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Proceedings of the Chemical Society, Vol. 28, No. 401 |
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Proceedings of the Chemical Society, London,
Volume 28,
Issue 401,
1912,
Page 123-134
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PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl.28. No. 401. Thursday, May 2nd, 1912, at 8.30 p.m., Professor E. J. MILLS, D.Sc., F.R.S., 'Vice-Yresident, in the Chair. Certificates were read for the first time in favour of Messrs. : Cyril Douglas Birks, Cobnar Gardens, Woodseats, Sheffield. William Henry Bowater, School of Mines, Charters Towers, Queensland. Alfred Varlow Campbell, Rothamsted Experimental Station, Harpenden. Bamacharan Chatterji, &LA., Scottish Churches College, Calcutta. George Cruden Dieff enthaller, 7, Darcueil Lane, Belmont, Port of Spain, Trinidad. Leonard Harding, Fern Lea, Russell Street, Eccles. Harold Heron, 110, Fenchurch Street, E.C. Thomas John Keenan, 751, East Nineteenth Street, Brooklyn, 6-.S.A. Percival Edward Meadon, B.A.,6, Stanley Road, Oxford.Eric Keightley Rideal, B.A., 28, Victoria Street, S.W. Percy W harton Waters, Glenbervie, Melrose Avenue, Brooklands, Sale, Manchester. 124 A Baht for the election of Fellows was held, and the following were subsequently declared duly elected : Daniel Arkell, B.Sc. Richard Arnold Seymour-Jones, 11.S~. Arthur Leslie Bartow. Archibald Knox. Arthur Anderson Bones. Edwin Charles Lacey, B.Sc. Eruest Gowcr Bryant. Leslie Herbert Lanipitt, M.Sc. Charles Rugeley Bury, B.A. Harold John de Quetteville Lenfestey. Jatindranath Chakraborty, B. A. William Thornton Lucas, B. A. Evelyn Ashley Cooper, RSc. Ambat Kttsava Menon, B.A. Raymond Edwin Crowther. Robert John Milbourne. William Dallas. James O'Mara, B.A.Robert Percy Dougla3. George Macaulny Painter, B.Sc. Frederick Charles Eastick, B. A. John Rennie. Elliott Alfred Evans. Henry Alfred Shiite, B. Sc. aolin Burke Farlie, jun. Bawa Iiartar Singh, B.A. Edward Percy Frankland, B.A., Ph.D., Arthur Thompson. M. sc. John Scott Thoinson. Walter Elmslie gawkins, B.Sc. George Walker. James Grninger Hill. Arthur Wallace, B.A., B.Sc. Oliver Richard Howells, B. Sc. Frederick George Whittick. John Owen Hughes, B.Sc. Charles Reginald Wilkins, B.Sc. Edgar Dingle Junes. Of the following papers, those marked +(-were read: "102. '' Nor-hyoscyamine and nor-atropine ; alkaloids occurring in various solanaceous plants." By Francis Howard Carr and William Colebrook Reynolds. Nor-hyoscyamine-the secondary base corresponding with hyos- cyamine-was described, and shown to occur in a number of different species of plants of the natural order Solanacez, namely, in Scopolicz japonica, Dotura mctel, Datura meteloides, Duboisia myoporoides, and Mandrayorcc vernalis, all of which also contain hyoscyamine. The chemical constitution is expressed by the formula : CH,*CH*CH, C,H, I AH h*O-CO*hHI II ICH,.CH*CH, CH,*OH which is supported by the evidence: (1) that the alkaloid contains no NMe group; (2) that it forms a nitrosoamine, and therefore contains an :NH group; (3) that methyi iodide reacts with it, form-ing hyoscyamine; and (4) that it yields by hydrolysis tropic acid and nor-tropanol-a previously known baae.Nor-hyoscyamirie is laevorot'atory, and is racemised by the action of dilute alkali.The racemic base, nor-atropine, gives atropine oil methylation with methyl iodide. It therefore bears the sa,me relation to atropine as nor-hyoscyamine does to hyoscyamine. The properties of these two new alkaloids and their salts were described. Evidence was given to prove that the supposed isomeride of hyoscyamine, called $-liyoscyamine, described by Merck, is in reality nor-hyoscyamine. The best method of distinguishing nor-hyoscyamine and nor-atropine from each other and from the other mydriatic alkaloids, is by the melting points and crystalline form of various salts, particularly the oxalates, aurichlorides, and picrates. Nor-hyoscyamine and nor-atropine produce contraction of the pupil of the eye of the cat, but the activity is about one-eighth that of the corresponding ,%‘-methyl derivative.