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Proceedings of the Chemical Society, Vol. 20, No. 281 |
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Proceedings of the Chemical Society, London,
Volume 20,
Issue 281,
1904,
Page 121-130
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. Val. 20. No. 281. ~-.___ Wednesday, May 18th, 1904. Professor W. A. TILDEN,D.Sc., E.R.S., President, in the Chair. Before entering on the ordinary business of tho meeting, the PRESIDENTsaid he thought it would be consonant with the wishes of the Fellows if he gave expression to the deep feeling of regret with which they had all received the news of the death of one of the most eminent of their past Presidents, Professor Williamson. A man of philosophic mind and great intellectual activity, he had been led in the later years of his life to abandon research in connection with chemistry in favour of other pursuits. Hence it was difficult for chemists of the present generation to realise how great had been the influence exercised by his experimental researches and his writings on the progress of theoretical chemistry forty years ago.Williamson served the Society during many years on the Council, as vice-Presi-dent, and for two separate periods as President. The Society had, of course, been represented at the funeral, at which many past and present officers of the Society-including himself and the Treasurer- had assembled, and a resolution of condolence with the family had that day been passed at the meeting of the Council. Messrs. N. J. Bluman, J. C. Evans, G. Pinchbeck, and M. W. Stevens were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Frank Harold Lowe, B.Sc., 598, Fulham Park Gardens, S.W.Henry Stanley Shelton, 4,Larden Road, Acton Vale, W. Herbert Jenkins, 52, Criffel Avenue, Streatham Hill, S.W. Rudolf Lessing, Ph.D., 31, Brunawick Square, W.C. Robert Rodger, 54, Rostrevor Road, S.W. W-illiam Edward Oakden, 2,Gledhow Terrace, South Kensington,S. W. Charles John Sawer, 6, Cleveland Road, Brighton. A ballot for t-he election of Honorary and Foreign members was held, and the following were subsequently declared duly elected : Prof. hntoine Henri Becquerel. Prof. Cornelis Adrisan Lobry de Bruyn. Prof. Frank Wigglesworth Clarke. Madame Marie Curie. Prof. Carl Theodor Liebermann. Prof. Edward Williams Morley. In reply to Prof. Divers, the PRESIDENTstated that Counsel’s opinion had been taken on the question whether women were eligible for election as ordinary Fellows of the Society under the present Cbarter, and that the opinion was adverse.*87. “The action of nitrosyl chloride on pinene.” ByWilliam Augustus Tilden. Pinene nitrosochloride having been shown by von Baeyer to bave the double formula (CloH,,*KOCl),, it occurred to the author that the unsatisfactory yield of this compound by the usual processes might be improved by using a mixture of equal quantities of d-and I-pinenes which is optically inactive. Whereas previously the yield of nitroso- chloride from ordinary d-pinene was about 32 per cent. of the pinene, and the product from the more highly rotatory pinene obtained from French turpentine was still less, the employment of a mixture prepared so as to be optically inactive gives 55 per cent.The melting point of pure pinene nitrosochloride is not 103O, as originally given, but 115’ (circa). Attempts to resolve pinylamim into two optically active bases proved unsuocessful. For the regeneration of pinene from the nitrosochloride, methyl- aniline is recommended in preference to aniline, as there is no violent action and the yield of pinene is greater. Finally, it is shown that when the nitrosochloride is converted into nitrosocyanide (Tilden and Burrows, Proc., 1902, 18, 161) or into 123 the piperidylnitrolami ne, the compound becomes monomolecular at the same time that the nitroso-group assumes the isonitroso- or oxime structure. DISCUSSION.Professor MELDOLAsuggested that the base produced by the action of dimethylaniline on pinene nitrosochloride might be Bindschedler’s green resulting from the secondary interaction between nitrosodimethyl- aniline and the excess of dimethylaniline present under the conditions of the experiment (Be?..,1883, 16,864). ”88. (‘The electrolytic estimation of minute quantities of arsenic.’’ By Henry Julius Salmon Sand and John Edward Hackford. A high supertension of the cathode is requisite for the reduction of arsenic acid to metallic arsenic, the reaction being most readily effected in the presence of metals having this property, such as lead or zinc and probably also mercury. Platinum, having a low super-tension, is quite inefficient. The production of arsenic trihydride from arsenites is accomplished more readily by platinum cathodes than by those of copper, which have a much higher supertension.In this case, mercury, with an extremely high supertension, is quite unsuitable. A certain amount of supertension, however, appears to be necessary, for platinised platinum with no supertension is inefficient. The authors recommend the use of lead electrodes for the estima- tion of minute quantities of arsenic as their application causes a simplification of previous methods. Errors which may arise in the electrolytic methods owing to the presence of foreign metals can be rectified by the addition of lead acetate or zinc sulphate to the electro- lyte except when the foreign metal is mercury.When lead and zinc cathodes are used, the smallest amount of arsenic which can be detected in alkaline solutions of arsenates and arsenites is about thirty times as great as in acid solution, but platinum cathodes are quite unsuitable. DISCUSSION. Dr. F. M. PERKINremarked that although the electrolytic apparatus gave good results even with very minute quantities of arsenic, it was, however, a great advantage to have an apparatus in which lead was employed for the cathode instead of the very expensive platinum, The fact that a mercury cathode did not give good results, although there mas considerable over-voltage, was due to the formation 124 of an arsenic amalgam, which then escaped the reducing action of the hydrogen.An aluminium cathode is suitable for dilute sulphuric acid solutions, because in this case there is considerable over-voltage and the metal is very slightly attacked, and is, moreover, free from arsenic. Had nickel electrodes been tried in an alkaline solution ? The only drawback to the electrolytic method for detecting arsenic is the trouble of preparing the mirrors, especially when special standards are made for each substance tested. Dr. STEVENSONasked what was the authors’ evidence that the lead of commerce can be obtained free from arsenic. Mr. SAND,in reply, said the electrolytic experiments in alkaline solutions had not been found satisfactory, and had, moreover, not been tried in the case of nickel. The preparation of mirrors for each kind of material examined was not absolutely necessary, but, nevertheless, this precaution rendered the comparisons more certain.Several grams of commercial lead had been examined for arsenic with a negative result. The lead most frequently used for cathodes was purest assay lead, whereas pure commercial lead was employed for anodes. New electrodes often contain a small amount of arsenic on the surface, but in all cases they were t’ested by blank experiments. *89. “The action of sodium methoxide and its homologues on benzophenone chloride and henzylidene chloride. Part 11.” By John Edwin Nackenzie and Alfred Francis Joseph. The authors have found that benzhydrol is formed in the prepara- tion of diisopropyloxy-, diisobutyloxy-, and diisoamyloxy-dipheny1-methanes by the action of the respective sodium alkyloxides on benzo- phenone chloride (compare Trans.! 1901, 79, 1204).It is also shown that dibenzoxydiphenylmethane, like its homologues, readily splits up into benzophenone and dibenzyl oxide. The anhydride of phenyldi-P-hydroxynaphthylmethane has been obtained by the action of benzylidene chloride on /I-naphthol, and found to agree in properties with the substance prepared by Claisen (AnnaZern, 1887,237, 261) from benzaldehyde and P-naphthol. This product was also obtained when the reaction was carried out in xylene solution and when sodium naphthoxide was used instead of naphthol. Claisen’s dihydroxy-compound could not be isolated. Nitration experiments on the anhydride led to the formation of sub-stances containing from two to six nitro-groups.When treated with fuming sulphuric acid, the anhydride yielded a 125 p-napbtholdisulphonic acid, but concentrated sulphuric acid gave rise to a product dissolving in water to a bright red solution, the colour of which