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Proceedings of the Chemical Society, Vol. 23, No. 322 |
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Proceedings of the Chemical Society, London,
Volume 23,
Issue 322,
1907,
Page 69-79
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摘要:
Issued 15/3/07 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 23. No.322. Thursday, March 7th, 1907, at 8.30 p.m., Professor R. MELDOLA, F.R.S., President, in the Chair. Messrs. Frank Baker, F. S. Benton, L. H. Berry, F. J. Harris, A, T. King, B. D. Porritt, F. G. P. Remfry, A. H. Salway, and Frank Tutin were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : John Arthur Cunningham, B.A,, Presidency College, Calcutta, India. Samuel Duckmorth, M.Sc., 78, Alexandra Road, Lowestoft, Suffolk. Arbhur George Harrington, Rochford, Westbury Road, Ealing, W. Frederic William Rixon, M.Sc., Ph.D., Powderham Road, Newton Abbot., Devonshire. William Griffiths Tonner, B.Sc., 26, Gordon Road, Kingston-on- Thnmes.The CHAIRMANread the names of the Fellows recommended by the Council for election as official and ordinary Members of Council, and announced that the name of Mr. F. H. Streatfeild had been proposed by another Fellow as an ordinary Member of Council. 70 Of the following papers, those marked * were read : *50. The constitution of chaulmoogric and hydnocarpic acids." By Marmaduke Barrowcliff and Frederick Belding Power. In previous communications (Power and Gornall, Trccns., 1904, 85, 838, 851) the isolation and properties of chaulmoogric acid, C18H3,02 (m. p. 68O), were described. It is optically active, having [a],, +56O, and mas shown to contain both a closed ring and an ethylenic linking. When chaulmoogric acid is oxidised in alkaline solution with limited quantities of potassium permanganate it yields a-dihydroxy-dihyd~~ocha~l~~zoogricacid, C,,N,,O,(OH), (m.p. 105" ; [.ID + 11*6O), P-dihydroxydihydrochclulmoogvic acid, C,,H,,O,(OH), (m. p. 93" ; [aID -14*2O),and hydroxyketodi~~ydroc~~~~l~oogriccccid, C18H3,04. Further oxidation gives, on the one hand, an optically inact.ive tri- carboxylic acid, C18H,,0, (m. p. 68"), which is n-pentadecane-aa'y-tricarboxylic acid, CO,K*[CH,],* CH(C0,H) *[CH,], ,*CO,H, and, on the other hand, formic acid and a keto-acid, C17H3005,previously described (Zoc. cit.), which is now shown to possess the formula CO2H*[CH,I2*CO*[CH2],,*C0,H. The latter compound, on oxidation, yields n-dodecanedicrtrboxjlic acid, [CH,],,(CO,H),, and n-undecanedicarboxylic acid, ~CH2111(CO,~),~By the addition of hydrogen bromide to chaulmoogric acid, and its subsequent elimination, an optically active mixture of acids is obtained, which, when oxidised, furnishes a keto-acid, C18H3205(m.p. 126O), to which the formula, C0,H*CH,*CHMe*CO*[CH2]12-C0,H,is ascribed. The results obtained caD be explained by assigning to chaulmoogric acid both the following formulae, and considering it to exist in a state of tautomerism between the two structures, CH CH, /\ /\f.'H ~H[CH,],,*CO,H 2-~H-~[CH,Il,*CO,H. CH,*CH, CII,*CH, 1-a-Carboxy-n-dodecyl-h4-cyclopentene. 1-a-Carboxy-n-dodecyl-1 :4-bicy clopentane. Its constitution may therefore be represented by the following formula : CH /i\f.'H-H-*$J[ CH,] 12*C02H.CH,--CH, 71 To the dihydroxydihydrochaulmoogric acids the formulae : yHtO”)* CH(oH)>CHIC K,],,*CO,H andCH2--CH2 ~H(oH).CHqC(OH)[CH2],,*C0,HCH,-CH, are ascribed, whilst dihydrochaulmoogric acid, C,,H,,O,, is considered to be a mixture of a-carboxy-n-dodecykyclopentaneand i-a-carboxy- n-dodecyl-2-methy lcyclobutane. Hydnocarpic acid, C,GH2,02 (m. p. 60’ ;[aID+68O), a homologue of chaulmoogric acid (Trans.,1905, 87, 884), yielded on oxidation an acid, C,,H2,0G (m. p. 60°),which is n-tridecane-aa’y-tricwboxylicacid, CO,H*[CH,],*CH( C0,H)*[CH2],o*C0,H, together with n-decanedi-carboxylic acid, [CH,] C02H),. Its constitution may accordingly be represented by the following formula : CH /i\QH-H.**Q[CH2]l,-,*C0,H~ CH,--CH, *51.