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Proceedings of the Chemical Society, Vol. 19, No. 268 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 268,
1903,
Page 155-177
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PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 19. No. 268. Thursday, June 4th, 1903. Dr. W. H. PERKIN,F.R.S., Vice-President, in t.he Chair. Cextificates were read for the first time in favour of Messrs. : Ernest Derwent, 36, Sixth and Railroad, Ironton, Ohio, U.S.A. William Forster, 6, North Railway Street, Seaham Harbour. Edwin Reginald Hughes, 106, Queen Victoria Street, London, E.C. Walter Ernest Jennings, 8, Rawdon Terrace, Ashby de la Zouch. William Parry, B.Sc., 23, Mount Pleasant, Waterloo, Liverpool. The following certificate was au-thorised by Council under Bye-Law 1 (3). Wilfrid William Ogilvy Beveridge, A.M.S. Laboratory, Pretoria. Of the following papers, those marked * were read : *83. “Formation of an anhydride of camphoryloxime.” By T.M. Lomy. When nitrocamphor is boiled with concentrated hydrochloric acid, the greater part of the substance passes into solution and is converted into camphoryloxime. Daring the investigation of this isomeric change (Tmzs., 1898, 73, lOOZ), a considerable quantity of a resinous by- product was accumulated ;this substance has now been examined and found to contain an anhydride, %H14>C:N*O*N:C<o. %HI4bo, of cam-co-0 phoryloxim, which, after crystallisation from alcohol, softens at about 2 15*, melts at 220°, and has [OL ID= + 26’ in acetone. *84. “Mutarotation of glucose as influenced by acids, bases and salts.” By T. M. Lowry. Both acids and bases have an accelerating effect on the muta-rotation of glucose, whilst potassium chloride is without influence.If the mutarotation is conditioned by the presence in the glucose of an exceedingly minute quantity of basic impurity or a some-what larger amount of acid impurity, a retardation should be produced when the base or acid is neutralised by adding hydrogen chloride or potassium hydroxide respectively. Careful quantitative experiments showed that this retardation does not occur, and the con- clusion is drawn that although the mutarotation is accelerated by bobh acids and bases, its occurrence is independent of the presence of these impurities. Probably the water alone is sufficient to condition the change if enough impurity is present to render it an electrolyte. *85. ‘‘ The solubility of dynamic isomerides.” By T.M. Lowry. Whilst the rotatory power affords a general method for studying the dynamic isomerism of optically active substances, no similar method is available in the case of inactive bodies. The measurements of electrical conductivity, so effectively employed by Ha,ntzsch in the study of pseudo-acids, pseudo-salts, and pseudo-bases, can only be made when one of the isomerides is an electrolyte and at least moderately soluble in water. OF the other physical properties, density, molecular solution volume, refractive index, dispersion, and magnetic rotatory power differ relatively little in isomeric compounds, and the melting point, colour and ultra-violet absorption cannot easily be made the 157 basis of quantitative measurements.The solubility of dynamic isomerides is, however, usually very different, and under cerkain con- ditions it is possible to follow experimentally the gradual change of solubility as a substance is converted into a dynamic isomeride. This method, which has been devised and tested in the case of optically active substances, will, it is believed, be of service in the study of inactive bodies, and thus render possible the quantitative examin-ation of many changes that have hitherto been examined only qunli tatively. If the less soluble isomeride is initially in contact with the solvent, the solubility gradually increases until the liquid phase contains a normal proportion of the two forms. If, however, the more soluble isomeride is used, the solubility increases until the liquid is saturated with both forms ;the solution then contains a much greater proportion of the more soluble isomeride and isomeric change proceeds con-tinuously, the more soluble modification dissolving whilst the less soluble form separates from the solution; finally, when the whole of the more soluble form has dissolved, the solubility decreases to a constant value identical with that obtained when the less soluble isomeride alone is used.Measurements of the solubility of pseudo-p-bromonitrocamphor in benzene show that at, 10' the solubility gradually increases from 2.3 to 9.3 grams per 100 grams of benzene, whilst when both forms are present in the solid phase the solution contains nearly 14 per cent.of the substances. "86. " The rusting of iron." By Q. T. Moody. The contention of Dunstan (Proceedings of the Royal ArtiZZery Institution, 1899, No. 5, 26; this vol. p. 150) that carbon dioxide is not essentially concerned in the process of rusting and that this change is caused by hydrogen peroxide is Lased on the observation that solutions of chromium trioxide, potassium dichromate, potassium ferrocyanide, sodium nitrite and other substances which decompose hydrogen per- oxide, entirely or nearly entirely prevent rusting. The author finds that the retarding action exercised by these substances is due to the influence they exert on the absorption of carbon dioxide. For example, when exposed to the gas under exactly the same conditions, water absorbed 90.6 volumes, whilst a 15 per cent.solution of chromium trioxide and a 20 per cent. solution of sodium nitrite absorbed 4.2 volumes and 5.6 volumes respectively. A solution of chromium tri- oxide-which itself does not attack iron-appears all the more to exert a protectiag influence because of the ease with which it dissolves 158 ferric oxide. Iron, when