was destroyed by alkalis and restored by acids. DISCUSSION. Professor MELDOLAsaid that in his opinion the constitution of Claisen’s compound might be more correctly represented by the follow- ing formula : as it was more in harmony with the general properties of P-naphthol that the a-ortho-position, and not the second P-position, should be first attacked. Dr. HEWITTstated that the hydroxylic compound, C,H,*CH(C,,H,*OH),, is easily produced by condensing benzaldehyde and P-naphthol in cold acetic acid solution by the aid of hydrochloric acid, and from this the anhydro-substance can be obtained in good yield by heating with acetic acid in sealed tubes.The coloration observed on dissolving the anhydride in strong sulphuric acid is probably due to oxidation and formation of a carboxonium salt similar to those already studied by Werner, Fosse, and himself. Dr. MACKBNZIEreplied that at present he had no decided views in favour of the 2 : 3-structure of the anhydride molecule as against the 1:2-configuration; he had not yet obtained any substitution products in support of either of these constitutions. “90. ‘‘The bromination of phenolic compounds.’’ By John Theodore Hewitt, James Kenner, and Harry Silk.When one molecular proportion of bromine acts on phenol, the character and proportions of the products obtained vary with the con- ditions under which the reaction is carried out. In aqueous solution, the phenol is apparently not all brominated, some of the bromine being used in forming higher substitution products. Absence of water and presence of a strong mineral acid favours the formation of p-bromo- phenol ; the quantity of the para-compound diminishes, however, if sodium acetate is added to a glacial acetic acid solution of phenol before bromination, but is slightly increased by the addition of con-centrated sulphuric acid. 126 If more than one molecular proportion of bromine is added to a solution of phenol in concentrated sulphuric and glacial acetic acids, the second molecule of bromine is utilised very slowly, the sulphuric acid hindering substitution in the ortho-position, but by brominating phenol in excess of 73 per cent.sulphuric acid, the halogen rapidly enters into reaction, and a nearly quantitative yield of 2 :4-dibromophenol is obtained, apparently without any admixture of tribromophenol. 5-Bromosalicylic acid can be conveniently prepared by brominating salicylic acid in a mixture of sulphuric and acetic acids. 4-Bromo-a-naphthol cannot, however, be obtained from a-naphthol under similar conditions, dibromination taking place. DISCUSSION. Professor MELDOLApointed out that in the case of the naphthols it was well known that the first action of bromine isko produce additive products from which hydrogen bromide is expelled by heat.With reference to the influence of temperature as determining the formation of o-bromophenol instead of the para-compound, he called attention to Merck's German patent (No. 76597, of 1893), in which it is claimed that by chlorinating or brominating phenol at 150-180' the corre- sponding halogenated ortho-derivative is produced, 91. ''The decomposition of the alkylureas. A preliminary note." By Charles Edward Fawsitt. The author has already shown (Zeit. physikal. Chew., 1902, 41, 601) that the decomposition of urea by acids is not a case of ordinary hydrolysis, but is the result of a secondary decomposition, following an isomeric transformation into ammonium cyanate.An investigation of the velocity of decomposition of the alkylureas with acids by similar methods shows an exact parallel with the case of urea. The hydro- lysis is indirect, and is effected as a secondary reaction of the acid with the alkylammonium cganate. Methyl urea is decomposed more slowly than urea, but dimethylurea much more rapidly. '92. (( The formation of periodides in nitrobenzene solution. Part XI. Periodides of the alkali and alkaline earth metals." By Harry Medforth Dawson and Ethel Elizabeth Goodson. Previous experiments relating to the nature of the periodides which are formed in nitrobenzene solutions containing iodine and potassium iodide (Dawson and Gawler, Trans., 1902,81, 524) have been extended to the iodides of the other alkali metals, arid to those of the 127 alkaline earth metals, and ammonium and substituted ammoniums.In general, these iodides