(c Hydrolysis of amygdalin by acids.” By Robert John Caldwell and Stephen Lewis Courtauld. With the object of obtaining further evidence as to the constitution of amygdalin, the authors have systematically studied the action of acids in comparison with that of enzymes on this ‘‘bioside.” The results show that, although amygdalin is ultimately resolved by acids into hydrogen cyanide, benzaldehyde, and two molecular propor- tions of glucose, the separation of the glucose is effected in two stages. The hydrolysis of the biose section of the molecule proceeds only at about one-sixth of the rate at which maltose is hydrolysed under like conditions. By carefully hydrolysing amygdalin by means of a normal solution of hydrogen chloride at 60°, the authors have pre- pared the mandelonitrile glucoside which E.Fischer obtained by sub- jecting the bioside to the action of an extract of yeast ; this method of obtaining the glucoside appears to be in some respects advantageous, the product being more easily purified. *52. “Mandelonitrile glucosides. Prulaurasin.” By Robert John Caldwell and Stephen Lewis Courtauld. In order to ascertain whether the glucoside prepared by hydro- lysing amygdalin is a direct product or one which has undergone isomeric 72 change, the authors have subjected it to the action of alkalis; they find that it is converted into a substance identical with the isomeric substance prulaurasin, isolated by Hdrissey from laurel leaves.Fischer’s glucoside therefore bears the same relation to prulaurasin as amygdalin bears to the isoamygdalin described by Dakin, which is to be regarded as the derivative of inactive mandelonitrile, amygdalin and Fischer’s glucoside being derived from E-mandelonitrile. As the rotatory power of prulaurasin is intermediate between that of Fischer’s glucoside and that of sambunigrin, the second isomeride of Fischer’s glucoside recently described by Bourquelot and Danjou, the latter must be regarded as the P-glucoside of d-mandelonitrile. Characteristic acetyl derivatives have been prepared from amygdalin, isoamygdalin, Fischer’s glucoside, and prulaurasin. “53. “The hydrolysis of amygdalin by emulsin.” By Samuel James Manson Auld.Although amygdalin is generally described as the maltoside of benzaldehydecyanohydrin since on hydrolysis it produces two molecules of dextrose, it is probable that the biose residue is an unknown @-disaccharide capable of hydrolysis both by emulsin and maltase. The hydrolysis of amygdalin by emulsin may proceed in three ways, depending on the mode of attachment of the emulsin. Either mandelonitrile glucoside and dextrose are first produced with subse- quent hydrolysis of the former, or benzaldehydecyanohydrin and the ufl-disaccharide are formed, and the latter then resolves into two mole- cules of dextrose, or, lastly, the arnygdaiin may undergo fission into the three components by direct abstraction of the dextrose residue attached to the benzaldehydecyanohydrin molecule. The experiments so far carriedout indicate that the second process of cleavage is the true one.DISCUSSION(on the three foregoing papers). Dr. MCKENZIEasked whether two mandelonitrile glucosides had been obtained, where the relationship is similar to that which exists between amygdalin and isoamygdalin, and, further, if the mandelonitrile glucoside described was racemic as regards the mandelic complex, had the fractional hydrolysis of this compound been studied ‘3 Dr. HENRYstated that the report on “ Cyanogenesis in Plants,” prepared by Professor Dunstan and himself for the York Meeting of the British Association, was mainly a compilation of the published information then available on the subject, and consequently the refer- once there to amygdalin as a derivative of maltose did not commit the 73 authors of the Report to that view of the constitution of the biose residue of the glucoside, and, in fact, the nature of the sugar residue of amygdalin was then under iuvestigation by Dr.Auld, who had been associated recently with the authors in their work on cyanogenetic glucosides. The interest shown of late in this subject had been created by the work done at the Imperial Institute since 1900, and it had been the intention of Professor Dunstan and himself to investigate fully the relationship of Fischer’s mandelonitrile glucoside to prulaurasin