placed under a 1per cent. solution of chrom-ium trioxide exposed to air, remains bright for some weeks, although the metal is slowly passing into solution. Eventually rust commences to form on the metal, although the solution still contains free chromic acid. When iron is exposed to water and oxygen previously freed as far as possible from carbon dioxide, the volume of oxygen remains practically unchanged. On admitting carbon dioxide, the volume of oxygen diminishes rapidly and rusting becomes visible.The interaction of iron with aqueous carbonic acid appears to be strictly comparable with that occurring between iron and sulphuric acid. A solution of carbonic acid, formed by saturating 2.4 litres of water at 18' with carbon dioxide, when left in contact with 500 grams of clean iron turnings yielded 635 C.C. of hydrogen in 7 days. After remaining for one week, the solution contained 0.1 per cent. of iron present as ferrous bicarbonate, ft substance which is readily de- composed by atmospheric oxygen yielding a mixture of ferrous carbon- ate and ferric oxide, whilst a part of the carbonic acid is regenerated, On account of the ease with which this change takes place, it follows that in presence of oxygen a definite weight of carbonic acid will exert a greater corroding influence on iron than will its equivalent of sulphuric or hydrochloric acid.The author contends that the primary action in rusting involves the interaction of iron and acid and that rust is formed by the subsequent oxidation of ferrous salt. DISCUSSION. Mr. C. E. GROVESsaid it was known that iron immersed in potassium carbonate solution did not rust, and asked whether the author had examined the action on iron of a solution of potassium hydrogen carbonate saturated with carbon dioxide. He believed it was not generally known that solid caustic potash containing about 5 per cent.of water, when fused at a gentle heat in contact with steel, readily attacked it, the iron apparently forming a ferrous compound. Fused caustic soda, however, had practically no action on iron. Dr. JOWETTsaid that, having cooperated with Professor Dunstan in the work to which Dr. Moody had referred, he must point out that much of the criticism seemed to be based on a misunderstanding. The rusting of iron was the sum of several chemical reactions each of which had been separately studied, It was not stated or thought that the oxidation in which hydrogen peroxide might take part constituted the whole phenomenon of rusting, and one of the experiments shown by Dr. Moody, namely, the evolution of hydrogen from a mixture of 1.59 aqueous carbonic acid and iron, was referred to in Professor Dunstan’s note.The oxidation in which it was suggested that hydrogen peroxide was involved, occurred when oxygen, water, and pure iron were used, and it was a fact that substances which decomposed hydrogen peroxide prevented oxidation under conditioiis similitr to those in which the peroxide was produced during the oxidation of zinc. Finally, although the analyses of rust produced under ordinary atmospheric conditions generally showed the presence of carbon dioxide, they agreed closely with the formula Fe,O,(OH),, which was also found to represent the composition of the product formed by the oxidation of iron under the conditions previously mentioned. Dr. SCOTTasked if the chromic acid was free from sulphuric and nitric acids.He mentioned that Dr. Russell’s experiments on the action of various metals on photographic plates showed that zinc very readily gave hydrogen peroxide and even mercury containing 1/300th per cent. of zinc produced sufficient to affect a photographic plate. Dr. KOHNasked whether any experiments had been tried on the influence of light on the action of carbonic acid, since many changes effected by air and moisture and attributed to the formation of hydrogen peroxide did not occur or were diminished in absence of light. Such experiments might indicate whether hydrogen peroxide had any contributory action. ?Mi-. -4.C. CHAPMANasked whether Dr. Moody had assured himself that the amount of hydrogen evolved in the experiment, referred to was not greater than that which would correspond with the carbon dioxide present, and also whether he had made any experiments as to the influence of the purity of the iron employed on the quantity of gas evolved.In other words, was the hydrogen solely the result of re-placement, or might not some of it have been produced by electrolytic action pure and simple. Dr. HENRYpointed out that in the course of the experiments referred to in Prof. Dunstan’s note, a specimen of pure sheet iron with bright surfaces had been immersed for more than six years in a 4 per cent. aqueous solution of chromic acid contained in a loosely stoppered jar ;during the whole of that tiue the surfaces had remained perfectly bright and there was no evidence of either the reduction of the chromic acid or the formation of iron rust, although the solution was in contact with atmospheric carbon dioxide.He suggested that the rusting observed by the author when iron was kept in solutions of dilute chromic acid in presence of carbon dioxide might be due to the employment either of commercial iron or chromic acid containing impurities; it was known that the presence of neutral salts such as 1GO sodium chloride in water in which iron n7as immersed accelerated the rate of rusting. Dr. LOWRYsaid that if hydrogeu peroxide were a prodiict of the initial stage in the rusting of iron, its destruction by chromic acid might be expected to assist rather than retard the oxidation.Dr. MOODY,in reply, said that in discussing this subject it was necessary to be agreed as to what was meant by rusting. He under- stood rusting to mean the corrosion taking place when metals were left' exposed to air under