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Proceedings of the Chemical Society, Vol. 22, No. 306 |
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Proceedings of the Chemical Society, London,
Volume 22,
Issue 306,
1906,
Page 69-75
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摘要:
Issued 9/3/06 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 22. No.306. Thursday, March lst, 1906, at 8.30 p.m. Mr. A. G. VERNON HARCOURT,F.R.S., Past President, in the Chair. Messrs. A. T. Braid, H. E. Fierz, W. P. Hayworth, H. A. D. Neville, F. W. Walker, E. Wechsler, and J. L. White were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Xdwin Rodney Chrystall, Forest Villa, Prince’s Road, Buckhurst, Hill, Essex. Robert K. Duncan, University of Kansas, U.S.A. Ernest Feilmann, BSc., Ph.D., F.I.C., 2a, Dartmouth Road, Brondesbury, N.W. James Louis Foucar, B.Sc., 20, St. John’s Park, Blackhentb, S.E. Richard John Hall, M.Sc., F.I.C., ‘‘ Sandycroft,” Serpentine Road, Egremont, Liverpool. Walter Daly Scouller, B.Sc., 7, Stamp OfficePlace, Wakefield.James Frederick Spencer, MSc., Ph.D., 134, Rice Lane, Walton, Liverpool. Francis W. Storey, B.Sc., 43, Ellerdale Street, Lewisham, S.E. George Augustus Turner, ‘L Alma House,” Strandtown, Belfast. A certificate has been authorised by the Council for presentation to ballot under Bye-Law I (3) in favour of : Hem Chandra Dutt Gupta, 6LGuptanibar,”Krishnagar, Bengal, India Of the following papers, those marked * were read : “45. (‘Studies of dynamic isomerism. Part IV. Stereoisomeric halogen derivatives of camphor.” By Thomas Martin Lowry. Measurements were given of the solubility in alcohol of a-chloro- and a-bromo-camphors, UP-and ar-dibromocamphors, and UP-and ar-chloro- bromocamphors, both alone and in presence of a small proportion of sodium ethoxide.In each case it was found that the addition of alkali resulted in an increase of solubility in the ratio of about 0.9 to 1. No such increase was observed in the case of 6-bromocamphor, or of compounds in which both the a-and a’-hydrogen atoins were dis-placed. The increase of solubility is ascribed to the formation in the solution of a small proportion (7 to 12 per cent.) of the stereoisomeric a’-compound (compare Kipping, Proc., 1905, 21, 124 and 125). *46. (( The coagulating action of colloids. Part I.” By William Porter Dreaper and Alertander Wilson. The addition of tannic acid to an organic colloid like gelatin or albumin in the hydrosol state determines the amount of gallic acid absorbed by the coagulurn.The gallic acid may be present before or after the addition of tannic acid. Acids like hydrochloric or acetic reduce this absorption. Salts, on-fhe other hand, increase it. These acids do not seem to replace the gallic acid by mass action or otherwise. Gelatin in the hydrogel state absorbs gallic acid, although no pre-cipitation takes place if the former is in the hydrosol state. Salts increase absorption, but alcohol reduces it. Albumin absorbs gallic acid when precipitated by either tannic acid or heat. Alcohol prevents this action and also the absorption of tannic acid by albumin. Addition of gallic acid to a ‘‘ solution ” containing tannic acid and albumin causes rapid coagulation.This reaction is dependent on concentration. In very concentrated solutions, gallic acid will precipitate albumin. Absorption by silk is greatly reduced in presence of alcohol, the tannic acid absorbed is reduced from 15 to 1.2 per cent. Hide powder behaves in a similar way, the tannic acid absorbed being reduced from 72 to 10 per cent. Solutions of gelatin, ‘(Collin,” and albumin give these reactions. The results obtained by the author throw further light on dyeing and tanning processes. The influence of gallic acid in the manufacture of leather seems to be of a more direct nature than was previously supposed. DISCUSSION. Mr. DREAPER,in reply to questions from Ih. Chin, qtnted that, ‘I Collin ” was a form of soluble gelatin used by Parker and Payne in the estimation of tannic acid ; it did not enter the hyclrogel state at the ordinary temperature.The tannic and gallic acids were estimated by the process he had suggested some time ago. The tannic acid was titrated with copper sulphate solution in the presence of calcium carbonate. The separation of the two acids was brought about by precipitating the former as lead tannate in the presence of a definite excess of acetic acid, which pre- vented the gallate being precipitated at the same time. The gallic acid in the filtrate was then estimated as copper salt. ‘6*47. Studies on optically active carbimides. 