and sambunigrin. In view of the fact that Professor Dunstan and he were well known to be at work in this field, it was unfortunate that Messrs.Caldwell and Courtauld had, without consultation, commenced work on these three isomerides. Dr. AULDregretted that he was not aware that this investigation had been undertaken, as he had been at work on the problem of the constitution of the biose residue of amggdalin for some time. It was an entirely erroneous assumption that the maltose structure of this residue had been taken for granted. Dr. Henry’s article in Science Progress (July, 1906) clearly showed that the exact nature of the sugar residue in these glucosides had not been settled. The results of Messrs. Caldwell and Courtauld’s communication did not throw much new light on the actual configuration of the biose residue.“54. ‘‘Electrolytic reduction. Part 111.” By Herbert Drake Law. The products of electrolytic reduction of the aromatic aldehydes in alkaline solution are compounds of the hydrobenzoin type, but thie reaction is completely altered when a methyl group is substituted in the ortho-or meta-position of the benzene nucleus. In the latter case, compounds of a resinous nature are obtained. Thus p-tolualdehyde gives a well-defined crystalline substance, whilst m-and o-tolualdehydes yield nothing but resins. The resinifying effect of a single substitu- tion may, however, be neutralised by the introduction of a second group in a similar position on the opposite side of the nucleus. Thus with 3 :5-dimethylbenzaldehyde a crystalline product is obtained, whilst 2 :4-dimethylbenzaldehyde yields 40 per ccnt.of resin. Similar results were given by other aldehydes. In acid solution, the products differed greatly at different tempera- tures. Thus in cold solutions primary alcohols were obtained to a large extent, but at 40’ the product was of the hydrobenzoin type. Stilbenes and saturated hydrocarbons were also obtained. 74 DISCUSSION. The PRESIDENTasked whether, in writing the formulae of the aromatic aldehydes sometimes with the Kekul6 benzene ring and at others with the ‘(centric ” arrangement of bonds, the author intended to convey the idea that the Kekuli! formula represented the benzene molecule as unsaturated, and the “ centric ” formula as saturated. Mr.LAW,in reply, said that the concentric formula best represents the constitution of the benzene nucleus. The introduction of a strain across the molecule distorts this configuration, the greatest mechanical effect being produced for a substitution in the ortho-position. In the latter case, Kekuld’s formula probably nearly represents the state of the molecule. Between these two extremes it is possible that many other forms may exist. “55. (‘New cerium salts.” By Gilbert Thomas Morgan and Edward Cahen. Although in many cases the cerous salts of carboxylic acids, such as the cinnamate, are insoluble, uncrystallisable substances, it has now been shown that the aromatic sulphonates of this element are usually soluble, crystalline compounds resembling the thorium sulphonates previously described by one of the authors (dbstr., 1904, i, 892). A representative series of these cerous sulphonates has been prepared together with several other salts of inorganic and organic acids.DISCUSSION. Dr. POWERcalled attention to the formula of cerium oxalate, which Dr. Morgan had referred to as being Ce2(C204),,9H20, and stated that an investigation of this salt, conducted some years ago by Mr. Frank Shedden and himself (J.SOC.Chem Ilzd., 1900, 19, 636), had con- clusively shown that it contains 10 molecules of water. It was thus perfectly analogous in composition to the oxalates of lanthanum and didymium, which may be represented by the general formula R”’,(C20J3,1OH,O. Dr. MORUAN stated that he had, quite incidentally, represented cerous oxalate as Ce2(C20,)3,9H,0, as this appeared to be the accepted formula for this well-known salt, and was thus given in current works on pharmacy.He had not noticed Dr. Power’s correction which showed that the oxalate was in reality a decahydrate, Ce2(C204),,10H,0. 