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Proceedings of the Chemical Society, Vol. 28, No. 407 |
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Proceedings of the Chemical Society, London,
Volume 28,
Issue 407,
1912,
Page 311-322
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[Issued 12,42112 P R 0 C E E .DI N (3 S OF THE CHEMICAL SOCIETY. VOl. 28 No.407. Thursday, December 5th, 1912, at 8.30 p.m., Dr. M. 0. FORSTER, F.R.S., Vice-president, in the Chair. Captain G. I. Davys was formally admitted a Fellow of the Society. The CHAIRMANannounced that the Council had decided: (1) That in order to obtain a more equal division of abstracts, those of Physiological Chemistry and the Chemistry of Vegetable Physiology and Agriculture shall, in future, be included in Part I. of the Abstracts, instead of in Part II. (2) That persons requiring expanded Abstracts or translations of papers published in other Journals should apply to the Editor. Ten shillings per printed page (about 500 words) will be charged, and payment should bo made to the Editor at the time the request for a translation or fuller abstract is forwarded to him.Certificates were read for the first time in favour of Messrs.: Theodore William Gull Acland, B.A., 19, Bryanston $quare, W. Albert Brier, M.Sc., 19, Alexander Road, Ulverston. Charles George Cutbush, 59, Byne Road, Sydenham, S.E. Thomas Lenton Elliott, Lincoln House, Heckmondwike, Yorks. Robert Gilmour, B.Sc., Ph.D., Scores Villa, West, St. Andrews. James Arthur Hewitt, B.Sc., 3, South Bridge Street, St. Andrews. 312 William Joseph Holt, 31, Spruce Hills Road, Walthamstow, N.E. Paul Murphy, Burnside, Sidcup, Kent. Jonathan Harold Naylor, M.Sc., 73, Castle Street, Bolton. Harold Victor Taylcr, Royal College of Science, S.Kensington, S.W. Percy James Thompson, The Avenue, Clytha Square, Newport, Mon. Thomas Willoughby Turnill, Stibbington, Wansford, Northamp- tonshire. Edward Webb, B.Sc., Berwyn, Totteridge, Whetstone. A Ballot for the election of Fellows was held, and the following were subsequently declared duly elected : Rdwin John Amies, B.Sc. Francis Maxwell. William Llewelyn Baily. George Francis Morrell, Ph.D., KSc. James Henry Young Baker. Ernest Moore Mumford, B. Sc. Douglas Andrrsm Bowak. Tanjore S. Natrajan. Edniund Arthur Buckle. Leslie Frank Newman, B.A. Richard Westman Challinor. William Moore Nichols. Frank Andrew Coombs. Mnximilian Nierenstein, Ph. D. Walter Henry Dixon. Carl Alfred Nonak, B.Sc. H. H. Dodds, M.Sc. Lionel Orange, B.Sc.James Crawford Douglas. Ranini Paniker, M.A., M.kc. James Harry D!son. John William Patterson. Ridsdale Ellis, R. Sc. Charles Etty Potter, B.Sc. George Davidsoii Elsdon, B.Sc. Jitendra Nath Rekshit. Sydlrey Charles Gadd. Martin Remers, L.R.C.P., L.B. C.S. Harold Heith Gray, R.Sc. Herbert Carr Roper. Frederick Lyle Griitzmacher. Albert Sasson. Arthur James Hale, B.Sc. Harold Archibald Scarborough, H.Pc. Archie Haydon. Walter Scott. Edward Hope, M.Sc. Kunjn Behary Seal. Ardesir Naservanji Pevton Jamas, ill.A., Cyril Edgar Sladden, B.A. B.Sc. Alfred Thonlas Smith, B.Sc. Edgar Jobling, B.Sc. William Charles Smith. Shigeru Komatsu. Victor Steele. Frederick Russell Lankshear, B. 9., Alfred Ernest Stephen. 31. sc. William Compton Till, M.Sc. Stanley Isaac Levy, B.A., B.Sc. Hui Chun Tsao, B.Sc. Ernest Lawson Lomax, M.Sc. Paul Jenner Ure. Of the following papers those marked * were read: *308. c6 Chemical reactivity and absorption spectra. Part 11. The variation in absorption produced by a solvent.” By Edward Charles Cyril Baly and Francis Owen Rice. In two previous papers (Trans., 1912, 101, 1469, 1475) it was pointed out that every chemical molecule must be the centre of a condensed field of force. Each individual atom in any given 31 3 molecule possesses a certain amount of free affinity, which must be accompanied by the existence of lines of force in its immediate neighbourhood. Inasmuch as there exist two types of this affinity, acid and basic, it follows