescence spectrum. Applying this to the changes I, 2, 3, etc., if the wave- length connecting the substances 1 and 2 can vary over a wide range, it seems most reasonable to deduce that the wave-lengths connecting 2 with 3 may also vary considerably. In other words, the fluorescence spectrum would vary widely, on the Baly-Krulla hypothesis, since this postulates that the latter wave-lengths con-stitute the fluorescence. Moreover, Nichols a,nd Merritt (Zoc. cit.) have shown, after careful investigakion of the intensities of the fluorescence spectra of many substances, that even when the exciting source, A,, is made up of a band of spectra, slightly towards the red side of the point of most intense fluorescence, the emitted light is still of good intensity. In this case the exciting source (A*) has been varied, not only up to A,, but beyond this wave-length.The particular case A,=A, may be taken. On the Baly-Krulla hypothesis, this may be written : Absorption of As. Emission of h3. and it is hard to see what, in such a case, causes an emission of h,. The hypothesis can be regarded from yet another point of view. If it is true that an absorption of h, takes place in the process 1 -+ 2, and a simultaneous emission of A, in the process 3 -+2, the conclusion is inevitable that the amount of light absorbed difTers when a substance is fluorescing and when it is in darkness.This is contrary to the facts observed and recorded by Wood (Phil. Mag., 1908, [vi], 16, 940), who established the identical nature of the absorptions in these cases. Seeing that the consideration of this hypothesis leads to no clear conception of the special cases of absorbing substances which show fluorescence, offers no explanation of the change of wave-length and duration of the emission when the substance is in the solid state, does not meet the case of substances exhibiting fluorescence as solids and yet showing no traces of the phenomenon when dissolved (for example, barium platinocyanide), and does not increase our know- ledge of even tho simplest facts in connexion with the phenomenon, it cannot be regarded as a rational theory of fluorescence.275 280. “Hydrazoximes of benzil and diacetyl,” By Martin Oiislow Forster and Biman Bihari Dey. Unsubstituted hydrazoximes do not appear to have been studied ; accordingly, b enzilhgdrazoxime, C,,H,,ON,, and diacetylhydraz-oxime, C,H,ON,, were prepared, together with their acyl derivatives and products of condensation with benzaldehyde and acetone. 281. “The relation between constitution and rotatory power amongst derivatives of tetrahydroquinaldine.” By William Jackson Pope and Thomas Field Winmill. The authors have prepared a number of derivatives of I-tetra-hydroquinaldine, and have shown that a close relation is observable between the molecular compositioii and constitution and the rotation constants of these substances.282. “ The dehydration of iao-P-naphthol sulphide.” By Kenneth Ross and Samuel Smiles. When heated with certain dehydrating agents the unstable sulphide of @naphthol loses the elements of water, giving an isonaphthathioxin (m. p. 148O). It has already been shown that the stable fir normal sulphide also yields a naphthathioxin (m. p. 166O) wihh these reagents. With nitric acid (D 1.4) the iso-deriv- ative furnishes the oily nitrate of the sulphoxide, from which the solid base may be liberated by hydrolysis. This sulphoxide is attacked by warm hydrochloric acid, giving a mixture of chloro-derivatives of the naphthathioxin.If the reaction is carried out under suitable conditions, the chief constituent of the crude product is identical with the dichloro-derivative previously obtained (Christopher and Smiles, Trans., 1912, 101, 710) by chlorinating the monoch!oronaphthathioxin which is formed by the interaction of acetyl chloride and P-naphthasulphonium-quinone. The naphthathioxin derived from the stable sulphide of P-naphthol undergoes a preciseiy similar series of changes ;but the sulphoxide and chloro-derivatives are quite distinct from t,hose of the iso-series. The relations between these series are being examined, and will be discussed in connexion with the nature of the two sulphides of j3-nap ht hol. 276 283.