111. The resolution of a-phenyl-a’-4-hydroxyphenylethaneby means of Z-menthyl-carbimide.” By Robert Howson Pickard and William Oswald Little bury.A method of resolving racemic hydroxyl compounds by means of I-menthylcarbimide was described. The 6-menthylcarbamates thus obtained by the combination of these compounds can be separated by fractional crystallisation and are then hydrolysed by alcoholic sodium hydroxide. d-a-Pheny2-a’-4-hydrox yphen ylethane 1-mentl~ylcarbaruate separates in a pure condition from light petroleum and melts at 117”. When h yd rol ysed, it yields d-a-phenyl- a‘- 4-hydroxy~he~yIethccne, which melts at 64O and has [a], + 7-78”in benzene. DISCUSSION. Dr. A. MCKENZIEasked whether the authors had obtained any evidence of the partial resolution of an inactive phenol into its optical isomerides by the action of an amount of I-menthylcarbimide insufficient for complete interaction.A partial resolution might be expected to occur under such conditions if the velocity of inter- action of the d-phenol with the I-carbimide were different from that of the I-phenol. That an inactive alcohol may be partially resolved into its optical isomerides has been shown with sec-octyl alcohol (Bey., 1901, 34,474). It would be interesting to know whether the temperature condi- tions under which the fractional crystallisation described by the authors took place had much influence on the progress of the resolution. Dr. PICKARD,in reply to a question from Dr. Forster, stated that 72 the method of obtaining cnrbimides by the action of nitrous acid on the corresponding carbamides could not be used for the preparation of E-menthylcarbimide, as this reacts too readily with water. In reply to Dr.McKenzie, he said that in attempting the resolution of ~-phenyl-~'-4-hydroxyphenylethaneby treatment with half its equi-valent of I-menthylcarbimide, some experimental dieculties supervened and led to the adoption of the easier method of fractionally crystal- lising a mixture of the two modifications of the I-menthylcarbamates. No evidence of a transition temperature was observed during the investigation. "48. "Experimentn on the synthesis of the terpenes. Part VIII. Synthesis of the optically active modifications of A3-p-menthenol(8) and As:e(g)-p-menthadiene.'' By Francis William Kay and William Henry Perkin, jun.The terpenes and their derivatives, which have so far been obtained synthetically (T7*a9zs.,1904, 85, 654; 1905, 87,639, 655, 661, 1067, and 1083; Proc., 1905, 21, 255), have always been inactive, but the following optically active members belonging to this group have now been synthesised. A1-Tetrahydro-p-toh~cacid, CHMe<CH2,CH2CH2-CH>~* CO,H, contains an asymmetric carbon atom, and by the systematic cryatallisation of its brucine and strychnine salts the authors have resolved it into its dextro-and Isevo-modifications. The laevo-modification obtained from the brucine salt has a rotation of [u],,-loo", whereas the dextro-acid obtained from the strychnine salt has a corresponding rotation of [a]D + 101". The esters of these acids were prepared by the action of alcoholic sulphuric acid ; et?qE d-A1-tetrahydro-p-toEuateboiled at 154O/100 mm.and had [a],,+86", the laevo-modification boiled at 154O/100 mm, and had [a]D -84". On treating the latter with the theoretical amount of magnesium methyl iodide and then decomposing with water and dilute acid, l-A3-p-menthe?zoE(8), GHMe<E2<E>C*CMe2*OH, was ob-tained; this substance bds at 101°/14 mm. and has [ -67". When this menthenol isldigested with potassium hydrogen sulphate, partial racemisation takes place, and the resulting A' 'Y'Y'-p-memthadiene, CHMB<~~~-'~>C*C<;~, which distils at 185O/'i48 mm., has aCH,-CH, rotation [a], of only -10'. Pure d-A3 '8(Q)-p-memthadiene was, however, obtained by the direct action of excess of magnesium methyl iodide on the d-ester without 73 the aid of the acid snlphate; it boils at l84--286O/756 mm.and has [.ID + 9S3. The magnetic rotations and other physical constants of these interesting substances are being determined. “49. “Studies in the acridine series. 