have properties similar to those of the potassium derivative, and the experimental data indicate that ennea- iodides of the type MI, or MI,,, which are the essential com-ponents of such solutions when saturated with iodine, probably repre- sent the highest limiting type of periodide, for the solvent used in these experiments appears to be specially suited to the formation of such periodides, and saturation of the solution with iodine favours the formation of the most complex product. In the case of certain substituted ammonium radicles, enneaiodides have been already isolated and the analogous behaviour of the alkali and alkaline earth metals indicates the possibility of preparing enneaiodides of these metals under favourable conditions.Periodides are also formed by the bromides of the alkali metals in nitrobenzene solution and to a small extent by the chlorides. Compounds of lithium iodide with nitrobenzene and o-nitrotoluene, and of sodium penta-iodide with nitrobenzene have been isolated. 93. 6L The action of ozone on ethane. Preliminary note.” By William Arthur Bone and Julien Drugman. The authors have obtained ethyl alcohol by the interaction of ethane and ozoneat 100’. Two experiments have been carried out as follows: ethane and ozonised air (0,= about 2; per cent.) were separately led into the top of a vertical, wide glass tube, about 18 inches long, packed with glass beads and heated by a steam jacket.The proportions of the gases were so regulated that the ethane was always present in large excess, under which conditions the ozone entirely disappeared as the mixture slowly descended the tube. The gases were then drawn through a series of cooled glass worms containing water for the absorp- tion of soluble intermediate products. Each experiment extended over 3 or 4 days, during which about 5 litres of ethane and 13 to 15 litres of the ozonised air passed through the apparatus. Subsequent examination of the liquid from the coolers showed that it contained ethyl alcohol, acetaldehyde, and traces of formaldehyde.The presence of ethyl alcohol was proved by first oxidising the aldehydes by means of an excess of an ammoniacal silver solution at the ordinary tempera- ture (1 hour), then acidifying the liquid with dilute sulphuric acid and submitting it to distillation in steam. The distillate in each case at once gave the iodoform reaction; the precipitate was composed of microscopic crystals, which slowly formed the characteristic star-like aggregates. As a precaution, the absence of acetaldehyde from the distillate was proved by the negative result obtained with Schiff’s 128 reagent. An examination of the gaseous products showed that they did not contain acetylene, ethylene, or free hydrogen. There can be but little doubt, therefore, that ethyl alcohol is the primary product in the slow combustion of ethane.At bemperatures where ethane begins to react with oxygen with appreciable velocity, the alcohol is oxidised so many times faster that it is practically impossible actually to detect its formation (compare Bone and Stockings, this vol., p. 106). The authors propose to continue the experiments, and to extend them to ethylene, acetylene, and other typical hydro- carbons. I'94. Caproglthiocarbimide." By Augustus Edward Dixon. Caproyl chloride, dissolved in benzene, interacts spontaneously with finely-powdered ammonium thiocyanate, yielding caproylthio-cccrbinzide, C,H,,*CO*NCS; b. p. 108'/23 mm. ;sp. gr. = 1.0165 at 18'/15". This liquid is slowly hydrolysed by boiling water into caproic and thiocyanic acids; when heated with an alkaline lead salt, it yields metallic sulphide, together with thiocyanate, and is readily desulphurised by ammoniacal silver nitrate.If brought into con-tact with primary and secondary amines, direct union occurs, with formation of the corresponding thiocarbamides. ab-Caproylphen ylthioccw6amide, C,H,,*CO-NH*CS NHPh, separates from alcohol in felted masses of needles, melting at 77-7s" without decomposition; when dissolved in hot dilute caustic alkali, the caproyl group is removed, leaving phenylthiourea. ab-Caproyl-0-tolyllthiocurbanzidemelts at 97-98' and generally resembles the phenyl compound. When treated in hot alcoholic solu- tion with the calculated quantity of silver nitrate, it yields the corresponding ab-cuproyll-o-tolylurea (m.p. 