(( Salt8 of naphthathioxonium.” (Preliminary note.) By Thomas Joseph Nolan and Samuel Smiles. Previous attempts to obtain the thioxonium chloride by inter- action of hydrogen chloride and oxides of naphthathioxins have uniformly resulted (Trans., 1912, 101, 710) in the immediate production of chloro-derivatives of the nucleus, the thioxonium salt being apparently too unstable in presence of excess of this mineral acid to permit isolation. It has, however, been observed (Traits., 1910, 97, 1112) that phenazothionium bromide reacts very slug- gishly with hydrogen bromide, whereas the corresponding chloro- derivatives are very reactive. Taking advantage of this observation, it has been found that the thioxonium bromides may be obtained from the napht-hathioxin oxides by treatment with luke-warm liydrobromic acid.They are slowly converted by the boiling reagent into the bromonaphtha,thioxins ;t,he successive changes may he represented as follows : These thioxonium bromides are more easily obtained by the inter- action of bromine and P-naphthasulphonium-quinone in acetic anhydride or with the acetyl derivative of the unstable sulphide of &naphthol in the same solvent. 284. (‘Intramolecular rearrangements of o-sulphoxides. of diphenyl-amine. Part IV.” By Thomas Percy Hilditch and Samuel Smiles. Previous experiments (Trans., 1911, 99, 145) have shown that the o-sulphoxide of diphenylmethane when treated with hydrogen chloride or hot glacial acetic acid yields thioxanthenyl chloride or hhioxanthenol.Attempts have now been made to isolate similar derivatives from the products of rearrangement of the o-sulphoxides of diphenylamine; but they were not successful. It was shown, for example, that diphenylamine o-sulphoxide yields hydroxythio- diphenylamine when heated with acetic acid, whilst the tetrachloro- derivative furnished the phenazothionium hydroxide. Similar attempts to obtain the AT-chloro-derivative from the tetranitro- and tetrachloro-sulphoxides were unsuccessful. 27 7 285. bb Diphenyl-2 :3 :2’ : 3’-tetracarboxylic acid,” (Preliminary note.) By James Kenner. Dimethyl 3-iodophthaZate, C,H31(C0,;114e)2, forms prisms, m. p. 89O, and is converted by treatment with copper powder into tetra-methyl diphenyl-2 :3 :21 :3’-tetrac(~rboqlate, C,2H,(C0,Me)4, which forms needles melting at 161O.7Jiphenyl-2 :3 :21 :3/-tetracarboxylic acid, C,zH,(C02H),, crystal-Jises in plates melting at 265O, and is readily soluble in water. The reactions of this compound are being investigated in con-tiexion with the author’s studies 011 ring-foimation from derivat’ives of 2 :21-ditolyl. 286. b6 The reactions of dibenzocycloheptadieiione.” (Preliminary note.) By James Kenner and Emily Gertrude Turner. In connexion with the authors’ investigations of derivatives of 2 :gl-ditolyl (!Z’tuns., 1911, 99, 2lOl), a comparison of the reactions of dibenzocgc70heptBadieiionewith those of P-hydrindone has been undertaken. Unlike P-hydrindone, dibenzocycloheptadienone does not undergo condensation in the presence of alkali, and it yields a dibensylidene derivative, m.p. 227O. Further, whilst P-hydrindone is known to yield a diisonitroso-derivative (from which, by the action of iorinaldehyde and hydrochloric acid, the authors have prepared triketohydrindene hydrate), dibenzocycloheptadienone only gives rise to a monoisonitroso-derivative, m. p. 197O. With aniline, P-hydrindone yields the normal condensation product (leaflets, m. p. 97O), but the action of aniline on dibenzocycloheptadienone leads to tlie formation of phenylcarbylamine and a compound, golden-yellow prisms, m. p. 188O, the constitution of which has not yet been ascertained. Other reactions of the two ketones are under investigation.287. “Studies in the diphenyl series. Part 11. The dinitrobenz-idines : a new form of isomerism.” By John Cannell Cain, Albert Coulthard, and Frances Mary Gore Micklethwait. It has hitherto been assumed that the same o-dinitrobenzidine is obtained by the nitration of diacetyl- and diphthalyl-benzidine. It is now found that two different o-dinitrobenzidines are produced in these reactions. That irom diacstylbenzidine melts at 275O, gives a diacetyl derivative melting at 310°, and a dinitrodiphenyl melting at 197-198O (Brunner and Witt, Ber., 1887, 20, 1023), whilst that from diphthalylbenzidine melts at 233O, gives a diacetyl derivative 278 melting at 222O, and a dinitrodiphenyl melting at llOo. It was suggested that the series of compounds of higher melting points have the symmetrical (I) and those of lower melting points the unsyniinetrical (11)constitution (R =H, NH,, or NHAc) : R/\NO2 \/I so“,/\I R (I.) (11.) Bandrowski’s “ isodinitrobenzidine ” (Bey., 1884, 17, 1181; Monatsh., 1887, 8, 472) has been found to be a mixture of 2 :2/-di-nitrobenzidine and 3 :S’-dinitrobenzidine (m.p. 233O) with a small amount of 3-nitrobenzidine. 