75 56. ‘‘Volume changes which accompany transformations in the system N,z2S20,:5H20.” By Harry Medforth Dawson and Colin Gyrth Jackson. The changes which take place in the system Na,S20, :5H20 when subjected to certain temperature variations have been investigated by the dilatometric method. Volume temperature curves which indicate the relationship of the various forms of the system were described. At a temperature of 25’ the system has been obtained in the following six forms, each characterised by a definite volume : (1) primary pentahydrate, (2) secondary pentahydrate, (3) secondary tetrahydrate and saturated solution, (4) primary pentahydrate and saturated solution, (5) secondary monohydrate and saturated solution, (6) liquid.R7ith an accurately calibrated dilatometer the volume occupied by the supercooled liquid of the composition Na2S,0, :5H,O can be directly compared with the volumes of the primary and secondary pentahydrates and the specific gravities of these obtained with con-siderable accuracy. The transformation of the metastable secondary pentahydrate into the stable primary form affords an interesting lecture experiment. 57. “Depression of the freezing point of aqueous solutions of hydrogen peroxide by potassium persulphate and other com- pounds.” By Thomas Slater Price.Potassium persulphate causes a less molecular depression of the freeziug point of aqueous solutions of hydrogen peroxide than it does of water, and the conclusion is drawn that an unstable compound is formed in solution (compare Friend, Trans., 1906, 89, 1092) ; similar results hold for potassium sulphate and hydrogen peroxide. In the case of sulphuric acid the molecular depression of hydrogen peroxide solutions is greater than that of water; this confirms the results of Jones and Murray (Amer. Chern. J., 1903, 30, 205), that sulphuric acid is dissociated to a greater extent in aqueous hydrogen peroxide than in water.Potassium hydrogen sulphate and hydrogen peroxide interact in concentrated solution with the production of potassium permonosulphate-no potassium persulphate (K2S,0,) is formed-but it was not possible to obtain the pure salt. It was pointed out that a solution of potassium permonosulphate, in the presence of free acid, is much more stable than has been hitherto supposed. 76 58. '' The formation and reactions of imino-compounds. Part 111. The formation of 1 :3-naphthylenediamine and its derivatives from o-toluonitrile." By Ernest Francis Joseph Atkinson, Harry Ingham, and Jocelyn Field Thorpe. In Part I1 of this series it was shown that derivatives of benzene containing a saturated side chain of three carbon atoms substituted in the a-position by the nitrile group and in the /I-position by the imino- group pass on treatment with cold concentrated sulphuric acid into derivatives of 1 :3-naphthylenediamine.The authors have now applied this reaction to those derivatives of benzene which possess a saturated side chain of two carbon atoms substituted in the a-position by a nitrile group and in the p-position by an imino-group, and which contain a methyl group in the benzene ring in the ortho- position in respect to the side chain. The two compounds chosen to illustrate this generalisation were ethyl p-imino-a-cyano-p-o-tolylpro-pionate (I),which was found to be quantitatively converted into ethyl 1 :3-naphthylenediamine-2-carboxylate(11)on being dissolved in cold concentrated sulphuric acid : (1) (11) and /3-imino-a-cyano-a-phenyl-/3-o-tolylethane (111), which under the same conditions passed into 1 : 3-diamino-2-phenylnsphthalene(IV): Evidence was also brought forward indicating that the closing of the ring both in the present instances and also in those dealt with in Part 11 is due to the formation of a definite addition product formed by the action of concentrated sulphuric acid on the nitrile group.77 59. 6‘ The action of ethylene dibromide and of propylene dibromide on the disodium derivative of diacetylacetone.” By Alexander William Bain. By the action of ethylene dibromide on anhydrous disodium di-acetylacetone, the author has isolated a compound having the formula CH,*q//?