Issued 10/3/05 PROCEEDINGS OF TBE CHEMICAL SOCIETY. VOl. 21. No. 291. D.Sc., F.R.S.,Thursday, March 2nd, 1905. Professor W. A. TILDEN, President, in the Chair. Messrs. Kobert J. Caldwell, Edward Evans, Lewis Eynon, and E. J. Fairhall were formally admitted Fellows of the Society. Certificates mere read for the first time in favour of Messrs. : John George Baxter, Court Sole, Cliffe, Nr. Rochester, Kent. Roger Dodds, Bigods Hall, Dunmow, Essex. Sydney Dunstan, 107, Jesmond Road, Newcastle-on-Tyne. A1berb Gillies, Government Laboratories, Johannesburg, S. Africa. Henry Isaac Gorman, 126, Quay, Waterford. Ernest Green, 113, Hulton Street, Moss Side, Manchester. John Hawthorne, 7, Roseneath Villas, Military Road, Cork. -4rthur Lonsdale Hetherington, B.A.,Government Collegiate School, Rangoon, Burma.Sydney A. Kay, D.Sc., 72, Market Street, St. Andrew’s. Leonard Gibbs Killby, B.A., 10, Aberdeen Park, Highbury, N. Ernest Isaac Lewis, B.A., B.Sc., Felstead School, Felstead. Alfons O’Farrelly, M. A,, 3, Holles Street, Dublin. William Sarginson, B.Sc., 500, Cauldon Road, Stoke-on-Trent. Robert Reed Swam, B.Sc., The Sgricultural College, Aspatria, Cumberland. 72 Of the following papers, those marked * were read : *24. ‘‘The relation between natural and synthetical glyceryl- phosphoric acids.” By Frederick Belding Power and Frank Tutin. Glycerylphosphoric acid was first prepared synthetically by Pelouze (Compt. retad., 1845, 21, 718, and J.pi-. Chem., 1845, 36, 257), who, from the analyses of some of its salts, concluded that it mas identical with that obtained from lecithin, By the interaction of glycerol and phosphoric acid, it is possible that several esters may be formed, and three of these are now known, namely : the mono-ester, or glycerylphosphoric acid, C3H5(OH),*O*PO(OH)2; the so-called di-ester, and the tri-ester, C3H5:P04.The authors have shown that the discrepancies of statement respect- ing the composition and characters of the salts of glycerylphosphoric acid (compare Portes and Prunier, J. Phccmt. China., 1894, 29,393 ; Petit and Polonomsky, ibid., 1894, 30, 193 ; and Adrian and Trillat, ibid., 1898, 7, 226) are due, as has been suggested by Carre (Co?1qvt. re?zd., 1903, 137, 1070), to their contamination with salts of the above-mentioned di-ester.It was therefore deemed of interest to ascertain the characters of the salts of glycerylphosphoric acid when prepared under such conditions as are known to exclude t7he forma- tion of the di-ester, and a number of these have been described and analysed. In the course of the authors’ work, Willstiitter and Ludecke described an investigation (Be?..,1904, 37, 3753) in which they compared the barium and calcium salts of the natural and synthetical glyceryl- phosphoric acids, and came to the conclusion that the differences between them are not those which are usually observed in the case of optically active and racemic compounds. These differences consisted in the amount of metal contained in the respective salts, in the varying amounts of water believed to be retained by them when dried at certain temperatures, and in their relative solubility in water.The authors have shown, however, that the conclusions of Willstatter and Ludecke are not valid, inasmuch as their synthetical glycerylphosphoric acid was prepared under conditions which are known to afford some of the di-ester, and that the discrepancies they have observed are to a large extent due to the Contamination of their salts of the synthetical acid with those of the di-ester rather than to the amount of water retained by them when subjected to heat. The fact mas also noted that the natural glycerylphospboric acid has in no instance been prepared from a lecithin which was known to be cz pure individual substance.Although the preparations obtained from this source by Willstatter and Ludecke possessed optical activity, which proved the presence of the unsymmetrical acid, no evidence can as yet be adduced that they did not contain some of the sym- metrical isomeride. *25. (‘ The