288. ‘‘ The velocity of reaction between potassium chloroacetate and some aliphatic amines.” By Tom Sidney Moore, Donald Bradley Somervell, and John Newton Derry. The rates of reaction of potassium chloroacetate with ammonia, the three methylamines, the three ethylamines, and dipropylamine in aqueous solution at 25O have been measured, and the velocity constants calculated from the measurement6 have been compared with those found by Menschutkin for the reactions of the same bases with methyl, ethyl, propyl, and ally1 bromides.289. ‘‘The absenoe of optical activity in the a-and p-2:5-dimethyl-piperazines.” By William Jackson Pope and John Read. The authors have been unable to effect the resolution of either a-or p-2 :5-dimethylpiperazine into optically active components by crystallisation with optically active acids or by condensation with d-oxymethylenecamphor. 279 ADDITIONS TO THE LIBRARY. I. Donations. Predrick. A treatise on adulterations of food, and culinaryACCUIII, poisons, exhibiting tho fraudulent sophistications .. .and methods of detecting them. London 1820. pp. xvi +372. (Reference.) From Dr. Alexander Scott, F.R.S. Armstrong, E’dwnrd Frankld. The simple carbohydrates and the glucosides. 2nd edition. London 1912. pp. viii +171. 5s. net. (Recd. 25/9/13.) From the Publishers : Messrs. Longmans, Green and Co. Arrhenius, Svante. Theories of solutions. New Haven 19 12. pp. xx+247. 12s. 6d. net. (Recd. 19/9/12.) From the Publishers : Oxford University Press. Bolton, Edward Richards, and Revis, Cecil. Fatty foods, their practical examination. A handbook for the use of analytical and technical chemists. London [1912]. pp. x+371. ill. 10s. 6d. net. (Recd. 4/11/12). From the Publishers : Messrs. J. & A. Churchill. Cathcart, E.P. The physiology of protein metabolism. London 1912.pp. viiif 142. 4s. 6d. net. (Recd. 14/10/12.) From the Pubbhers : Messrs. Longmans, Green and Co. Chapman, AZfred Chaston,. Brewing. Cambridge 19 12. pp. xii+ 130. ill, Is. net. (Recd. 11/10/12.) From the Author. Dakin, Henry Drysdale. Oxidations and reductions in the animal body. London 1912. pp. viii+ 135. 4s. net. (Recd. 27/10/12.) From the Publishers : Messrs. Longmans, Greenkand Co. Harris, Prank. Gravitation. London 1912. pp. xi+ 107. ill, 23/6 net. (Recd. 17/9/12.) Prom the Publishers : Messrs. Longmans, Green and Co. Martin, Geofrep. Triumphs and wonders of modern chemistry. London [1912]. 7/6 net. pp. xviif358. ill. (Recd. 26/S/19.) From the Author. Martindale, WilEiam Harrison, and Westcott, W. Tym. The Extra Pharmacopeia. 15th edition.London 1 12. 2 vols. pp. xxxi +1114, viii +370. 211- net. (Recd. 31/7/12.) From the Authors. Michelson, A. A. Light waves and their uses. Chicago [1903]. pp. vi +166. ill. (Becd. 25/7/12.) From the University of Chicago. Pepper, John Zenry. The Boy’s Playbook of Science. Rewritten by John, Mastin. London [1912]. pp. ix+ 680. ill. 5s. (Recd. 3/lop2.) From Dr. John Mastin. 280 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 2nd, 1912. All persons who received grants in December, 1911, or in December OF any previous year, whose accounts have not been declared closed by the Council, are reminded that reports must be in the hands of the Hon.Secretaries not later than Monday, December 2~d. 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. At the next Ordinary Scientific Meeting on Thursday, November 21st, 1912, at 8.30 p.m., the following papers will b3 communicated : (( The change in the boiling points of the trioxide and tetroxide of nitrogen on drying.’’ By H.B. Baker and M. Baker. “The tendency of atomic weights to approximate to integral and semi-integral values.” By E. Feilmann. “The constituents of Taraxacum root.” By F. B. Power and H. Browning, jun. “The condensation of a-keto-P-anilino-ap-diphenylethaneand its homologues with phenylcarbimide and with phenylthiocarbimide.” By S. A. Brazier and H. McC‘ombie. “Keutral salt action. Part 11. The influence of sodium saIts of organic acids on the rate of hydrolysis by alkali.” By G. Senter and F. Bulle. ‘‘ The constitution of aconitine.” (Preliminary note.) By 0. L. Brady. __ -~ __~ R. CLAP AXD SOSS, LTD., BRUNSWICII ST., STbMFORD ST., S.E., ASD BUNGAY. SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9122800213
出版商:RSC
年代:1912
数据来源: RSC
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