111. The methylation of chrysaniline.” By Albert Ernest Dunstan and John Theodore Hewitt. The authors have continued the research on the lines laid down by Hewitt and Fox (T~ans.,1904, 85,529, and 1905, 87, lOSS), and have prepared the diacetyl and tetra-acetyl derivatives of chrysaniline, starting from the purified base. By treatment with methyl iodide and methyl alcohol, the diacetyl derivative afforded an acridinium methiodide, which on hydrolysis immediately gave an anhydro-base ; this substance was also prepared by the use of methyl sulphate and subsequent hydrolysis and precipita- tion with ammonia.50. “Note on the application of the electrolytic method to the estimation of arsenic in wall-papers, fabrics, &c.” By Thomas Edward Thorpe. Known quantities of the material, as a rule about 2 grams, are moistened with lime water, mixed with calcined magnesia, dried, and charred. The ash is treated with dilute sulphuric acid, half a gram of potassium metabisulphite added, the solution boiled and diluted to a definite volume, and the whole or an aliquot portion, depending on the amount of arsenic suspected to be present, is added to the electro- lytic arrangement already described (Trcc~.,1903, 83, 974).The deposit of arsenic so obtained is then compared with deposits obtained in precisely the same way by the addition of known quantities of arsenic, ranging from 0.005 to 0.0125 milligram of arsenious oxide, to materials free from arsenic, as in the method of testing brewing materials for arsenic already described (Zoc. cit.). A single incinera- tion of the suspected material suffices for several tests. The amounts of lime-water and magnesia recommended to be used have been proved by direct experiment to retain amounts of arsenic ranging from 0.0025 to 5 milligrams when contained in 2 grams of wool or paper. Many samples of woollen materials met with in commerce contain very notable quantities of arsenic, arising probably from the wide- spread use of arsenical dips.74 51. ‘‘Nitrogen halides from camphoryl-+-carbamide.” By Martin Onslow Forster and Hans Grossmann. The action of potassium hypobroruite and hypochlorite on camphoryl- +-carbainide has been foiind to give rise to dihalogen derivatives which have all the properties of compounds containing halogen attached to nitrogen. Normal carnphorylcarbamide yields the same substances, owing to the readiness with which it changes into the pseudo-modification under ’ the influence of alkalis. Corresponding mono-halogen derivatives have been obtained from camphorylmethyl-+-carbamide and its normal modification. 52. “The relation of position isomerism to optical activity. VI.The rotation of the menthyl esters of the isomeric chloronitro- benzoic acids.’’ By Julius Berend Cohen and Henry Percy Armes. It was pointed out in a previous paper on this subject (Tvans., 1905, 87, 11 92) that whereas chlorine and bromine atoms in the ortho-position to the active group lower its rotation, the nitro-group has the opposite effect of greatly increasing it. In the present investigation, the com- bined effect of halogen and nitro-group on the activity of the menthyl group has been examined. The authors have studied the rotations of eight out of the ten isomeric chloronitrobenzoic esters, the 2-chloro-3- nitro- and 3-chloro-2-nitro-compoundsbeing omitted owing to difficulties of preparation. ADDITIONS TO THE LIBRARY.I. Donations. Lbb, 7VaZther. Electrochemistry of organic compounds. Authorised translation from the 3rd edition by H. TI/: I;: Lorenz. pp. x+ 308. ill. New York 1906. (Red 28/2/06.) From the Publishers : Messrs. Wiley Bs Sons. Stas, Jean Seruais. Untersuchungen uber die Gesetze der chemischen Proportionen, uber die Atomgewichte und ihre gegenseitigen Ver-hiiltnisse. Uebersetzt von L. Aronstein. pp. xii + 347. Leipzig 1867. (Recd. 15/2/06.) From Dr. A. Scott, F.R.S. 11. By Purci~nse. LOW,Albert H. Technical methods of ore analysis. pp. x+ 273, ill. New York 1905. (Recd. 20/2/06.) 75 ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the election of Officers and Council and other business will be held on Friday, 30th March, 1906, at 5 o’clock in the afternoon.willThe PRESIDENT deliver his address entitled : (‘The living organism as a chemical agency : A review of some of the problems of photosynthesis by growing plants.” At the next Ordinary Meeting, on Thursday, Narch 15th. 1906, at 8.30p.m., the following papers will be communicated : “The interaction of well-dried mixtures of hydrocarbons and oxygen.” By W. A. Bone and G. W. Andrew. “The explosive combustion of hydrocarbons.” By W. A. Bone and J. Drugman. ‘‘ The occurrence of marsh gas amongst the decomposition products of certain nitrogenous bases as a source of error in the determination of nitrogen by the absolute method.” By P. Haas. ‘‘Studies on comparative cryoscopy. Part IV. The hydrocarbons and their halogen derivatives in phenol solution.” By P. W. Robert son. “The displacement of acid radicles. I. Displacement of the chloride and nitrate radicles.” By A. F. Joseph. R. OLAY AND 80h8, LTD., HIEAD BT. BILL, L.C., AND BUNGAY, SUPFOLK.
ISSN:0369-8718
DOI:10.1039/PL9062200069
出版商:RSC
年代:1906
数据来源: RSC
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