transmutation of geometrical isomerides.” By Alfred Walter Stewart. In order to explain this series of phenomena, the author assumes as a phase of the reaction the formation and disruption of a tetramethylene cornpound. In the case of maleic and fumaric acids, the intermediate compound mould be a tetramethylene-1 : 3 : 3 : 4-tetracarboxylic acid, in which, probably, the carboxyl groups attached to the 1 : 2-carbon atoms would lie on the side of the ring opposite to those attached to the 3 : 4-atoms.Such a tetrainethylene ring might split up in two ways ; either by breaking the linkings between 1 and 2, 3 and 4 ; or by breaking those joining 1 to 4 and 2 to 3. In the former case, fumaric acid is formed ; in the latter, maleic acid is regenerated. If, however, fnmaric acid is produced, owing to its higher melting point, it is immediately withdrawn from further action, while maleic acid is free to undergo the same series of changes. Fumaric acid, when distilled in presence of phosphoric oxide, is assumed to form the same type of tetramethylene derivative ; but in this case water is abstracted from the carboxyl groups attached to the 1 : 2-carbon atoms, and also from those attached to the 3 : 4-atoms, the groups in each pair being in the cis-position to one another. Owing to the presence of the two anhydride chains, the tetramethylene ring cannot now break across in either of two mays, as in the last case, and consequently its disruption produces maleic anhydride.The complete series of changes : Fumaric acid Maleic acid +---Maleic anhydride Fumaryl chloride can be thus explained; and also the transformations undergone by stereoisomeric oximes, hydrazones, and diazo-compounds. The author gives instances in which the tetramethylene intermediate product has actually been isolated, when it is found that its behaviour fulfils the conditions required by the hypothesis. 74 DISCUSSION.Dr. COLMANpointed out that tetrametliylene-mono-and -di-carboxylic acids are very stable substances, and that it therefore hardly seemed probable that the tetramethylenetetracarbovylic acid, assumed by the author to be the intermediate product between fuinaric acid and maleic anhydride, would be so readily resolved quant’itatively into two molecules of maleic acid. “26. ‘‘Linin.” By James Stuart Hills and William Palmer Wynne. According to Pagenstecher (Buclmer’s Repegst. Pltamz ., 1840, 72, 311 ; 1842, ’76,313 ; 1843, 79, 216) and Schroder (J>ues Repert. Ylmrm., 1861, 10, 1I), purging flax (Li.nunz catlmdcmt), a small indigenous herb, contains a substance, linin, to which the former investigator attributed the purgative properties of the drug.The authors believe the active principle to be a glncoside, which, however, has not been isolated in a pure state owing to its uncrystal- lisable nature. On hydrolysis with dilute acids or with lime, the glucoside is resolved into glucose and a substance which, so far as the comparison can be made, seems to be identical with Schroder’s linin. The yield of crude linin amounts to about 0.13 per cent. by weight of the drug. Linin, C,,H,,O, (mol. wt. 445 and 451 in naphthalene ; 453 and 437 by the boiling point method in acetone), crystallises froni alcohol in needles,and melts at about 203O,the exact melting point depending on the mode of heating ;it is insoluble in water, sparingly soluble in the usual organic solvents, and gives a deep purple coloration with concentrated sulphuric acid.It contains four methoxyl groups, as determined by the Zeisel method ; the demethylated derivative proved to be uncrys- tallisable. At tempts to prepare acetyl and benzoyl derivatives of linin were fruitless, and inconclusive results were obtained by fusion with caustic potash. Oxalic acid was the only recognisable product when it was oxidised with nitric acid or potassium permanganate under varied conditions. Linin is destitute of purgative properties. *27. (‘The constitution of phenylmethylacridol.” By James John- ston Dobbie and Charles Kenneth Tinkler. When phenylacridine methiodide is treated