99-100').ab-Caproyl-p-tolythiocurbamide (m. p. 90-9lo), when treated with silver nitrate, yields cup~oyl-p-tolyllurea, me1 ting at 131-1 32" (corr.). n-Caproy~henylbepzaylthiourecc,C,H,,*CO*N:C(SH)*NBzPh, was ob-tained from benzylaniline and the thiocarbimide ;it separated from alcohol in vitreous prisms melting at 77-78", and was not affected by boiling with neutral or ammoniacal silver nitrate ; when boiled with caustic alkali, the caproyl group is eliminated, leaving a residue which can be desulphurised by an alkaline solution of lead. Since, by interaction with water, the parent oil gives thiocyanic acid instead of carbon oxysulphide, its behaviour in these circum-stances must be accounted that of a thiocyanate; on the other hand, the power to combine with nitrogenous bases, thereby yielding sub- stituted thiocarbamides, places it among the isothiocyanates.This 129 dual capacity is in accordance with the view developed in earlier ,papers by the author (Trans., 1901, 79, 542 ; this vol. p. 350),that a variety of tautomerism subsists amongst the thiocyanates of electro-negative radicles, the characteristic sulphuretted group of which may act either as *SCN or *NCS. Moreover, in certain cases, both forms appear to be simultaneously active (Doran, Proc., 1904, 20, ZO), the preponderance of one or other depending almost entirely on the temperature at which interaction is caused to take place.ADDITIONS TO THE LIBRARY. IT. By Purchase. Caro, N., Ludwig, A,, und Vogel, J. H. Handbuch fur Acetylen in kechnischer und missenschaftlicher Hinsicht. Herausgegeben von J. H. Vogel. pp. xiv + SSO. ill. Braunschweig 1904. Noelting, E., und Lehne, A. Anilinschwilrz und seine Anwendung in Fiirberei und Zeugdruck. Zweite Auflsge. pp. 178. ill. Berlin 1904. Ostwald, Wilhelm. Grundtinien der anorganischen Chemie. Zweite Auflage. pp. xx+ 808. ill. Leipzig 1904. Ostwald, Wilhelm. Malerbriefe, Beitriige zur Theorie und Praxis der Malerei. pp. viii+ 165. Leipzig 1904. Spaeth, Eduard. Die chemische und mikroskopische Untersuchung des Harnes. pp. xx+ 533. ill. Leipzig 1903. III. Pamphlets. Beach, S. A,, Clark, V. A., and Taylor, 0. &I.Spray mixtures and spray machinery, (New York Agric.Exper. Station. Bulletin No. 243.) Fairley, Thomas. The uses of lime on land. (From the AmuaZ Report, YorJcshire Agric. Soc., 1904.) Grindley, H. S., and Rlojonnier, Timothy. Experiments on losses in cooking meat. (U. S. Dept. of Agriculture, Office of Experiment Stations. Bulletin KO.141.) Washington 1904. New York Agricultural Experimental Station. Directors' Report for -1903. (Bulletin No. 244.) 130 Parrot, P. J., Beach, S. A., and Woodwortb, H. C. The lime-sulphur-soda wash for orchard treatment. (New York Agric. Exper. Station. Bulletin No. 247.) Sherman, Penoyer, L. The gutta-percha and rubber of the Philippine Islands. Manila 1903. Sodeau, William H. The decomposition of chlorates.(From the Proc. Univ.of Durham I’M.Xoc., 2, pt. 3.) --The estimation of unburnt products in chimney gases by means of a modified Orsat apparatus. (From the Chemical News, 89.) Taylor, 0. M., and Clark, V. A. An experiment in shading straw-berries. (New York Agric. Exper. Station. Bulletin No. 246.) Van Slyke, L. L., and Hart, E. B. Chemical changes in the souring of milk and their relations to cottage cheese. (New York Agric. Exper. Station. Bulletin No. 245.) Wheeler, W. P. The importance of mineral matter and the value of grit for chicks. (New York Agric. Exper. Station. Bulletin No. 242.) RESEARCH FUND. A Meeting of the Eesearch 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 June 6th.At the next Ordinary Meeting, on Thursday, June 2nd, 1904, at 8 p.m., tho following papers will be communicated : ‘‘isoNitrosocamphor.” By M. 0. Forster. ‘(Imino-ethers and allied compounds corresponding with the substituted oxamic esters.” By G. D. Lander. ‘(The action of heat on a-hydroxycarboxylic acids. Part I. a-Hydroxystearic acid.” By H. R. Le Sueur. “The basic properties of oxygen. Additive derivatives of the halogen acids and organic compounds and the higher valencies of oxygen. Asymmetric oxygen.” By E. H. Archibald and D. McIntosh. R CLAY AND SONS LTD., BREAD ST. HILL, E.C., AND UUNQAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9042000121
出版商:RSC
年代:1904
数据来源: RSC
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