that the independent existence of these lines of force in a molecule must be a metastable condition, and thatJ the various force iines must condense together with the escape of free energy.The chemical reactivity of the resulting condensed system will be very much reduced, and in some cases may fall to zero. It has been shown how these systems can be unlocked by the action of light, and how the reactivity thereby may be increased. In many cases the closed system can partly be opened by the influence of a solvent, and under the influence of light they may still further be opened. A quantitative measure of the amount of light absorbed by substances at various concentrations in suitable solvents has been carried out. As a result of this theory it would be expected, in the case when a substance is opened up by a solvent, that the amount of light absorbed should increase with the dilution until a maximum is reached. Further dilution should then cause a decrease in the amount of light absorbed, and finally the solution should become diactinic.This result has experimentally been found. “309.6L Studies in the camphane series. Part XXXIII. Orientation of Tiernann’s isoarninocamphor. ” By Hartin Onslow Forster and Hubert Arthur Harry Howard. Tiemann’s isoaminocamphor, produced by the action of hydriodic acid on camphoroxime, was found to have the aminegroup in the position occupied by the substituent in P-chlorocamphor, 8-bromo- camphor, and Reychler’s camphorsulphonic acid.It is therefore re-named P-aminocamphor, and by hydrolysing the hydroxycamphor semicnrbazone, Cl,H190,N3, which arises by exchange of the amino- group for hydroxyl when semicarbazide acetate acts on &amino-camphor, ,&I-hydroxycamphor, C10H1602, has been prepared ; the substance is short-lived, rapidly changing into the isomeric dihydro- campholenolactone. 310. ‘‘A study of some organic derivatives of tin as regards their relation to the corresponding silicon compounds.” By Thomas Alfred Smith and Frederic Stanley Kipping. As the results of a comparison of optically active derivatives of tin with the corresponding silicon compounds might lead to impor-tant conclusions, attempts have been made to synthesise dl-dibenzyl- ethylpropylstannanesulphonic acid, SnEtPr(CE,*C,H,) *CH,*C,H4*S0,B, 314 by methods analogous to those employed in the preparation of dibenzglethylpropylsilicanesulphonic acid (Challenger and Kipping, Trans., 1910, 97, 142, 755).These experiments were successful only up to a certain point, for although dibenzylethylpropyl-stannane was, in fact, obtained, the dl-monosulphonic derivative of this compound could not be prepared. The following benzyl and benzylalkyl derivatives of stannic chloride were described : Dibeneylstannic chloride, bromide, iodide, ad acetate ;tetrabenzyktannan,e, tribenzyletltylstannane, dibenzyl- diethylstunname, and dibenzylethylpropylstannane. Ethylpropyl-stannic chloride was also obtained. ‘b311. Contributions to the chemistry of the terpenea.Part XV. Synthesis of a menthadiene from carvacrol.” By George eerald Henderson and Schachno Peisach Schotz. Carvomenthol, CloHl,*OH, prepared by hydrogenating carvacrol according to the method of Sabatier and Senderens, yields Al-menthene, C10H18,when heated with anhydrous oxalic acid. The hydrocarbon forms an oily dibromide, C10H18Br2, which, when heated with alcoholic potassium hydroxide or with anhydrous sodium acetate and acetic acid, is converted into a menthadi’ene, Cl,H16, a colourless liquid with a pleasant odour, which boils at 172-1 74O. It waa expected that the product of these reactions would be either a-or p-phellandrene, but this was not the case; at least, it could not be converted into a nitrite.On the other hand, the menthadiene obtained in this way from carvacrol has considerable resemblance to the corresponding hydrocarbon formerly obtained from thymol by a similar process, although it has not been proved that they are identical. 