*103.‘b Researches on the constitution of physostigmine. Part I.” By Arthur Henry Salway. Physostigmine, when distilled with zinc dust, yields a mixture of 1-and 2-methylindoles. The author concludes that physostigmine contains a benzene nucleus attached to nitrogen, whilst it is not improbable that the atomic grouping, C,H,<N>C, is also present C in the alkaloid. The hydrolytic product of physostigmine, namely, eseroline, Cl,H,,0N2, first prepared by Ehrenberg in 1893, has been found to be a monacidic tertiary base, containing one methyl group attached to nitrogen. Its hydrochlorqde, picrate, and muthiodide were described. The oxidation products of physostigmine and eseroline have also been investigated.The so-called (‘eserine blue ” has now been isolated in a pure condition. This base, C17H2302N3, yields crystal- line salts with two equivalents of an acid. It has an intensely blue colour, and in the presence of acids shows a brilliant carmine-red fluorescence. When physostigmine or eseroline is allowed to absorb two atoms of oxygen in the presence of alkalis, rubreserine, CI3H,,O2N,,is formed. This substance, previously isolated by Eber (J’JLnrnz. Zeit., 1888, 33,611), has been re-examined. It is a neutral substance, but yields salts both with acids and bases. Its ccwicAloridc, 12ydro-chloride, picrate, and silver salt were described.I26 +104. ‘‘The resolution of benzoglalanine into its optically active components.” By William Jackson Pope and Charles Stanley Gibson. The equilihrium method of Pope and I’cachey can be conveni- ently applied in the resolution of externally coinpensated benzoyl- alanine into its optically acLive compcnents. Tlic rotation constJants of d-and I-benzoyialanine have been clct~ermined in R number of solvents for mercury-green, mercury-yellow, and sodium light. 105. ‘I The ‘ true ’ ionisation and hydration constants of ammonia and some amines, with a note on the forniulation of nitrogen compounds.” By Tom Sidney Noore. The author has applied the method of calcuIation previously described by him (Tmita., 1907, 91, 1373) to the results of the measurements of the partition-coeficients and apparent ” ionisn-tion constants of ammonia, the methylamines, the ethylamines, and primary and secondary propylamines carried out by Winmill (this vol., 1).109). The results do not bring to light aiiy simple relation between the constitution of am amine and the value of its ionisation constant and hydration constant, but show that there is a great contrast in ioiiising power between .the quaternary hydr- oxides and the hydroxides of primary, secondary, and tertiary aimines. A modification of Werner’s theory of nmrnoniurn compounds has been proposed to explain the observed relations. 106. ‘‘ The conversion of d-glucosamine into d-glucose.” By James Colquhoun Irvine and Alexander Hynd.The esssntial resulis of t,liis invesiigation have already been published iii r2 preliminary note (/’roc., 1912, 28,54). It has now been found that a-anliiiounetllylglucoside and it,s A7-alkyl homologues, which are obtained as intermediate compouii cis in the convcrsioa of glucosauiine intjo glucose, are not to be regarded as simple glucosides. The reactions of the free bases are best explained by the general structure : oH cH, cIJ (oH ,-0-) c:H*CH (OH ) c€5-& 13 IN----~’H,,/I\R R Me where R=-the methyl group or bydrogen. It was also sliomn that 127 marly of the reactions of glucosainine may be explained in terms of a formula of the above type. The possibility of the conversion of glucosamine into glucose being accompanied by a Walden inversion was discussed, and reasons were given lor the conclusion that a structural change of this nature does not take place.Glucosariiiiie may tlius be regarded as a-amino- d-glucose. 