with an alkali, a hydroxide is formed which was supposed at one time to be the base corresponding with the original salt.Hantzsch, however, from the results of con-ductivity experiments, concluded that it is really a carbinol formed by the shifting of the hydroxgl group from the nitrogen atom to an adjacent carbon atom at the moment of precipitation. Confirmation of this view is afforded by the fact that whilst the absorption specOra of phenylacridine inethiodide and of the hydroxide derived from it diff er widely, the spectra of the latter substance agree very closely with those of dihydrophenylacridine. This resemblance is inexplicable unless we regard the hydroxide as a carbinol bearing the same relation to dihydro- phenylacridine that cotarnine bears to hydrocotarnine or hydrastinine to hydrohydrastinine (Trccns.,1903, 83,598 ; 1904, 85,1005).28. ‘‘The ultra-violet absorption spectra of certain diazo-com-pounds in relation to their constit ntion.” By James Johnston Dobbie and Charles Kenneth Tinkler. The anthors have applied the spectroscopic method to the investiga- tion of isomerism in the diazo-group. They find that the stable and unstable forms of the isomeric diazosulphonates and of the isomeric diazocyanides derived fromp-anisidine and p-chloroaniline give identical spectra, or spectra agreeing more closely than those of any isomerides which difier strncturally from one another. They regard this result as nffording confirmation of the correctness of Hantzsch’s view according t,o which these substances are syta-and anti-modifications, differing from one another in the same way as the sp and mati-oximes.On the other hand, the isomeric potassiuni benzenediazotates, as also the two forms of the potassium compound obtained from diazotised sulphanilic acid, give widely different spectra. The spectra of the more stable (Schraube and Schmidt’s) potassium benzenediazotate are almost identical with those of phenylmethylnitrosoamine, from which the authors infer that these compounds are constituted alike and are repre- sented respectively by the foimtilze C,H,*NK*NOand C,H,*N(CH,)*NO. 29. “The latent heat of evaporation of benzene and some other compounds.” By James Campbell Brown. An improved apparatus has been emploJed in determining exactly the latent heat of benzene and its homologues. The latent heats of tert.-amyl alcohol and propyl isobutyrate are also recorded, together with Trouton’s values (compare Trans., 1903, 83,987).30. ‘(The reduction of isophthalic acid ” By William Henry Perkin, jun., and Samuel Shrowder Pickles. When isophtlialic acid is reduced with sodium amalgam at 45’, it yields two tetrahydro-acids (A2 and &-A5), and, from these, two 76 further acids are obtained by the methods mentioned below. Since there can only be four tetrahydroisophthalic acids, namely : x H-X X-H it follows that the authors have been successful in isolating all the possible modifications. A2-Tetra?~~di.oisop?~t?~a~icacid melts at 16S0, is very solnble in water, and is characterised by yielding a rather sparingly soluble calcium salt and an anhydride which melts at 78' ; it combines with hydrogen bromide and with bromine to form 2-bromohexahydroisophthalic acid (m. p.185-1 87') and 2 :3-dibromohexahydroisophthalicacid (m. p. 302') respectively. When oxidised fire t with permanganate and then with chromic acid, it yields succinic acid. As-Zbtra?~~droisop?~t?~aZ~cacid is produced when the other tetra-hydroisophthalic acids are boiled with strong caustic potash, intra- molecular change taking place ; it melts at 244" and is very sparingly soluble in water. When it is dige.ted with acetic anhydride and then distilled, it is converted into the anhydride of the A2-acid. It com-bines with hydrogen bromide with difficulty, yielding a syrup which appears to be 4-bromohexahydroisophthalic acid and readily absorbs bromine vapour with formation of 3 :4-dibromohexahydroisoph thalic acid (m.p. about 230O). The latter acid is decomposed by boiling with caustic potash with formation of a dihydroisophthalic acid which melts at 255' and is very sparingly soluble in water. When the A3-tetra- hydro-acid is oxidised with permanganate or with nitric acid, it yields isophthalic and oxalic acids. cis-A5-Tetra?