312. ‘‘ The action of halogens on silver salts.” By Hugh Stott Taylor. Iodine reacts with silver salts in a manner analogous to that observed in reactions with chlorine and bromine, to yield insoluble silver iodide, hypoiodous acid, and another acid. The reaction occurring may be represented by the equation: AgX +I, +H,O =AgI +HI0 +HX. Owing to the instability of hypoiodous acid, a second reaction occurs, accelerated by rise of temperature, increase in concentra- tion, or presence of soluble silver salts, in which the hypoiodous acid is converted into iodide and i0dat.e.This secondary reaction may be generally represented thus: 3HIO +3AgX= 2AgI +AgIO, + 3HX. 315 The progress of this second reaction has been followed k various concentrations of the reacting solutions. The simple equation of Birnbaum (Anmlen, 1869, 152, 111) and of Normand and Cumming (Trum., 1912, 101, 1852): 3%+ 3820 + 6AgX=5AgI +AgIQ + 6HX represents +!hesum of the two preceding equations. 313. The formation of tetrahydro-oxazoles from a-hydroxy-P-anilino-ap-diphenylethane and its homologues.” By Horace Leslie Crowther and Hamilton McCombie. Tetrahydro-osazoles cannot be prepared from the dihydro-oxazoles described by McCombie and Parkes (Trans., 1912, 101, 1991) by simple reduction.If, however, u-keto+?-anilino-a&diphenyl-ethane is reduced to the corresponding hydroxy-compound (I) by means of sodium amalgam in alcohol, this compound then undergoes condensation with carbonyl chloride to yield 3 :4 :5-triphenyL 2 :3.4 :5-tetrahydro-2-oxazolone(11): .. HO*CHPh*CHPh. NHPh (1.1 (11.) Similar compounds have been prepared from the corresponding in-and p-toluidines and P-naphthylamine analogues of (I). The tetrahydro-oxazoles obtained are very stable substances, which resist the action of reducing agents and phosphorus tri-chloride, and do not form salts with hydrochloric acid or with picric acid. Attempts were also made to condense a-hydroxy-B-anilino-afl-diphenylethane and its homologues with thionyl chloride and sulphuryl chloride, but these were unsuccessful.314. The precipitation of lead thiosnlphate and its behaviour on boiling with water.” By William Hughes Perkins and Albert Theodore King. The addition of sodium thiosulphate to a solution of lead acetate produces a precipitate the composition of which varies with the dilution of the solutions, and with the proportions in which they are mixed. From concentrated solutions, especially those containing excess of the lead salt, the precipitate consists of the double salt Pb(C,H30,),,2PbS20,, whilst from dilute solutions or with excess of thiosulphate it has a composition corresponding with PbhO,. It is therefore advisable when pure lead thiosulphate is required to obtain it from lead nitrate.The well-known blackening of this 316 salt on warming takes place most readily in the presence of excess of sodium thiosulphate according to the equation PbS,O, + 3Na&&O,=PbS +45+ SNa,SO,. Without the (sodium salt the reaction is slower and more complex, but it still proceeds mainly according to the equation 4YbS203=PbS +4s + SPbSO,. The authors’ results are in conflict with those of Fogh (Ann, Chim. Phys., 1890, [vi], 21, 56), who prepared his thiosulphate from moderately concentrated lead acetate solution, and repremnted its decomposition on boiling by the equation 2PbSzO,=PbS + PbSSO,. 315. ‘(Studies on cyclic ketones. Part 11.” By Siegfried Ruhemann and Stanley Isaac Levy.The work on cyclic ketones (Ruhemann, Trans., 1912, 101, 1729) has been continued on the same iines as before; in particular, the authors have examined the hydroxymethylene derivatives of various cyclic ketones. They find that 2-hydroxymethylene-l-hydrindore, C6H4<Et2> C:CH*OH, a colourless solid soluble in alcohol, under- goes on warming a remarkable transformation, involving the elimination of one molecule of formic acid from two molecules of the substance; the condensation product, C,H,<:::>C: CH*CH<:$C,H,, is a deep red solid, insoluble in alcohol, and decomposing at 232O. The corresponding