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Issued 8112/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 20. No.286. Thursday, December lst, 1904. Professor W. A. TILDEN, D.Sc., F.R.S., President, in the Chair. Messrs. A. D. Cowper and E. S. Simpson were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs : Andrea Angel, M.A ., 41, Wellington Bquare, Oxford. James H. Campbell, 3, Morrison Terrace, North Road, Bellshill, N.B. Bernard Collitt, 79, Eastbourne Terrace, Gainsborough. Herbert Goodier, 16, Hall Royd, Shipley. George Moss Lloyd, M.A., M.Sc., Queen’s Road, Rock Ferry, Thomas Pennycuick, B.Sc., 6, Lorne Street, Fairfield, Liverpool. Bert Perrott, Ael-y-Bryn, Penywern Road, Neath, Glam. William Henry Hstcliffe, B.Sc., 18, Wheeler Street, Maidstone.Frederick George Richards, 21, Dutton Street, Manchester. Harold Rudolph Rogers, B.A., 75, South Side, ClaphamCommon, S.W. The PRESIDENTdrew attention to the stand for the display of certificates of candidates for election which had been placed in the Library, and stated that, as the certificates are now printed in full in the “Proceedings,” they would not in future be brought down from the Library on the occasion of the ballot, 240 A Ballot for the electioii of Fellows was held, and the following were subsequently declared duly elected : William Harold Richard Allen. John Richard Johnson. Walter Henry Bentley, B.A. Horace Francis Jones. John Wyclif Black. Willism App Jones, Ph. I).,A. M, Thomas Story Busher, B.A.Alfred Fraiicis Joseph. Lawrence Cal deco tt. Gristav Kon)ppa, 1’h.D. Robert John Caldwell, B.Sc. James StRiiley Laudrr. Peter Skinner Clark, M.B., Ch.BZ. AIthur Garfield Levy, U. Sc. Frederick Clarkson-Harold. James Patrick Longstnff, KSc. Jabez Horace Cooper, B.A. Arthur Thomas McDougdl, R. A. William Crabb, B. Sc. Harold Joseph Clnike Mathews. James Edward Cuniiinghain. Ernest Wcstby Millar. Williaiii Herbert Dal toil, George Frederick Phillips, B.8c. Harold Deane, B.Sc. Marie Jcan Louis Ernest Rouillard, Francis Dickinson. 13. sc. Edward Evans. Pcrcy Edwiii Spielmann. John Evans. Harry Stanley, B.Sc. Thomas Wallace Fagan, B.A. Thomas Sutcl iffe. Johii Kerr Forrest. Ynnl John Thibault. Archie Will oughhg Henzell. Arnold Bertram Tonkin. Thomas Reginald Hodgson.Douglas Frank Twiss, M.Sc. George William Thomas Horrod. Edwin Roy Watson, R.A., R.Sc. John Kenneth Harold Inglis, Herbert Wood Watson, B.Sc*. M.A.,B.Sc. Henry Bridges Weeks. Thomas Campbell James, B. A., William Henry Willcox, N.1).,B. Sc. BSc. Frank John Wyeth, M.A. Walter Richmond James. Of the following papers, those marked * were read : “201. The nitrites of the alkali metals and metals of the alkaline‘I earths and their decomposition by heat.” By Prafulla Chandra RQy. Solutions of the nitrites of barium and calcium, like those of the alkali metals, can be safely evaporated to dryness st the boiling temperature witbout decompositiou or oxidatiori taking place. A solution of magnesium nitrite prepared by the double decomposition between barium nitrite and magnesium srilphate is perfectly stable at the ordinary temperature, but it cannot be concentrated on the water- bath as it undergoes decomposition even at 60°, evolving nitric oxide.The solution, when concentrated under reduced pressure over sulphuric acid, yields the hydrated salt Mg(N0,),,3H20, which, when kept in a desiccator, loses only one molecule of water, the dehydration not going any further. All the nitrites described have a faint yellow colour. When barium nitrite is heated under reduced pressure at 225-300°, the following reactions occur : 24 I 3Sa(NO,), = 2Ba0 + Ra(N 03)2+ 4 NO, 2 Ea(NO,), = BaO + Ba( NO,), + NO + N ; whereas at temperatures between 300' and 500' or upwards the follow- ing change takes place : Bs(NO,), = BaO + 3N0, + 0,.The other nitrites behave similarly. In the earlier stages, the gasecus products of decomposition are mainly nitric oxide and nitrogen, in the second they are chiefly nitrogen peroxide and oxygen. It, is difficult to distinguish sharply between these two stages, and an intermediate phase has been observed : Bs(N03),= Ba(NO,), + 0,. The decomposition of magnesium nitrite begins at 60', and at 120' that of the first strtee is complete, resulting in the formation of a basic nitrate, Mg(NO,),,MgO, which is stable even at 1'75'. "202. The metallic derivatives of nitrogen iodide and their6' bearing on its constitution." By Oswald Silberrad, On examining Guyard's copper derivative (compare Compt.rend., 1884, 97, 526), the compound was found to be a cuprosamine pwiodide, Cu,Z,(5NH,)I4,H,O, and not a derivative of nitrogen iodide ; it is not explosive, and has the properties of a periodide. On heating, it evolves iodine vapour, and by treating with potassium iodide solution the loosely combined iodine is removed quantitatively. The regeneration of nitrogen iodide from the cuprosamine periodide by ammonia must also be regarded as distinct evidence of its periodide character, for, according to this view, the loosely combined iodine reacts with ammonia precisely as does potassium periodide. Cupro~camineIodide, Cu,I2,NH,,4H,O.