~ydroisopl~tJiuZiccccicl melts at about 165",is very reaclily soluble in water and, when digested with acetic anhydride ant1 distilled, yields the anhydride of the A,-acid. It combines with bromine with formation of 5 : 6-dibromo-cis-hexahydroisophthalicacid, which melts at about 220'.trans-A5-Tetl.al~ydroisop?~t?~alicmid is prodncecl when the cis-acid is heated with hydrochloric acid at 170'. It melts at 225-22'7", is very sparingly soluble in water, and combiiies with bromine to form 5 :64%-bromo-ti*cc~zs-hexahydroisophthalicacid, which decomposes at about 230-235'. The reasons which have led the authors t.0 assign to the various tetrasydroisophthalic acids the constitutions given above are discussed in the detailed paper. 77 31. "The influence of temperature on the interaction between acetyl thiocyanate and certain bases. Thiocarbamides, including carboxy-aromatic groups.'' By the late Robert Elliott Doran (compiled by Augustas Edward Dixon). Miquel's acetyl thiocyanate (AWL Clk. Phys., 1877, [v], 11, 295), when brought into contact at low temperature with aniline dissolved in benzene, showed little sign of thiocarbiniidic character, the principal change being the following double decomposition :AcSCN + ZPhNH, = PhNH,,HSCN +AcNHPh.On the other hand, when these inaterials were caused to interact at higher temperatures, the thiocyanic character diminished and the thiocarbimidic reaction increased, until, in the neighbourhood of 85O, about 90 per cent. of the additive-compound (acetylphenylthiocarbamide) was obtained, according to the equation AcNCS + PhNH, = AcNH*CS*NHPh. With o-tolnidine this was not the case, an experiment condncted at 85' giving 91 per cent. of the available sulphnr in the form of acetyl-o-tolylthiocarbamide, whilst at -3' the yield of this substance \FRS only a few per cenf;,JBR By combining acetyl thiocyanate with methylaniline in hot benzene, acet?/ln~et?~~Iphen?/Zthiozcyeawas obtained in white crystals melting at 93-94'.Acet?/Zp?~eiz?/Zbe,2xyZt?~iozcs.eccseparated from dilute alcohol in fine, rhombic crystals melting at 110-1 1lo. Piperidine gave no acetylpiperidylthioiirea, but piperidylthiourea instead, together with piperidyl thiocyanate ;the former melted at 126-127', the tempera- ture given by Wallach (Bey., 1899, 32, 1872), and by treatment with acetic anhydride yielded the ncetyl derivative, AcN:C(SH)*NC,H,, (long prisms, melting at 112-1 13'). Ry passing ammonia gas through a boiling solution of acetyl thiocyanate in benzene, 21 per cent.of the available sulphnr was obtained as acetylthiourea, hcN:C(SH)*NH,. Phenyl chlorocarbonate, PhO*COCI, when dissolved in benzene and left in contact with potassinm thiocyaiiate until free from halogen, gave a solution of cai.boxyp?~enyZtliocnl.bii,~icle; by treatment with met hylamine, this afforded carbox~pl~e~z?lZi~~etl~?/Ztl~ioccc1.baiizide, PhO.CO-KH CS-XHMe {long, glistening prisms melting at 175-1$63), isomeric with the author's carboxymethylphenylthiocarballzide, JIeO*CO*KH-CS*NHPh {m. p. 158') (Pimas., 1901, 79, 905). isCnl.boxy~~?Len?/lisoccI,z~Ztl~iocnrbccrniclea crystalline solid (m. p. 99-1 OOO), isomeric with carboxyisoamylphenylthiocarbamide (Zoc. cd., 914). PhenyZcc~rbox~~)lLei2~Ztl~iocarbaniide, PhO- CO-N€1.CS* NHPh, was ob-fnined (a) froin aniline, and (b) by expelling by means of phenyl 78 chlorocarbonate the acetyl group from acetylphenylthiocarbamide ; it melted at 148-149O. CarboxyguaiacoZphe~~ylthiocarbnmide, MeO*C6H,0 CO*NH*CS*NHPh, from guaiacol chlorocarbonate and acetylphenylthiocarbamide, melted at 154-155’ and was freely desulphurised by warming with alkaline lead solution. 