107. The chlorination of iodophenols. Part I. The chlorination of y-iodophenol.” By Sidney Albert Brazier and Hamilton McCombie. When an ice-cold solution of p-iodophenol in carbon tetrachloride is saturated with chlorine, an iodo-dichloride separates, which decomposes will1 evolutioii of hydrogen chloride, arid the formation of 3-cliloro-4-iodoplienol. This compound, in turn, when chlorinated, yields an unstable iodo-dichioride, which, on decomposition, furnishes 2 :C;-dicliloro-4-iodopheiioi. In a similar way, 2 :3 :6-trichloro-4-iodo-phenol arid 2 :3 :5 :6-tetrachloro-4-iodoplienol can be obtained.In contradistinction to the free phenols, the acetyl and the benzoyl derivatives yield ext,remely stable iodo-dichlorides, which liave been prepared and analysed. There is one exception to this, namely, the acetyl derivative of p-iodophenol, the iodo-dichloride of which decomposes after being kept for ten days. When a solution of 11-iodophenol in carbon tetrachloride kept at a teinpernture of 50--GOo is saturated with chlorine, there are obtained 2 : 3 : 5 : 6 -tetracl1ioro-4-iodoplienol, pentachloro~>Iienol, 2 :3 :4 :4 ;5 :6-hexachloroc!/cloheundieiioiie (Zincke and Schaurn, Bw., 1894, 27, 546), and cliloroanil. It was found that no iodo-dichloricle could he prepared when the two ortho-positions relative to tlic iodine atom were occupied by chlorine atoms.This is in agreement with the observations of Willgerodt (Ber., 1910, 43, 2755 ;,1utiukti, 1911, 385, 351). Another interesting case of steric hindrance was encountered in attempting to prepare the benzoyl derivatives of phenols in which the two ortho-positions relative to the hydroxyl group were occupied nitli clilorine atoms. The ordinary Schotten-Baumann reaction failed in these cases, but Ihe pyridine method yielded quite satisfac- tory resulLs. 108. ‘‘The monohalogen derivatives of acenaphthene.” By Holland Crompton and Maggie Walker. The preparation and some of the physical properties of chloro-, bromo-, and iodo-acenapbi,liene were described.Tbe melting points of mixtures of these compounds with each other, and aIso of their mixtures with acenaphthenc, have been determined. Chloro- and bronio-acenaphthenc form isomorphous mixtures, but there is no indication of the formation of such mixtures in any of the other cases. 109. ‘(Quinone-ammonium derivatives. Part I. The methylation products of picramic and isopicramic acids.” By Raphael Meldola and William Francis Hollely. The product OP extreme methylation of isopicramic acid by methyl sulphate in presence of alkali described in a preliminary note published in 1910 (Piac., 26,232) has been studied in detail, and its coinposition as a trimethyl derivative confirmed. The production of a similar compound from picramic acid has also been observed.Full consideration of the possible formula: for these compounds has led to the conclusion that they are nitro-derivatives of the hypo- 0thetical quinone-ammonium type, C6H4< 1 or C6Ha<iEl , the NH, 9 trimethyl derivatives of which were prepared by Griess in 1850 (Bcr., 13,246 and 647). This has been proved by the synthesis of the new nitro-derivatives by the direct nitration of Griess’s compounds. The forrnu1E proposed are : O:C’,H,(NO,),:N(CH,), or O*C,H,(N0,),*N(CH3)3.1 1 Alternative formulae in which one of the nitro-groups assumes the “ ;Lei ”-form have also been considered, and the question of internal linkiiig is for the present left undecided. The compound from isopicramic acid forms a scarlet hydrate, which beconies ochrcous on drying owing to conversion into the quinone-ammonium derivative.The authors have discussed iii a preliminary way the connexion between the colour and cheniical constitution of these compounds, and have arrived at the conclusion that the red hydrate has the structure of a “ quinole.” 