ordinary conditions. Water condensed frcjm air contains carbonic acid, which in contact with iron immediately gives rise to a ferrous salt. Since ferrous salts equally with chromic acid, sodium nitrate, and potassium ferrocyanide establish a condition in which the prodiiction of hydrogen peroxide is inhibited, it follows that the theory advanced by Dunstan can have no bearing on the nt>rnospheric rnstipg of iron. 87. '' Imino-ethers corresponding with ortho-substituted benzenoid amides." By G.D.Lander and F. T. Jewson. Pinner's method of synthesis of imino-ethers fails either partially or completely with aryl cyanides containing an ortho-snbstituenb, and one of the authors has shown that the main product of the action of ethyl iodide and dry silver oxide on o-toluamide in boiling alcoholic solution is a nitrile (Tyans., 1901, 77, 695). When boiling alcohol is employed as a medium, the alkylation of other amides by this method seems to be characterised by the forma-tion of nitriles, but whilst the yield of imino-ether from o-tolnamido is rnly 13.6 per cent., the proportion is 70 per cent. in the case of p-toluamide ; this result is explained by supposing that the o-compound more readily loses alcohol than its p-isomeride, C,H,*C:NH*OEt = C,H,*CN +EtOH.The same constitutive factor, however, renders the o-imino-ether more stable as regards hydrolysis by aqueous hydro- chloric acid, C,H7C:NH*OEt +H,O + HCl= C,H,*CO,Et +NH,CI. Although better yields of the imino-ether are obtained when the synthesis is carried out in boiling ethereal solution, yet in this case, nitrile is also produced. The hydrochloride of o-chlorobenziminoethyl ether decomposes at 105", yielding o-chlorobenzamide ; the methyl analogue forms R J~ydrochloride which decomposes at about 110". o-ChlorobenxmetJAyt-nmide is also a product of the methylation of o-chlorobenzamide, and forms colourless needles melting at 92-94". o-Toluiminonzetlr!/letlhev was prepared by the action of methyl iodide on the silver derivative of o-toluamide ; it's lryrhocldo~idedecomposes between llOo and 115".161 o-Toluiminoethyl ether, when mixed with nitrile, distils without change between 106’ and 1 18’ under 20-25 mm.pressure, and yields a hydro-cAZode which decomposes at 105-106°. 88. The hydrolysis of ethyl mandelate by lipase.” By H. D. Dakin. Optical isomerides are frequently very differantly affected by en- zymes as well as by living organisms, but the production of an optically active substance from inactive material as the result of simple enzyme action has not hitherto been conclusively demonstrated. If the conception of an enzyme as an optically active asymmetric complex is correct, and, morever, if combination occurred between the enzyme and the substance acted on, it should be possible to show that when an enzyme acts on an optically inactive substance, the two optical components are decomposed with unequal velocity. This was shown to be the case when inactive ethyl mandelate was hydrolysed by the enzyme lipase.In all cases, provided hydrolysis was incomplete, the separated mandelic acid was fouud to be stxongly dextrorotatory whilst the unchanged ester was laevorotatory. The reaction would appear to bear a close analogy to the hydrolysis of esters prepared from an optically active alcohol and an inactive acid (Marckwald and McKenzie, Ber., 1901, 34, 469). 89. “ Isomeric change in benzene derivatives. The conditions in-fluencing the interchange of halogen and hydroxyl in benzene-diazonium hydroxides.” By X. J.P. Orton. The supposed s-tribromophenylnitrospamine, obtained by Hantzsch and Pohl (Bey., 1902, 35, 2964) from s-tribromobenzenediazonium acetate under conditions which, according to the author’s earlier in- vestigations (Proc. Roy. Xoc., 1903, 71, 153), are favoursble to the replacement by hydroxyl of the bromine atom in the ortho-position relatively to the diazo-group, is now shown, by an exact repetition of Hantzsch and Pohl’s experiments, to consist of R mixture of 3 :5-di-bromo-o-quinonediazide (3 :5-dibromo-o-diazophenol) and an amorphous condensation product, probably a hydroxyazo-derivative, either when prepared from the diazonium salt or from the corresponding alkali diazo-oxide (diazotate).Moreover, the hydrochloride obtained by IIantzsch and Pohl by passing hydrogen chloride into an ethereal solution of the original yellow material and thought by them to be the hydrochloride of the nitrosoarnine, is, in fact, the hydrochloride of the quinonediazide, which can readily be prepared from it by hydrolysis with water. 162 The transformation of the diazonium acetates derived from 2 :4 :6-tri-bromo-3-nitroaniline, 2 :3 :4:6-tetrabromoaniline, 3 : 5-dibromo-p-tolu-idine, 2 : 6-dibi*omoaniline, 2 :4-dichloroaniline, and 3 :4-dibromo-5-nitroaniline have been examined. When a nitro-group is in the meta-position relatively to the diazo-group, the replacement of the 0-or p-bromine atom by hydroxyl takes placevery readily, the diazo-compound in this respect resembling the naphthalene derivatives (Proc., 1902,18, 252).It is remarkable that 3 :5-dibromo-p-toluenediazonium acetate does not lose bromine. 