\0 \C;‘:CH, C,H,,O,, to which he ascribes the constitution C\i /CHI c/ ICH,-CH, This substance melts at 62-63’, and possesses the remarkable faculty of undergoing isomeric change to a pyrone derivative, namely, 0,CH3*F//J \S*CH, C\I , when heated with concentrated hydrochloricI C/ICH,-CH, acid.The hydrochloride and platinichloride of this derivative have been prepared and analysed. CH3*fi//NH, \F:CH,. Ammonia reacts with the compound to give a\ /CHI ‘CO/ I CH,--CH, Similar derivatives have been prepared by the action of propylene dibromide, but both alkyl and alkylene halides of higher molecular weight react with great difficulty and then only to give very unstable compounds. ADDITIONS TO THE LIBRARY I.Donchtions. Archbutt, Leonard, and Deeley, R. Mountford. Lubrication and lubricants. A treatise on the theory and practice of lubrication, and on the nature, properties, and testing of lubricants. 2nd edition. pp. xxxi +528. ill. London 1907. (Recd. 6/3/07.) From L. Archbutt, Esq. Bernthsen, A. A text-book of organic chemistry. The English translation from the German, edited and revised to date by J. J. Sudborough. pp. xvi +658. London 1906. (Recd. 6/3/07.) From Professor J. J. Sudborough. 78 Freeman, John R. On the safeguarding of life in theatres. An Address made at the opening of the Annual Meeting of the American Society of Mechanical Engineers in New York City, December 4, 1905. Reprinted from the Transactions of the Society. pp.106. ill. [New York] 1906. (Recd. 1/3/07.) From the Author. Pauli, Wolfgang. Physical chemistry in the service of medicine. Authorised translation by Mavtin H. Fischer. pp. ix+ 156. New York 1907. (Recd. 27/2/07.j From the Publishers : Messrs. John Wiley and Sons. Plimmer, R.E. Aders. Practical physiological chemistry. 2 vols. pp. 55, 83. London [1907]. (Recd. 5/3/07.) From the Author. Pozzi-Escot, Em. The toxins and venoms, and their antibodies. Authorised translation by Alfred I. Cohn. pp. vii + 101. New York 1906. (Recd. 27/2/07.) From the Publishers : Messrs. John Wiley and Sons. Shepperson, William. Field to dairy. 2nd edition. pp. 65. London 1907. (Recd. 28/2/07.) Prom the Author. West Indies, Imperiul Department of Agricultwe.Lectures to sugar planters. pp. viii + 176. [Barbados] 1906. (Recd. 23/2/07.) From the Department. 11. By Purclmse. Hammarsten, Olof. Festschrift Olof Hammersten zu seinem f iinfundsechzigsten Geburtstage den 21 sten August 1906, gewidmet. pp. xxxi +[635]. Upsala 1906. (Recd.23/2/07.) Ries, Heinrich. Clays : their occurrence, properties, and uses. With especial reference to those of the United States. pp. xvi + 490, ill. New York 1906. (Recd. 23/2/07.) Thomson, J. J. Conduction of electricity through gases. 2nd edition. pp. viii + 678. ill. Cambridge 1906. (Recd. 23/2/07.) 79 ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Whitehall Rooms, Hotel Metropole, at 6.30 for 7 o’clock, on Friday, March SBnd, 1907 (the day fixed for the Annual General Meeting).The price of the tickets will be One Guinea each, including wine. All applications for tickets must be received not later than Friday, March 15th next. Tickets will be forwarded to Fellows on receipt of a remittance for the number required, made payable to ‘(Mr. S. E. Carr ” and addressed to the Assistant Secretary, Chemical Society, Burlington House, W. At the Annual General Meeting on Friday, March 22nd, the President will deliver an address entitled “The Position and Prospects of Chemical Research in Great Britain.” At the next Ordinary Meeting on Thursday, March 21, 1907, the following papers will be communicated : ‘( The synthesis of polypeptides.” By Emil Fischer. (‘Organic derivatives of silicon. Part 111. dl-Benzylme thylethyl- propylsilicane and experiments on the resolution of its sulphonic derivative.” By F. S. Kipping. “The reduction of carbon dioxide to formaldehyde in aqueous solutions.” By H. J. H. Fenton. (( The mechanism of the rusting of iron.” By G. T. Moody.(‘Some compounds of guanidine with sugars. Part I.” By R. S. Morrell and A. E. Bellars. K. CLAY AND SONS, LTD , BREAD ST. HILL, E.C., AKD BUNGAP, SUFFOLIC.
ISSN:0369-8718
DOI:10.1039/PL9072300069
出版商:RSC
年代:1907
数据来源: RSC
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