110. “Latent heats of vaporisation of mixed liquids. Part 111. Mixtures of associated with non-associated liquids. New criteria for the detection of solvates in mixtures of liquids.” By Daniel Tgrer. In continuation of previous work, the latent heats of mixed liquids have been determined in the following cases: (1) Benzene and ctliyl alcohol, (2) chloroform and methyl alcohol, (3) chloroform and acetone, (4) carbon tetrachloride and ethyl alcohol.129 In each case one of the constituents is an associated liquid. In addition, determinations have been made of the boiling points of the mixtures and the compositions of the mixed saturated vapours. It was found that case (3) gives a maximum boiling point, and the other three cases all give minimum boiling points. At these maximum and minimum points the curves for the latent heats at constant pressure and constant composition intersect. By the aid of the additive law of mixtures, which was previously shown to be approximately true for latent heats, the apparent latent heats of the associated constituents in each mixture have been calculated. It was found that, as the concentration of the associated constituent diminishes, its .apparent latent heat, instead of gradually diminish- ing as would be expected as a result of the progressive dissociation of the associated molecules, in all cases increases, at, least over a portion of the range.This was shown to be clesr indication of the existence of solvates in these mixtures. 111. 4( Nickelo-and palladio-dithio-oxalic acids.” By Humphrey Owen Jones and Charles Stanley Robinson. The highly coloured and stable complex salts derived from the dibasic acids, nickelo- and palladio-dithio-oxalic acids, were described in a former paper (Trans., 1912, 101, 62). These two acids have now been isolated and examined. iv~cEelodithio-oxalic acicl, Ni(COS),H2,4H,O, separates from aqueous solutions in lustrous, black prisms often exceeding 1 centi-metre in length.Solutions of the acid have higher electrical conduc- tivities than equivalent solutions of sulphuric acid. The acid decomposes in solution at looo to give four gram-molecules of hydrogen sulphide and one of nickel oxalate from one gram-molecule of the acid, together with oxalic acid, carbon monoxide, and carbon dioxide in variable proportions, the sum of the oxalic acid and carbon monoxide being one gram-molecule. YalladiodctA.20-0xdic acid, Pd(CO S),H,,SH,O, separates from concentrated aqueous solutions in small, dark brown plates. It is a strong acid, but is less stable than the corresponding nickelo-acid. 112. Dithiomalonates.” By Humphrey Owen Jones and Charles Stanley Robinson. By the action of potassium hydrosulphide on amyl dithiomalonate in alcoholic solution, potassium dithiomalonate, CH,(COS),K,, is obtained.This salt reacts wibh metallic salts in a very similar 130 manner to potassium dithio-oxalate, and with aniline hydrochloride yields malonanilide and hydrogen sulphide. The colour oi the complex nickelodithiomalonate is perceptible at, a dilution of 1 part of nickel in 4,000,000 of water, whilst that of the corresponding dithio-oxalate is perceptible at dilutions of 1 in 40,000,000. Several salts of the complex nickelodithiomalonic acid, NilCH,( COS),],H,, and palladiodithiomalonic acid, Pd[CH,(COS),l,H,, were described. 113. ‘‘The ‘crude fat ’ of Beta vulgaris.” By Allen Neville.The ethereal extract of the dry matter of the conimoii inangel was examined and found to contain triglycerides, free fatty acids, and two neutral substances. The free and combined fatty acids consisted largely of palmitic, oleic, and erucic acids, whilst the two neutral substances were of phytosterol nature, and gave results on analysis corresponding with the empirical formulz C,,H,,02 and C29H4502 respectively. 114. ‘(An experimental investigation of the bleaching process. Part 11. Tbe action of neutral salts on bleaching solutions.” By Sydney Herbert Higgins. The author showed that chlorides of sodium and calcium stimu- late the bleaching actions of chlorine-water and of hypochlorous acid, as well as that of hypochlorite solutions.In all cases the action is precisely the same; it is an immediate one, after which action the solutions behave as though the chlorides had not been added. These observations are opposed to the representation of the bleaching action of hypochlorites in the presence of chlorides as being due to the