2 :6-Dibromobenzenediazonium acetate slowly undergoes this change, but chlorine ions are scarcely appreciable in a solution of 2 : 4-dichloro-benzenediazonium acetate, even after several days. Bromine is, however, rapidly displaced when a nitro-group is in the meta-position relatively to the diazo-group, as in the 3 :4-dibromo-5-nitrobenzene diazo-compounds. This interchange takes place not only with the diazonium acetates and hydrogen carbomtes, but also in a similar manner with the salts of other weak acids, such as the cyanides and the nitrites, but with these salts, however, other reactions occur simultaneously, thus 2 :4 : 6-tribromo-1-nitrobenzene is also formed from the nitrite.When the diazonium salt is present as sulpbate, the change is extremely slow at the ordinary temperature, but at SOo nearly one atomic proportion of bromine is eliminated in four hours, a fact which no doubt accounts for the apparent impossibility of obtaining s-tri- bromophenol by heating aqueous solutions of s-tribromobenzenediazon-ium salts. The following substances mere described : 2 : 4:6-tribromobenzeizecc20-P-nibphthol, melting at 17 3-174" ;3 :5-dib~omophenol-3-uczo-~-na~lit~~ol~ copper-coloured plates melting at 214-215' ; 3 : 5-dibromo-2-nitro-p-puimonediuzide (3 :5-clibromo-2-nit~o-p-clia~ophenol),prepared from 2 :4:6-tribromo-3-nitroaniline, crystallises in yellow plates decomposing at 196' ;ti8ibromoquinonedicLxide (6ribroniodiaxop~~enoI),prepared from 2 :3 : 4 :6-tetrabromoaniline, forms orange crystals melting and de-composing at 124."; 3-bi~onao-o-qui~aonediazide(3-bro?,~O-o-diaxO~l~~~~Ol), prepared from 2 :6-dibromoaniline, crystallises in orange needles melt- ing and decomposing at 103' ;2 :4-dicJ~lorobenxerzeaso-~-nuphtl~ol,scarlet prisms melting at 190"; chZoi.op~enola~o-P-)iapl~thol,minute needles melting at 265' ; 3 :5-diB1.onzo-p-tolueneaxo-P-n~~p~t~~o~,scarlet prisms melting at 141O.163 90. "The synthesis of my-trimethylglutaric acid, of the cis-and trans-modifications of /3-hydroxy-say-trimethylglntaric acid, and of aay-trimethylglutaconic acid." By W.H.Perkin, jnn., and Alice E.Smith. A mixture of ethyl dimethylmalonate and ethyl acetate is readily acted on by sodium, yielding the sodium compound of ethyl aa-di- met.hylacetonedicarboxylate, CO2Et*CR~e,*CO.CHKa*C0~Et,and if this is treated with methyl iodide, ethyl aay-trimethylacetonedicarbox?/lccte, C'O,Et*CMe,*C'O*CHMe*CO,Et,is produced as a nearly colourless oil boiling at 195-197O under 100 mm. pressiire, which, in alcoholic solution, gives a violet coloration with ferric chloride. When this ester is redaced with sodium amalgam, it yields a mixture of the cis-and tvuns-modifications of p-~/droxy-aay-trimetl~yEglutaricacid, CO,K*CMe,*CH(OH)*CHMe~CO,H.The trans-acid melts at 155" and when rapidly heated under reduced pressure distils with very little decomposition. The cis-acid melts at 115O and on distillation yields a crystalline substance, C,H,,0,7 which melts at 88" and is probably the anhydride of cis-aay-trinaeth~llglzctaconic c~cz'd, Both the cis-and trctm-modi6cations of the hydroxy-acid, when treated successively with phosphorus pentachlorids and diethylaniline, or when digested with fuming hydriodic acid, are :converted into trans- aay-tl.imetiLylgluttcco?zicacid ; this acid, which melts at 150° and, when heated in small quantities, volatilises to R certain extent without decomposition, is reduced with difficulty, but by the action of a large excess of alcohol and sodium becomes converted into aay-tri-methylglutcwic acid, CO,H*CMe,*CH,*CHMe*CO,H,melting at 98".When subjected to the action of dry bromine vapour, trans-aay-tri- methylglutaconic acid is converted into py-dibl.onao-aay-trinzethylglutccric acid, which crystallises from formic acid and melts at 205-207°. 'I91, Hexamethyleneoctocarboxylic acid and the cis-and trans-modifications of hexamethylenetetracarboxylic acid (hexahydro- pyromellitic acid)." By T. W. D. Gregory and W.H. Perkin, jun, When ethyl propanetetracarboxylate, (CO,Et),CH.CH,*CH( CO,Et);, is treated with bromine, it yields eti$ clib1ioino23ropanet~t~acc~rbo~y~te, (C0,Et)2CBr*CH,*CBr(C0,Et)2,which melts at 55". This bromo-ester reacts with the disodium compound of ethyl 164 propanetet racarboxy Iat e giving an a1most quantitative yield of etlq2 a colourleas,hezcunethyleneoctocarbox&te, (C02Et),.t:.CH2.~.(C02Etj2, (CO,Et),* C*CH,-C*(CO,E t)2 crystalline substance (m.p. 46’1, which, when digested with hydro- chloric acid, yields the free iLexurnetTLyleneoctocccrboxylic acid ; this sub- stance decomposes at 218”,giving rise to the cis-and trans-modifications CO,H*YH*CH2*YH*CO2Hof hexccinethylenetetrucurboxylic mid, CO,H CII CH,*CH*C0,H’ The cis-acid melts at 140°, and ibs anhydride at 60’; the trans-acid melts at 175O, and yields the latter compound on digestion with acetic anhydride and subsequent distillation. 92. *‘The bases contained in Scottish shale oil. Part 11.” By F. C. Garrett and J. A. Smythe. The only bases obtained in a state of purity from the fractions of Scottish shale oil boiling between 164’ and 180’ are 3 : 3-cEimetiqZ-pyridiTze and 2 : 4 : 6-trimethylpyridine.The lower homolope, which has not been described, is a liquid lighter than, and insoluble in, water, having a pleasant aromatic smell and boiling at 163-164’ under 768 rnm. pressure. Its mercurichloride melts at 120’ and its uurichlor-ide at 96’; its platinichloride melts and decomposes at 216’. The trimethylpyridine boils at 171O under 768 mm. pressure and gives an aurichloride containing one molecule of water of cry stallisation and welting at 53’; when anhydrous, the salt melts at 113”. 93. “A direct method for determining the latent heat of evaporation.” By J. Campbell Brown.The latent heats of thirteen alcohols, seven acids, and twenty-eight esters have been directly determined by means of an apparatus adapted for ascertaining the weight of liquid evaporated by a determinate amount of heat applied at the boiling point of the substance, when this is surrounded by a double jacket containing its ow11 vupour. 