methylenedioxy-derivative, undergoes the same change at a somewhat higher temperature; but the hydroxymebhylene derivatives of 1:3-dimethyl-A3-cydohexen-5-on*, CHMe<CH2--c&C(CH*oH)*Co>CH, which is a yellow oil, and of l-methylcycZopentan-3-one, CHMe< C‘H,*FO which is a very CH,*C:CH*OH’ volatile, colourless solid, can both be distilled in a vacuum without change.In other respects the hydroxymethylene derivatives of the hydrili- done series resemble thme already examined by Claisen and his pupils; thus they yield green copper salts, and anilides, and react with semicarbazide, and with phenylhydrazine, in the latter care forming pyrazole derivatives. 317 316. ''Some hydrogen ferrocy anides." By Herbert Ernest Williams. By treating solutions of the ferrocyanides of the alkali or alkaline earth metals with hydrochloric acid, ferrocyanic acid is liberated.The ferrocyanides of the heavy metals, however, behave differ- ently ; thus, when cupric ferrocyanide is boiled with concentrated hydrochloric acid, half of the copper is replaced by hydrogen, and there is obtained a yellow, insoluble cupric hydrogen f errocyanide, CuH,Fe( CN),,4H,O. In a similar manner, but with slight variation of conditions, such as lower temperature or diluted acid, double hydrogen salts of nickel, cobalt, manganese, zinc, and cadmium can be obtained. By thse means the following compounds have been prepared and examined : Cobalt hydrogeib ferrocyanide, CoH,Fe(CN),,4H20 ; manganese hpdrogen ferrocyanide, &fnH,Fe(CN),,5H20 ;and nickel hydrogen ferrocyanide, NiH,Fe(CN),,3'A20. These acid salts are insoluble in water, and decompose alkali carbonates readily with liberation of casbon dioxide, and when digested in solutions of the chlorides of the alkali metals, hydro- chloric acid is liberated.The cupric salt, when digested with solutions of potassium or ammonium chlorides, liberates two equivalents of hydrochloric acid, and forms the corresponding cupric potassium or cupric ammonium f err ocy anide respectively . With potassium chloride the reaction ,is r,epresented by the equation : CuH,Fe(GN), + 2KC1= CUI(P~(C'N)~ +2HC1. With sodium chloride solution in the cold only half the hydrogen of the copper compound is replaced, thus: CuH,Fe(CN), + NaCl= CUNaHFe(CN), + HC1, forming the triple salt, cupric sodium hydroyen ferrocyam.de, which has a dirty brown colour.When this triple salt is digested in a solution of potassium or ammonium chloride, the remaining hydro- gen atom is replaced, forming one equivalent of hydrochloric acid and cupric sodium potassium or cupric sodium ammonium ferro- cyanide respectively. 317. '' The formulae of ipuranol and some related compounds." By Prank Tutin and Hubert William Bentley Clewer. In a paper published some time ago (Amer. J. Pharm., 1908, 80, 264) Power and Rogerson described the isolation from Zpomaa prpurea of a substance which was designated ipuranol, and since then the same compound has repeatedly been obtained from a 318 variety of plants. The analysis of the ipuranol, and of its acetyl derivative, appeared to indicate that the substance in question was a dihydric alcohol possessing the formula C2,H3,02(OH),.It has since been observed, however, that the analytical results agree equally well for a higher formula, C2,H4,0,(OH),. The present authors have recently analysed benzoylipuranol, when figures were obtained which were not in harmony with the formula C!?3H3804(C0*C6H5)2,but were in exact agreement with those theoretically required for the tribenzoyl derivative of a substance possessing the higher formula mentioned above. In the following table the theoretical analytical figures for the two formulze are compared: C%H390.2(OH)4. ~,H4,O,(OH),.Required for alcohol.................. C=72*6 ; H=10.5. C=72-8 ; €I=10-5. ,, ,, acetyl derivative ...C=69*8; H= 9-5. C=69'5; H= 9.2. ,, ,, henzoyl derivative ... C=75*5 ; I<= 8'2. C=76-0 ; H= 7-8. A molecular-weight determination of the acetyl derivative was subsequently made, when