32. “The influence of solvents on the rotation of optically active compounds. Part VIII. Ethyl tartrate in chloroform.” By Thomas Stewart Patterson. Data relative to the rotation of ethyl tartrate in chloroform at various concentrations and temperatures are given. Chloroform has a marked effect in depressing the rotation of the ester. It is shown that the variation of rotation is in agreement with the change in solution- volume of the dissolved tartrate.33. ‘;Afurther note on the addition of sodium hydrogen sulphite to ketonic compounds.” By Alfred Walter Stewart. The author has applied the method already described (Trcms., 1905, 87, 185) to some other compounds containing the carbonyl group. The rate of addition of sodium hydrogen sulphite to ethyl aceto- acetate having already been found to be much more rapid than was anticipated, it was thought advisable to try experiments with diethyl acetonedicarboxylate. The results were as follows : After 10 20 30 40 50 60 70 minutes. 40.2 55.3 61.0 64.5 68.1 71.2 73 0 per cent. of bisulphite compound. Comparing this with the numbers already fouiid in the cases of acetone and ethyl acetoacetate, it appears that the replacement of hydrogen by a carboxyl group increases the velocity of addition, and when a second carboxyl group is introduced instead OF another hydro- gen atom, the velocity is further accelerated.This seemed to point to the addition of sodium hydrogen sulphite to the carboxyl group itself, but when this hypothesis was tested by determining the addition of sodium hydrogen sulphite to ethyl acetnt’e, no interaction could be detected. Diacetylacetone and aceton!-lacetone mere also tried, one equivalent of sodium hydrogen sulphite solution for each carbonyl group present being used. The percentages for each carbonyl group were : Bisnlphitecompmnd.After10 20 30 40 50 60 minutes. Diacetylacetone... 14.6 17.8 21.3 23.9 26.3 27.5 per cent. Acetonylacetone ... 5.7 S.8 11.5 14.6 16.6 19.5 ,, Potassium P-camphorsulphonate, prepared by Reychler’s method (Bull. Soc. china., 1898, [iii], 19, 120), gave a constant value of 3.5 per cent. The figures for maltose, glucose, and lactose are : After 10 20 30 minutes. Maltose ... 2.6 3.9 3.1 per cent. of bisulphite compound. Glucose ... 5.2 5-2 5.2 ,, ’3 Lactose ... 7.7 8.4 9.0 ,, 9, Unsuccessful attempts to prove tho existecce of additive products were made with epichlorohydrin, carbamide, acetamide, formamide, ally1 alcohol, and ethyl cinnamate. Dimethylpyrone gave traces of some additive compound, but concordant results were not obtained.34. (‘Action of bydrogen peroxide on carbohydrates in the presence of ferrous sulphate. Part V.” By Robert Selby Horrell and Albert Ernest Bellars. In this communication, attempts have been made to trace the dis- appearance of different sugars during their oxidation by observing the decrease in the rotation angle, and from the determination of the initial and final reducing powers of the solutions, as well as their acidities, to obtain a fuller knowledge of the many oxidation stages which occur. The results of the change in the optical activity show that during successive additions of hydrogen peroxide up to 1 gram-molecule for the same weight of carbohydrate, the decrease in the angle is proportional to the amount of oxidising agent added.The relative diminution in the angle depends on the sugar oxidised; galactose shows a greater decrease than glucose or fructose, maltose less than sucrose, which, in turn, has a smaller decrease than lactose. Rhamnose becomes kevorotatory on oxidation, and the rotation is practically constant after 2 gram-atom3 of oxygen have been added. The high values of the final reducing powers must be due to the strong reducing powers of keto-acids and osones formed in the oxidation, The acidities of the solutions after oxidation are not large, and are insufficient to account even for the complete formation of one mono-basic hexose acid. The smaller the yield of osazone precipitated by phenylhydrazine in the cold, the greater is the acidity of the solution.Attempts were made in the case of arabinose and rhamnose to isolate the acids formed during the oxidation. The simpler acids, formic and oxalic, were easily detected, but the more important keto-acids