94. ‘‘ Isomeric partially racemic salts containing quinquevalent nitrogen. Part X. The four isomeric hydrindamine d-chloro- camphorsulphonates, NR, li2H3.” By F. S. Kipping. ’l’he isomeric partially racernic a-and p-salts obtained from &by drindamine and d-chlorocamphorsulphonic acid (Trans., 1900, 77, SS9) are not resolved into their components under canditions 165 similar to those employed in the resolution of the corresponding bromo-salts (YYoc.,1902, 18,SOS), but the four isomeric salts of the type NR,R,H,, from which the partially racemic compounds are formed, have been isolated and examined.d-Hydriodamine, prepared from the pure ad-bromo-salt (previously denoted aA-salt, PTOC.,Zoc. cit.), combines with d-chlorocamphor-sulphonic acid giving rise to two isomeric salts, one of which is formed in relatively very small quantities. The principal product, which corresponds with the ad-bromo-salt and is distinguished as the ad-isomeride, is easily obtained in B pure condition ; it separates from water in well-defined, compact, hydrated crystals, melts at 208-209°, and has a specific rotation + 46" in aqueous and + 15.5' in chloroform solution, It differs greatly in outward properties from the corresponding ad-salt of the bromo-acid, and also from all the other three isomeric chloro-salts.The second product, which corresponds with the Pd-bromosalt (previously denoted PA-salt), is only obtained in a pure cordition after a long course of fractional crystallisations ; it separates from water in long, hydrated needles, melts at 20%--203°, aud its specific rotation in aqueous solution is [a]n= +59", the value in chloroform being [alu= +50°. The great differelice between these isomerides is very noteworthy considering the fact that the corresponding bromocamphorsulphonates of hydrindamine and of methylhydrindamine (Tattersall and Kipping, this vol., p. 145) are so similar that the pd-isomeride cannot be obtained in a pure state.The pure ad-hydrindamine chlorocamphorsulphonate, decomposed with barium hydroxide solution, gives both the ad- and the pd-isomerides when regenerated from its coinponent acid aud base, a proof that these two salts are formed from structurally and optically identical components. I-Hydrindamine, prepared from the pure al-modification (previously denoted aB) of the bromo-salt, also combines with d-chlorocamphor- sulphonic acid giving rise to a mixture of very unequal quantities of two isomeric salts. The principal product, the ah-modification, comes-yonding with the ab-bromo-salt, separates from water in long, anhydrous needles, indistinguishable in appearance from those of the ab-homo-com- pound ; it melts at 118-1 1go and has a specific rotation [a],= + 44' in aqueous and + 45.5" in cbloroform solution.'The subsidiary product, namely, the pl-isomeride (formerly denoted PB), is only separated in a pure condition with very great difficulty ; it crystallises from water in lorry, anhydrous needles which generally melt at about 140-1 46O, the indefinite melting point being apparently due to dimcrphism, as iu 166 the case of the corresponding bromo-isomeride. Its specific rota tion is [aJD= +57*5” in aqueous and +60*3”in chloroform solution. When the pure al-chloro-salt is decomposed with barium hydroxide solution and then regenerated from its own acid and its own base, A mixture of the al-and pl-isomerides is obtained, just as from the original I-base.It is to be noted that the pd-and pZ-chloro-salts have n much ItigAey molecular rotation than that of d-chlorocamphorsulphonic acid, whereas in the case of the corresponding bromo-salts the position is reversed ; it follows, therefore, that the formation of these isomerides cannot be attributed to any partial racemisation of the acid or the base. The isolation of these four isomeric hydrindamine d-chlorocamphor- sulphonates seems to afford the final proof that the author’s explanation of the existence of the partially rscemic a-and P-salts is the true one (Trans.,Zoc. cit.). 95. (‘Isomeric compounds of the type NRIR,H,.” By F. S. Ripping. The isolation of the four isomeric hydrindamine cl-chlorocamphor- sulphonates (see previous abstract), the proof of the existence of four isomeric methylhydrindamine bromocamphorsulphonates (derived from one dl-base) (Tattersall and Kipping, this vol., 145), and other evidence fully confirm the author’s views as to the nature of the isomeric partially racemic salts which have been previously studied (Kipping, Trans., 1900, 77, 861 ; 1901, 79, 430), and establish the occurrence of isomerism in compounds of the type NR,R,H, (Proc., 1902, 18, 21 1).The stability of the isomeric salts in aqueous solution leads to the conclusion that there are two different ions NR,H,-for each optically active base, and, consequently, it should be possible to transfer such ions froin one acid to another without altering the configurations particular to them.Experiments bear out this conclusion. The partially racemic p-salt of hydrindamine and cl-bromocamphcir-sulphonic acid is not converted into the corresponding a-salt when it is repeatedly evaporated first with concentrated hydrochloric acid and then with water, or when it is successively treated in aqueous solution with sodium carbonate and hydrochloric acid, the solut,ion being then evaporated. The four basic ions of the p-salt can thus be transferred from the bromo-acid to hydrochloric or to carbonic acid, and back again to the bromo-acid without altering their relative pro- portions as long as the base is never in the free st.ate. The platinichlorides, prepared from the atl-, al-, and pl-modifications [previously called the a A-, aB-, and p B-modifications respectively (Proc., 1902, 18, 209)] of hj-drindamine d-bromocamphorsdphonate by pre-cipitating in presence of hydrochloric acid, seem to be identical in outward properties, and the hydrochlorides obtained froin the platini- chlorides by decomposing with hydrogen sulphide are also indis- tinguishable in appearance and in melting point; it mould seem, nevertheless, that each of the optically active hydrindamines gives rise to two different hydrochlorides (indistinguishable in ordinary propel-ties), firstly, because of the behavionr of the partially racemic @salt (see