the value 607 was obtained, compared with 604 required for C2gH,70,(CO*CH3)3 and 464 required for C23H3,04(CO*C'H3),. It is thus evident that ipuranol is a trihydric alcohol, possessing the formula C2gH4,02(OH)3. Similarly, it has been ascertained that cluytianol possesses the formula C&H,,O(OH),, and not C2,H3,0(OH),, as recently stated (this vol., p. 265). Power and Moore (Trans., 1910, 97, 102) described the isolation from colocynth of a new alcohol, designated as citrullol, which appeared to possess the formula C,,H,,O,(OH),, thus being a lower honiologue of ipuranol.A small quantity of this substance being available, it has now been re-investigated, with the result that it has been ascertained that citrullol should be represented by the formula C2,H4,02(OH),, a conclusion which is quite in harmony with the analytical results obtained by Power and Moore. The citrullol examined was analysed, with the following result : 0.0923 gave 0.2448 CO, and 0.0859 H,O. C=72.3; H=10.3. Ce8H,,O, requires C =72.4 ; H =10.3 per cent. Power and Moore found C=72*1; H-10.4 per cent. A molecular-weight determination of the acetyl derivative yielded the following result : 0-4019 in 23.96 benzene gave At -0.13O. M.W. =613. C34H5408requires M.W. =590. C26H4206 requires M.W. =450. Brnzoylcitrullol has not previously been described.It forms colourless needles, melting at 179-180° : 0.0947 gave 0.2640 CO, and 0.0650 H20. C =76.0 ;H =7.6. Ck,H6,0, requires C= 75.8 ; H =7.6 per cent. C36H46O6 ,, Cz75.2; H=8'0 99 319 In view of these results it would appear probable that some, at least, of the other alcohols related to ipuranol which have been isolated may possess higher formulae than those at present ascribed to them, but material for their re-investigation i8 not now available. 318. (( Xolecular conductivity and ionisation of nitrites.” By Prrtfulla Chandra Rig and Nilratan Dhar. Twenty-three nitrites have been studied from the point of view of their electrical conductivity and hydrolysis in aqueous solution. The nature of the complexes in the salts sodium mercurinitrite, Na2Hg(NOe)4, tetramethylanimonium mercurinitrite, NMe4Hg(NO2)3Jand mercurosomercurinitrite, HgHg,(NO,),, has been determined.The inadequacy of the expression A,/A,=p was also discussed. 319. “The latent heats of chloroform and benzene and of their mixtures between 0” and 80°.” By James Fletcher and Daniel Tyrer. A method was described for accurately determining latent heats at constant composition of mixtures over a wide range of tempera-ture. The latent heats of pure chloroform and pure benzene and mixture of these liquids of varying compositions have been deter- mined between the ordinary temperature and the boiling points, It is found that for any given mixture the latent heat is a linear function of the temperature, and for a given temperature the latent heat is approximately a linear function of the composition.320. ‘‘ Synthetic aminoglucosides derived from d-glucosamine.”By James Colquhoun Irvine and Alexander Hynd. It was shown that bromotriacetylglucosamine is a general reagent for the preparation of a-aminoglucosides, as it enters into reaction with widely different types of hydroxy-compounds, giving, in the rirst instance, acetylated aminoglucosides, from which the acyl groups may be removed by hydrolysis. Both the acetylated and unsubstituted aminoglucosides thus obtained may be divided into two classes, which differ in their behaviour towards hydrolytic agents, and in their capacity to form molecular cDmpIexes with metallic haloids.Some of the compounds are remarkably stable, and are only hydrolysed to give glucosamine salts when strongly heated with concentrated acid. In such cases they are also unaffected by enzymes, and form additive compounds with silver iodide. 