development of chlorine according to the equation : NaCl +NaOC1+ €€,O,= 2NaOH + Cl,, for this explamation does not account for the observations on the other bleaching solutions, and if it were true one would expect sodium chloride to cause a steady acceleration (and not a sudden action) as long as any sodium hypochlorite remained in solution. The reversible actions : (1) HCl +HOCl =R20+Cl,, (2) NaOH + Cl, =NaCl +HOC1, were found to explain all observations, including the behaviour of bleaching powder solution with neutral chlorides.The bleaching 131 trials were performed on weak solutions of dyestuffs, and on the colouring matters of cotton and iinen cloth. In all cases practically the same results were obtained, showing that the same chemical actions took place during the oxidation of all the colouriqg matters used. The action of carbon dioxide on bleaching powder was discussed from equation (2) in support of the author's previous statement (Y'ram., 1911, 99, S58). Solutions of neutral salts were also found to decrease the stability of solutions of potassium per-manganate in air and to increase their bleaching effect, so that for permanganate solutions, as for hypochlorites, it is evident that instability and bleaching effect are related.115. '(The chemistry of the aconitic acids." (Preliminary note.) By Norman Bland and Jocelyn Field Thorpe. A general method for the preparation of aconitic acid and of its alkyl derivatives has been found in the condensation of ethyl chlorofumarate and the sodium compound of ethyl malonate. Under ordinary conditions this condensation leads to the production of ethyl ryclopropanetetracarboxylate, thus (Ruhemann, Tram., 1902, 81, 1212): CO,EtmCH:CC1*CO,Et+CHNa(C0,Et)2 -+ C0,E t CH-co2Et*~H>~(~~,~t), + NaCI. but in the presence of excess of sodium ethoxide ring-formation is prevented, and the yellow sodium compound of ethyl carbethoxy- aconitate is produced : CO,Et*CH:CCl*CO,Et +CHNa(CO,Et), --+ OEt*C(ONa):CH*C(CO,Et):C(CO,Et),+XaCl+ EtOH.The sodium compound is not dissociated by water, and the aqueous solution yields the free ester when treated by carbon dioxide. From the fact that the ester is completely extracted by alkali from its solution in ether and gives a red coloration with ferric chloride, it follows that it is probably entirely enolic in structure. When liydrolysecl by acids it is converted into aconitic acid. The action of methyl iodide on the sodium compound produces ethyl carbethosy-y-methylaconitate (compare Ruhemann, lor. cit., p. l213), an ester which can be isolated in its structurally distinct ketonic and enolic forms. The keto-form, CO,Et*CMe:@(C02Et)*CH(CO,Et),, boils at 215O/18 mm., gives no coloration with ferric chloride, and is not extracted from its solution in ether by aqueous alkali. The eizol-form, C0,Et*CMe:C(C0,Et)=C(C02Et):C(OH)*OEt, an oilis which is stable at the ordinary temperature, but passes slowly back 132 to the ketonic modification on distillation.It gives a red coloration with ferric chloride, and is extracted from its ethereal solution by alkali. It is hoped that by this method alkylated and dialkylated deriv- atives of aconitic acid can be prepared, and that a comparison of these subskances with the corresponding derivatives of glutaconic acid will supply important evidence respecting the influence exerted by the carboxyl group on the &carbon atom of the three-carbon system.Aconitic acid is a remarkable example of the different effect produced by a pure and an impure reagent on the course of a reaction. When treated with acetyl chloride containing phosphorus trichloride [Kahlbaum's acetyl chloride (II)], it is quickly con-verted into the anhydro-acid (I), melting at 76O, as found by Anschiitz and Bertram (Bcr., 1904, 37,3967). If, however, pure acetyl chloride is used, dehydration takes place more slowly, and the product is the hydroxy-anhydro-acid (11) : EH*CO,H CH---CO c---GO C0,H.V bK,*CO>O CH:C(OH) M. 1). 