above), and, secondly, because the ,8Z-moditicatlion of hydrind-amine ~-ctilorocamphorsiilphon;ttecan be converted into a hydrochloride from which the original pl-salt is obtained on evaporating with the chloro-acid.The hydrochloride, prepared from the above-mentioned pl-bromo-salt,, gave with ammonium d-bromocamphorsulphonate what appeared to be the pure PZ-isomeride, but on repeating the experiment under different conditions, starting from the pZ-chloro-salt8, the akmodificntion was obtained : further investigation is necessary before this difference in behaviour can be explained, but it seems reasonable to conclude that fow isomeyic hgld~-ochZoi.idesof hydrindamine are capable of existence. The molecular rotations of the ad-and al-salts in dilute aqueous solution are in all cases practically normal, hut the pd-and pl-hyclrind-amine bromocamphorsulphonntes give values which are far too low, whereas the pd-and /3Z-hytlrindamine chlorocamphorsulphonates give numbers which are far too high ; molecular weight determinations in boiling aqueous solution seem to indicate that the salts of the p-series are not .so highly dissociated as the corresponding a-salts, but the evidence is very inconclusive.The existeiice of isomeric salt8s of the type NR,R,H, can be accounted for by assuming that the five valencies of the nitrogen atom are directed from the centre to the angles of a square-based pyramid, but in view o€ t'he highly conflicting experimental evidence bearing on the question of the configuration of the nitrogen atom, this subject cannot yet be profitably discussed; even in the case of trivalent nitrogen, there is gre,tt uncertainty, 3s no case is yet known of isomerides of the type NR,R,R,, although the existence of such compounds is R probable, if not .z necessary, consequence of the hypothesis of Hantzsch and Werner.168 ADDIl’IONd ‘L’O THE LIBRARY. Schiff, Ugo. ¶xione delle funxiotli basica ed acida per mezzo delh formaldeide. (Frona the Gaxx. C‘him. Ital., 33,pt. I, 1903.) Speroni, C. Di alcilni derivati aldeidici del solfito di anilina. (E’rona the Gmz. CIuinL. Itatl., 33,pt. 1, 1903.) Van Slyke, L. L. Some facts about; commercial fertilizers in New York State. (Baing BUZZ. LVO.230, New York Ayric. Exper. &ition, 1903.) Van Slyke, L. L., and E. B. Hart. The relation of carbon dioxide to proteolysis in the ripening of cheddar cheese.(BeiTzg UuEZ. No. 231, New York Agric. hpev. Station, 1903.) Voelcker, J. A,, aud A. D. Hall. The valuation of unexhausted manures obtained by the consumption of foods by stock. Wilay, EL W. Manufacture of table syrups from sugar cane. (h’ezny US‘.Llept. 01-Byrmic. Bureau oj. Chemistry, Bull. iVo. 53.) At the next meeting, on Wednesday, June 17th, at 5.30 p.m., there will be a ballot for the election of Fellows, and the following papers will be communicated :-‘‘ The electrolytic estimation of minute quantities of arsenic, more especially in brewing materials.” By T. E. Thorpe. &‘ The estimation of arsenic in fuel.” By T. E. Thorpe. “ Crystalliseci ammonium sulphate and the position of ammonium in the alkali series.” A. E.H. Tutton. ‘‘ Action of hydrogen on sodium.” By A. Holt, jun. “The action of halogens on compounds containing the carbonyl group.” By A. Lapworth.‘‘ Reactions involving the addition of hydrogen cyanide to carbon compounds.” By A. Lapworth. “The acetoacetic ester synthesis.” By A. C. 0, Hann and A. Lapworth.‘‘ Rimu resin.” By T. H. Ettsterfield and B. C. Aston. “Note on the Karaka fruit.” By T. H. Ensterfield and B. C. Aston. 6‘ The slow oxidation of methane at low temperatures. Part 11.’’ By W. A. Bone and R. V. Wheeler. 169 CER8'FIB'JCATES OF CANDIDATE8 FOR ELECTION ,4T THE NEXT BALLOT. N.B.-The cames of those who sign from '' Gmeral Knowledge " are printed iu italics.The following Candidates have been proposed for election. A ballot will be held on Wednesday, June 17th, 1903. Aubrey, Henry James, The Cross, Worcester. Analytical and Research Chemist. Member Pharmaceutical Society Gt. Britain. Certificated Society apothecaries, London. Original work done on the treatment of hop yards for the destruction of blight, &c. Herbert S. Shorthouse. Wallace C. Nickels. W. S. Howie. Charles Btzyliss. (r'eo. G'. Perry. Barger, George, 50, Guilford Street, W.C. Physiological chemist at the Wellcome Research Laboratories, Heme Hill, S.E. B.A. (Cantab.), B.S;c. (LonlL); late assistant at the Botanical Institute, Brussels University ; engaged in physiological chemical research ;published a paper in Ber.d. deutsch. Chesn. G'eselZsclL., 1902. S. Ruheruann. W. J. Sell. Charles T.Heycock. F. h'. Dootson. H. 0. Jones. Bennett, Colin Noel, 95, High Street, Citmden Town, N.W. Student Chemical Laboratory, University College, London. For the last 24 years student at Chemical Laboratory, University College, London, J. Norman Collie. Alex. K. Bsin. Edward C. Cyril BJy. 5. E. Sheppard. Morris W, Travers. William Ramsay. Bibby, Charles Drake, 69, Queens Road, Twickenham, Middlesex. Chemist. Assistant in the Chemical Laboratory of Msssrs. Burgoyne, Burbidges and Co., 1894 to 1899. Assistant Chemist in t.he Laboratories of the Pharmacie Centrale de France, Saint-Denis (Seine), 1899 to 1900. Student of Physiological Chemistry at King’s College, London.At present Chemist in the Laboratory of Messrs. Pmke, Davis and Go., Hounslow. Thos. Farries. Theophilus Pitt. Reginald G. Halstead. Georges Ponthieu. Alf. J. Parker. Brennand, Henry John Wolverton, 203, Macquarie Street,, Sydney. Medical Practitioner, employed as an Officer of the Government Statistician of New South Wales. Bachelor of Arts, Bachelor of Medicine, Master of Surgery, of the University of Sydney. (Honours in Chemistry.) At present engaged in bhe study of Physiological Chemistry. Formerly Teacher of Chemistry at Newington College, Sydney. Member of Royal Society of New South Wales. A. Liversidge. F. B. Guthrie. J. A. Schofield. Basil Turner. IVilZiani Af. Hamlet. Burghard,William Godsell, 180, High Holborn, W.C.Student. Have studied Chemistry, Physics, Biology, Mathematics, and Geology since 1894 at the Birkbeck Literary and Scientific Institution and elsewhere. Hold Science and Art Department Cer- tificates for Organic and Inorganic Chemistry. Now engaged in private chemical research work. John E. Mackenzie. H. P.C. Goltz. J. Woodward. Wm. W. S. Nicholls. Edward Jones. 