320 a-Aminoglucssides of this nature are regarded as cyclic nitrogen compounds of the general type described in a previous paper (Trans., 1912, 101, 1128). The examples of this class now described are a-amzrcoethylglucoside and a-aminoamylglucoside. A second type of aminoglucoside is formed when the group combined with the glucosamine residue contains a benzene ring, as then hydrolysis with dilute mineral acids proceeds quite normally, and t.hus the usual glucosidic formula: may be applied to the compounds.Representative members of this class are a-amino-benzylglucoside, a-amiiLohelicin, a-aminosalicin, and a-aminornorph- ineglucoside. In rnar,y respech acetylated arninGglucosides show a remarkable similarity in their behaviour towards both acids and alkalis to the simpler glucoproteins. The suggestion was made that the latter cornpounds may be constituted in an analogous manner to triacetyl- a-aminomethylglucoside, and thus conform to the general structure : I01CH,(OR5)-CH(OR,) CH*CH(OR,)*yH-YH N--0 , where G stands for the “glucosidic” group, and R,, R,, etc., for aminclacyl residues. Syntheses of complexes of this nature are now being carried out. ADDITIONS TO THE LIBRARY. I. Donations.Allmand, Arthua John. The principles of applied electrochemistry. London 1912. pp. xii + 547. ill. 18s. net. (Recd. 2/12/12.) From the Publisher : Mr. Edward Arnold. Barclay, William R., and Hainsworth, Cecil H. Electroplating. A treatise on the electro-deposition of metals, with a chapter on metal-colouring and bronzing. London 1912. pp. viii + 399. ill. 78. 6d. net. (Recd. 2/12/12.) From the Publisher : Mr. Edward Arnold. Makower, W.,and Geiger, H. Practical measurements in radio- activity. London 1912. pp. ix+151. ill. 58. net. (Becd. 23/11/12.) From the Publishers : Messrs. Longmans, Green & Co. 321 Martin, Geoflrey, [and others]. Industrial and manufacturing chemistry. Organic. London [1912]. pp. xx+726. ill.31s. net. (Recd. 3/12/12.) From the Publishers : Messrs. Crosby, Lockwood & Son. Mellor, Joseph WiEZiam. Modern inorganic chemistry. London 1912. pp. xxe871. ill. 7s. 6d. (Becd. 23/11/12.) From the Publishers : Messrs. Longmans, Green dz Co. Norton, Thomas H. Utilization of atmosplieric nitrogen. (US. Dept. Commerce and Labor, Bureau of manu€acturea. Special Agents Series, No. 52.) M’ashington 1912. pp. 178. ill. (Recd. 20/11/12.) From the Author. Price, Thornas Xlater. Per-acids and their salts, London 1912. pp. iv + 123. 3s. net. (Recd. 23/11/12.) From the Publishers : Messrs. Longmans, Green & Co. Russell, Edward John. Soil conditions and plant growth. London 1912. pp. viii+ 168. 5s. net. (Recd. 23/11/12.) From the Publishers : Messrs.Longmans, Green clh; Co 11. By Purchase. Cohen, Emst. Jacobus Henricus van’t Hoff. Sein Leben und Wirken. Leipzig 1912. pp. xv+ 638. ill. M. lii.-. (Recd. 30/11/12.) Thorpe, Xi?. Edward. A dictionary of appliad chemistry. Vol. 111. London 1912. pp. viii + 789. ill. 32 58. net. (Recd. 30/11/12.) ERRATUM. PROCEEDINGS,1912. Page 238, line 22,for “COPh*COPh’NPh*CO,Et”read “COPh*CHPh*NPh*CO,Et.” 322 At the next Ordinary Scientific Meeting on Thursday, Deoember 19th, 1912, at 8.30 p.m., the following papers will be communi- cated : ‘ Dibenzyl- and diphenyl-silicols and silicones.” By G. Martin. “An attempt to harmonise the relation between temperature and rotation for light of all refrangibilities of certain active substances, both in the homogeneous state and in solution.” By T.S. Patterson. “The photography of absorption spectra.” By T. R. Merton. ‘‘ The constitution of ortho-diazoimines. Part 11. The ptolyl-naphthatriazoles.” By G. T. Morgan and F. M. G. Micklethwait. “ Co-ordination compounds of vanadium. Part I. The acylaceton- ate.” By G. T. Morgan and H. W. Moss. ‘‘Optically active glycols derived from the phenyl-lactic acids. Part I.” By A. McKenzie and G. Martin. “Diphenylene. Part II.” By J. J. Dobbie, J. J. Fox, and A. J. H. Gauge. “A new method for the estimation of hypochlorites.” By H. G. Williams. B. CLAY AND SONS, LTD., BBUKSWICX ST., STAMFORD ST., S.E., AND BUNQAP, BUFFOLX.
ISSN:0369-8718
DOI:10.1039/PL9122800311
出版商:RSC
年代:1912
数据来源: RSC
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