133". (11.) The hydroxy-anhydro-acid crystallises from ethyl acetate in needles which melt at 133O. It behaves on titration as a clibasic acid, and gives a deep reddish-brown coloration with ferric chloride.It is probable that the anhydro-acid melting at 95O (Easterfield and Sell, Tmns., 1892, 61,1009) is a mixture of the two anhydrides mentioned above. The anhydro-acid melting at 76O is converted into the hydrosy-anhydro-acid melting at 133O by the action of acetyl ch1oride. ADDITIONS TO THE LIBRARY. T. Donations. Auld, Samuel Jnnzes Nunson. An introdnction to quantitative analysis. London 1912. pp. x+215. ill. 59. (Recd. 3/5/12,) From the Publishers: Messrs. Methuen and Co., Ltd. Hampshire, Chccdes H. Volumetric analysis for students of pharmaceutical and general chemistry. London 191.2. pp. vii +104. ill. 3s. 6d. net. (Recd. 26/4/12.) From the Publishers :Messrs. J. & A.Churchill. 133 Molinari, Ettore. Trattato di chimica organica generale e applicata all’industria. 2nd edition. Milano 1912. pp. xxiv. + 1087. ill. L.1S. (Red 26/ 4/12.) From the Publisher : Ulrico Hoepli. Tables annuelles de constantes et donnbes nuru6riquev de chimie, de physique et de technoiogie. Publikes sous le patronage de l’hssociation internationale des Academies par le Comitd international nommk par le VIP Congrbs de Chimie appliquee (Londres, 2 Juin, 1909). Volume I. hnn6e 1910. Paris 1912. (Reference.) pp. xxxix + 727. From the International Committee. Thole, Ferdinand Bernard. Qualitative organic analysis, London 1912. pp. x+6& ill. Is. 6d. (Recd. 3/5/12.) Prom the Publishers : Messrs. Methuen and Go., Ltd.111. Pamphlets. Schmidt, Ernat. Ueber die Polysulfhydrate des Brucins. (From the Apoth. Zeit.,1911.) Steinmann, A. Etude critique sur les essais de platine. (From the J. suis5e chim. phps., 1911.) Willard, J. T.,and Swanson, C. 0. The baking qualities of flour. (From the Chern. Yhys. Papers Kansas Acad. Xci., [1911].) RESEARCH FUND. A meeting of the Research Fund Committee will be held in June next. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on, or before, Monday, June 3rd, 1912. All persons who received grants in June, 1911, or in June 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 Saturday, June 1st. The Council wish to draw attention to the fact that the income arising from the donation of the Worshipful Company of Gold-smiths is more or less especially devoted to the encouragement of research in inorganic and metallurgical chemistry. Furthermore, that the income due to the sum accruing from the Perkin Memorial Fund is applied to investigations relating to problems connected with the coal-tar and allied industries. 134 ERRATA. PROCEEDINGS,1912. Page 77, line 5 from top, for ‘(March 25th ’’ read (‘March 28th.” ,, 94 ,) 12 ,, ,) “ethyl” read “methyl.” ,7,, 94 )) 22 ,, “tetramethyl” read “octaniethyl.” ), 98 ,, 15 from below, for ‘(Part I” read “Part VI.” 7) 101 9, 10 ,, ,, “CH’CH, ” read “ C‘li’CCl,.” The next Ordinary Scientific Meeting will be held on Thursday, May 16th, at 8.30 p.m., when the following papers will be com-municated : ’* Azo-dyestuffs of the triphenylmethane group.” By A.G. Green and R. N. Sen. “Aniline black and allied compounds. Part II.” By A. G. Green and A. E. Woodhead. “Action of Grignard reagents on esters of dibasic acids. (Pre-liminary note.) ” By J. T. Hewitt and D. B. Steinberg. “ Chemical examination of the bark of Euon.ymus Atropur-p~reus.’~By H. Rogerson. “ The constitution of aminotyrosine and the action of oxydases 011 some tyrosine derivatives.” By C. Funk. “ Furan-2 :5-dialdehyde.” By W. F. Cooper and W. H. Nuttall. “ The dynamic isomerism of ammmium thiocyanate and thio- carbamide.” By W. R. G. Atkiiis and E. A. Werner. .‘The distillation and densities of mixtures of ally1 alcohol and wa,ter. Part I.” By T. A. Wallace and W. R. G. Atkins. rL A modification of the Beckmann apparatus by which constant readings are obtained in determining the boiling points of aqueous soiutions.” By E. Knecht and J. P. Batey.
ISSN:0369-8718
DOI:10.1039/PL9122800123
出版商:RSC
年代:1912
数据来源: RSC
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