171 Bury, Ernest, M.Sc. Brackley Coke Works, Little Hulton, near Bolton, Lancs. Chemist to tho Bridgewater Trustees, and Superintendent of the Brackley Coke Works. Student in the Chemical Department, Oweus College, Manchester, 1891 -1 895. Graduated B.Sc. (Vict. Honours School of Chemistry) in 1695, and M.Sc. in 1899. Since 1895, he has filled the post of chemist to the Bridgewater Trustees, and is now in charge of their Brackley Bye-Product Coke Works at Little Hulton, near Bolton, Lancs.M7. H. Perkin, jun. So in an Smith. Harold B. Dison G. H. Bailey J. E’. Thorpe. William A. Bone. D. 1,. C‘hapnliin. Campbell, Thomas, 38, Eastbourne Street, Liverpool. Science Master at St. Bede’s Grammar School, Bradford. Winner of two open Science Scholarships (S35 per yr. for 2 years ;$65 per year for 3 years) atiuniversity Coll., Liverpool (Vict. Univ.), in which Chemistry was one of the subjects. Studied for one session under Dr. Tate at Liverpool School of Science (Chemistry). For 2 years was a student (Science) of University College, Liverpool. For 1 year was a student (Science) of Yorkshire College, Leeds (Victoria University).Have passed Inter. B.Sc. (Vict.) with Chemistryas one of the subjects. Have taught Chemistry (Theor. and Prac.) at above School since September last. W. Ramshaw. George Tate. Ernest Eowman Ludlaru. G‘eo. JY. Velcll. J. Campbell Brown. v.c‘oui?zgwood I VilliUltLs. Wm. E. Davidson. Kohert C. I/’nrmer. Carrier, Albert James, 30, Kingwood Road, Oldtield Park West, Bath. Teaching. I have worked in the laboratories of the Bath City Auslyst, of the Bath Technical Schools, and of the Bristol Merchant Ventiirers’ College, passing from the last named the Board of Education exumina- tions in Theoret. and Pract. Cheru. (Hononrs, Part. II),and also the B.Sc. exam. of the London University with 1st Class Honours in Chem Since Sept.1901, lecturer at the Eristol Xerchant Venturers’ College J. Wertheimer. Arnold Philip. G. P. Damell-Smith. Albert E. Thomas. Johsi. E. Mackenzif. 172 Fairhall, Edwin Jesse, 29, Winsham Grove, London, S.W. Analytical and research chemist in works, Four years at Central Technical College, South Kensington. Henry E. Armstrong. T. M. Lowry. William A. Davis. Edward W. Lewis. A. J. Cownley. Gandy, William Hunter, Brad ley Court, Mitcheldean, Gloucester. Principal of Farm and Colonial School. Have passed London Int. B. Science examination in Chemistry, Btc. Lecturer in Chemistry, both Agricultural and General, at Wellington Hall Agricultural School from 1895-1900. Lecturer in Chemistry at Norfolk Military College, Overstrand, Cromer, from 1900-1902.I have classes in Chemistry here. R. Bodmer. Fred. J. Lloyd. Rasil Wm. Valentin Bernard Bye?.. J. A. Basker. tK P. Skertcldy/. AIJi.ed C. Ckapmrm. Harmer, Francis Gerald, 14, Tivoli Place, Ilkley. Address for Letters, &c., Middle Class School, Leeds. Schoolmaster (Secondary School and School of Science-Head-master). Headmaster of School of Science. Teacher of Chemistry (in above), Leeds, S years, and also in London for 4 years. Lecturer in Evening Science and Art Classes in London 4 years. Arthur Smithells. Wm. A. Knigtit. W. Ludford Freeman. W. B. Hiirds. Thomas Hartley King, Frank William George, 15, Almond Road, Lower Tottenham, N. Chemist to the “ Veda Food Company,” Edinburgh.Studied Chemistry under Dr. J. T. Hewitt for 2 years. Junior Assistant to, Dr. Bernard Dyer 14 years. Assistant to J. HeroniEsq., 2 years. Bernard Dyer. J. F. H. Gilbard. John Heron. J. T. Hewitt. [Frank E. King. Levy, Henry Wolf€, Christian & Levy, 423~’Chancery Lane, Melbourne. Assnyer, Metallurgist, and Chemical Analyst, and member of the above firm, has studied Chemistry for four years under the tuition of Messrs A. H. Jackson, B.Sc., F.C.S., M.I.E.E., &c. David Avery, M.Sc., Heber Green, RI.Sc., &c., and has spent some two years studying in the Laboratory and working on Messrs. Jaques Bros. Metallurgical Plant, Richmond. He is one of the Founders and Honorary Secretary of the newly-formed Institute of Analysts, Assayers, and Metallurgists, Victoria, and is at present engaged on research work in connection with titanium.As he is desirous of admission into the Chemical Society in order to receive their publications so as to keep in touch with Chemical Progress, we, the undersigned, propose and recommend him as a proper person to become n Fellow t’hereof. Frederic Dunn. A. H. Jackson. Robert Law. Francis R.Power. Fred. W. Steel. Linday, John Howard, Fenton Hall, Gt. Fenton, Stoke-on-Trent’. Assistant Analytical Chemist. Studied at Ackmorth School under Dr. Lean, and at Longton under Dr. Harris. For two years Assistant Analyst to the Stafford Coal and Iron Co. Am desirous to obtain the Chemical Literature of the Society.Joseph West. Geo. W. Burman, Walter Harris. Bevm Lean. J. Howard Davidson. Livesey, Charles Edwin Leonard, 23, Swinton Place, Gt. Horton, Bradford. Science Teacher (Senior Science Master, St. Bede’s Ura,mmals School, Bradford). Degree of Bachelor of Science after 3 Years’ Course at the Yorkshire College. Two Years’ Science Teacher as above (Subjects : Chemistry and Physics). Arthur Smithells. H. M. Dawson. Julius B. Cohen. W. J1owson. Herwy Iz. Proctev. Mann, John Christopher, 9, Lambert Street, Hull. Manufacturing Chemist. Member Soc. Chem. Industry (since 1891). Fifteen years Analytical and Research Chemist at the Gas Light 174 and Coke Co.’s Products Works, Beckton, E. At present and for past 5 years Chemist and Nanager to Messrs.Major and Co., Ltd., Tar Distillers, Stc., Hull, John William Young. Frank H. Leeds. J. T. Hemitt. L. J. de Whslley. Rudolph Messel. Moore, Alfred Ernest, B.A., B.Sc.