which were expected could not be isolated, although qualitative experiments leave little doubt as to their presence. Fischer’s method (Ber., 1902, 35, 3141) has been applied to the formation of arabinosone from arabinose, rhamnosone from rhamnose, and by using o-nitrobenzaldehyde, glucos- azone and rhainnosazone may be made to yield the corresponding osones. Radium emanations were found to have no influence on the oxida- tion of fructose. When the conditions were arranged so that change in the concentration of the solutions became impossible, the optical activity of the sugar remained constant.35. ‘‘Studies in chlorination. The chlorination of the isomeric chloronitrobenzenes.” By Julius Berend Cohen and Hugh Garner Bennett. In a recent paper by Cohen and Dakin (Trans., 1904, 85,1274), attention was directed to the relation which was found to subsist between the position assume6 by the third and fourth entrant chlorine atoms obtained by chlorinating o-and p-dichlorobenzenes and the six isomeric dichlorotoluenes, on the one hand, and those occupied by the two entrant nitro-groups on the other, and again by the fourth chlorine atom and nitro-group in the case of 1 :2 :4-trichlorobenzene and the six trichlorotoluenes. The investigation has now been extended to the chlorination of m-dichlorobenzene and the mono-and di-chloronitrobenzenes.The results show remarkable conformity with the above rule, and no single exception has been recorded. It therefore follows that when the first two hydrogen atoms of benzene or toluene have been substituted by either two chlorine atoms or by one chlorine atoni and one nitro-group, the positions occupied by subsequent chlorine atoms or nitro-groups are t,he same. The principal table of results is too long to reproduce, but that of the derivatives of wdichloro- and m-chloro-nitrobenzenes will serve to illustrate the rule. The only secondary product recorded in this table is p-dichloro-p-dinitrobenzene. The remainder represent the sole products of each reaction : 81 c1 C1 ’‘%/\$ CIc1 C1 c1 I \.1 j/ I \ x 4 C1 c1 c1 C1 NO,//\ NO,/\~ (,/NO,\P C1 C1 ANNIVERSARY DINNER.It has been arranged that the Fellows of the Society and their friends shall dine together at the Whitehall Rooms, Hotel MQtroyde, at 6.30 for 7 o’clock, on Wednesday, March 2Qth, 1905 (the day fixed for the Annual General Meeting). The price of the tickets will be One Guinea each, including wine, All applications for tickets should be inade not later than Wednes-day,March 22nd next. Tickets will be forwarded to Fellows on receipt of a remittance for the number required, addressed and made payable to the Assistant Secretary, Chemical Society, Burlington House, London, W.ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the election of Officers and other business will be heldron Wednesday, March 29th 1905, at half-pa& four o’clock in the aft,ernoon. a2 At the next Ordinary Meeting, on Wednesday, March 15th, 1905, at 5.30 p.m., the following papers will be communicated : ‘‘ The velocity of oxime formation in certain ketones.” By A. W. Stewart. “ Catechin and acacatechin. Supplementary note.” By A. Q. Perkin. ‘‘ The action of ethyl dibromopropanetetracai-boxylate on the di-sodium coinpound of ethyl propanetetracarboxylate. A correction.” By W. H. Perkin, jun. “Glutaconic acid and the conversion of glutaric acid into trimethyl- enedicarboxylic acid.” By G. Tattersall. “ The ultra-violet absorption spectra of certain enol-keto-tanto- nierides.” By E.C. C. Bnly and C. H. Desch. “Esterification constants of substituted acrylic acids.” By J. J. Sudborough and D. J. Roberts. 6‘ a-Chlorocinnamic acids.” By J. J. Sudborough and T. C. James. ‘(Di-ortho-substituted benzoic acids. Part VI. Conversion of methyl into ethyl esters.” By J. J. Sudborough and T. H. Davies. “A simple method for the estimation of acetyl groups.’’ By J. J. Sudborough and W. Thomas. ‘6 Gynocardin, a new cyaiiogenetic glucoside.” By F. B. Power and F. H. Lees. n. LJ,AY AND SONS, LTD., BREAD ST. HILL, E.c.. AND BUNQAY. GUFFOLK.