(London), St. John’s College, Battersea, S.W. Lecturer in above College on Mathematics and Physical Science. Fourteen years Lecturer in Chemistry, and for Seven years Senior Lecturer in Physical Science, a position held at present. Edgar E. Horwill. Frank E. Weston. J. Bernard Coleman. J. C. Crocker. Frccnk Clozoes. Moore,Arthur, 83, Elgin Eoad, Seven Kings, Essex. Student of Chemistry, both Organic and Inorganic, 5 years at City of London College, Moorfields. Holder of several certi6catos in Chemistry, Board of Xducation. -4nxious to possess the Chemical Society’s Journal.Imic S. Scarf. Jos. S. Bridges. Chns. A. West. Harold W. Harrie. l’hos. 2’ym*. Norman,George Marshall, 5, Watford Villas, Battersea Park, S.W. Student Demonstrator. sssociate of Royal College of Science and of Institute of Chemistry and Bachelor of Science, London Univ. William A. Tilden. H. Burrows. 31. 0. Forster. Chapmari Jones. G. T. Morgan. James C. Philip. Parry,George Harry, The Level, Brierley Hill, Staffs. Head Chemist, Earl of Dudley, Tlevel New Furnaces, Brierley Hill. Educated at Stourbridge Grammar School, where took Chemistry ; afterwards studied under W. Whitehouse, Esq., Wolverhampton, and IF. Thompson, Eaq., F.C.S., Dudley; with H. Silvester, Esq., F.C.S., F.I.C., Borough Analyst, West Bromwich, Do., Do., Dudley, first as pupil, afterwards chief assistant 3 years.I am now Head Chemist to The Rt. Hon. The Earl of Dudley, Level New Furnaces, Brierley Hill, and have been so ten year$. Harry Silvest er. Robt. D. Connell. W. H. Pearsor. A. E. LVcKenzxie. Jurnes E. Feryuson. Purcell, Charles Stanley, 37, Acomb St., Greenheys, Manchester. Assistant Chemist. h Student for three years in the Brewing Depart. of the School of Technology, Manchester. Has obtained the Honours Certificate of City and Guilds in Brewing. Honours in Chemistry of Board of Xducation. Assistant Chemist to Messrs. Robertson and Sons, Manchester. William J. Pope. I;.G. Radcliffe. Jas. Grant.. F. S. Sinnatt. S. J. Peachey. J. Hubner.Rhind, Thomas, 69, Gloucester Road, Regent’s Park, London, N.W. Medical Practitioner. Member of Royal Collegs of Surgeons, Eng. Licentiate of Royal College of Physicians, London. Studying Sanitary Science and Chemistry. R. E. S. Richardson. H. N. B. Richardson. Lewis Ough. Henry Kenwood. John Atljeld. Smith, Charles Joseph, Sunnydale, Walton New Road, Stockton Heath. Brewer. Chemist at Messrs. Peter Walker and Son, Ltd., Warring- ton, Brewers. Member of Institute of Brewing. First cIass certificate for Brewing, Examination for which comprised Practical and Scientific Brewing and the Chemistry of Brewing ; First class certificates for Practical and Theoretical Inorganic and Organic Chemistry. For five years a student under Mr.F. G. Ruddock, F.I.C., SOC.Pub. Analysts. Jas. GranC. 5.Rymer Young. L. G. Radcliffe. 3’.8. Sinnntd. S. J. Peachey . Smith, James Cruickshank, B.Sc., 57, Great Ormond Street, Russell Square, W.C. Professional and business address, 20, Nassau Street, Mortimer Street, W. Technical Chemist (Member of the Society of Chemical Industry, Member of the Society of Arts), Formerly Chief Assistant 176 “ Young ” Laboratory of Technological Chemistry, Glasgow and West of Scotland Technical College. Afterwards Technical Chemist and Works Manager. Author of ‘‘ The Manufacture of Pltict ” (Scott, Greenwood and Co., 1901); (‘ Notes on the Technical Examination, Analysis, and Valuation of Oils and Lubricants ” (Lewis, Jameson and Co., 1903), and of numerous Articles and Papers in Scientific and Trade Journals.Edmund J. Mills. (2. G. Henderson. F, R. Japp. John B. Om. William Mai tland. Tyrrell, Dennis, 182, King Street, Norwich. Chemist and Brevrer. Chemist and Brewer for Messrs. Youngs, Craw-shay and Youngs, Ltd., Crown Brewery, Norwich. I have also attended classes in connection wikh S.K. for Chemistry, Organic and Inorganic (Theor. and Prac.), under S. Hewitt,, F.C.S., and R. S. Cahill, F.C.S., and am desirous of keeping in touch with the latest progress in Chemical Science. Francis Sutton. R.S. Cahill. 8. Hewitt. Hdip G. G. Moon. Alfred C. Young. A. Pecccoclc. C. E. VomersZe~/. Van Laer, Norbert, 69, Calais Road, Burton-on-Trent. Brewer and Chemist to Messrs.Truman, Hanbury, Buxton, & Co., Ltd. For three years a student at the Technical School and Muni- cipal Laboratories of the City of Ghent, Belgium. Also three years’ Scientific training at the Professional School of Brewing of Ghent,, and a Graduate of the same. C. O’Suliivan. C‘has. Geo. RZatt.hems. Jas. O’Sullivan. A. I,.Stern. George Harrow. Adrian J. Brown. Woolhouse, Sidney Herbert, 2, Durham Rd., Lr. Edmonton, London, N. Science Master, Parmiter’s School, Victoria Park, London, N.E. (Teacher since lSS9). M.A., B.Sc., Assoc. Royal College of Science, Dublin. W. N. Hartley. William A. Tilden. W. E.Adeney. Morris W. Travers. Hugh Ramage. 177 The following was authorised by the Council under Bye-Law I. (3) : Beveridge, Wilfrid William Ogilvy, A.M.S.Laboratory, Pretoria, S.A. Major Royal Army Medical Corps, In charge of A.M.S. Labora-tories for Transvaal, Orange River Colony, and Cape Colony. Written various reports for the Army on Food Stuffs, Disinfectants, etc. Walter C. C. Pakes. Alex. Crum Brown. William J. Pope. Leonard Dobbin. !A. CLAY AND SONS, LTAI., BXEAD 8'1'. lLILL, E.C., Ahll BI NGAY, SUkEOLli.
ISSN:0369-8718
DOI:10.1039/PL9031900155
出版商:RSC
年代:1903
数据来源: RSC
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