-When the foregoing per- iodide is treated with potassium iodide solution, the loosely combined iodine is removed and a green, crystalline residue remains behind, which dries to an olive-green, crystalline powder having the above formula; it is insoluble in water, but dissolves fairly readily in ammonia.The silver derivative formulated by Szuhay as AgNI, (Ber., 1893, 26,1933) was again investigated, but it was found that by following his method a compound of constant composition could not be prepared. By the addition of iodiue chloride soliltion to an ammoniacal silver solution, a pure product having the formula NI,NH,Ag was obtained. The substance decomposes readily, even at the ordinary temperature and especially when exposed to light ; in the dry state, it explodes on the slightest friction, It dissolves readily in potassium cyanide and is regenerated by the addition of ammoniacal silver nitrate.Sztihay 262 stated that an intermediate potassium salt was formed. This is dis- proved by an examination of the solution obtained by adding potassium cyanide to nitrogen iodide. Exactly 3 mols. of potassium cyanide were required to dissolve 1 mol. of nitrogen iodide, this number being independent of the excess of ammonia present. The products identi- fied were cyanogen iodide, potassium iodide, potassium carbonate, potassium cyanate, ammonia, and cyanogen. The mechanism of the change is as follows : 1. 3KCN+NH3N13+3H20=3CNI+3KOH+2NH,,. 2. CNI + 2KOH= KCNO +KI + H20. 3. 2 KCNO +3H20=K,CO, + 2NH3+CO,. At low temperatures and in concentrated solution, the cyanogen iodide is partially precipitated, but at the ordinary temperature it rapidly decomposes in solution.The action of potassium cyanide on the silver derivative took place in accordance with the equation : NI,:NH,Ag +4KCN +4H20=3CNI +AgCN +4KOH + 2NH,. It was also found that although cyanogen iodide produ3ed no pre-cipitate of nitrogen iodide when added to ammonia, yet in the presence of silver the compound NI,:NH,Ag was readily obtained. The behaviour of the silver compound towards potassium cyanide is thus fully explained without any necessity for assuming the existence of an intermediate potassium salt. "203. Synthesis of 1 :l-dimethylhexahydrobenzene." By Arthur'L William Crossley and Nora Renouf.5-Chloro-3-keto-1 : 1-dimethyl-A4-tetrahydrobenzene(Trans., 1903, 83, 117), when treated with sodium in moist ethereal solution, yields 3-hydroxy-I :1 dimethylhexahydrobenxene, (CH3;G<~~~~~~~~>can together with other substances not yet investigated. The product is a clear colourless liquid boiling at 99*5'/35 mm. and having a marked odour of peppermint. When treated with fuming hydrobrornic acid, it is converted into 3-brorno-1 :1-dimethylhexahydrobenxene,a colourless liquid boiling at 98O/50 mm. The bromine atom in this compound is readily replaced by hydrogen on heating with zinc dust in aqueous alcoholic solution, giving rise to 1 :l-dimsthyll~excchydrobenxene,which is a colourless refractive liquid boiling at 11 7'/743 mm.and having a geranium-like odour. In 1902, Zelinsky (Annalen, 1902, 319,318) described the prepara- 243 tion of dihydroisol~turolene, which hydrocarbon, be suggested, was 1: 1-dimethylhexahydrobenzene,and the nuthors are at present com- paring the properties of these two hydrocarbons, and also the pro- perties of 1 :1-dimethyltetrahydrobenzene, with the hydrocarbons of the formula C8HI4,which have at various times been obtained from derivatives of camphor. *204.I' The formation and reactions of imino-compounds. I. Conden-sation of ethyl cyanoacetate with its sodium derivative." By Harold Baron, Frederick George Percy Remfry, and Jocelyn Field Thorpe. Ethyl cyanoacetxte condenses with its sodium derivative forming the sodium compound of ethyl a-cyano-P-iminoglectcc1.ateY CO,Et*CHNn*C(:NH)*CH(CN)*CO,Et, which can readily be converted into ethyl a-cyccno-P-i.w~inoglutarat~, C02Et*CH,*C(:NH)*CH(CN)oC0,Et.This substance contains three (1)(3) (2) hydrogen atoms capsble of replacement by sodium in the order indicated by the numerals.Ethyl a-cyano-/3-jminogIutarate and its alkyl derivatives yield the corresponding ethy1 hy drogeri sslts, WO,H*CHR'C(: NH)*CR(CN)*CO,Et, on hydrolysis with sodium carbonate. These compounds, on heating above their melting points, are con- verted into derivatives of glutazine, which can be transformed into the corresponding derivatives of 2 :4 :6-trioxypyridine by suitable reagents. The same glutazine derivatives are formed by the action of concen-trated sulphuric acid OD the diethyl salts.The substitution derivatives of glutazine can react in the two forms : The mono-substitution derivatives react in the second form towards acid hydrolysing agents, and in the first form towards nitrous acid. The di-substitution derivatives react only in the second form, whilst the tri-substitution derivatives react in the first form. Ethyl a-cyano-P-iminoglutarnate, CONH,*clH,*C( :NH)*CH(CN).CO,E t, 244 can be converted into a derivative of glutmine in two ways. Thus, with concentrated sulphuric acid, it yields ethpl glutazinecarboxglnte, NH<~~.,,(,o~~J>C:NH, but with sodium carbonat,e solution it is converted into gluhzine cymide, NH<~~~~~~>C:NH.“205. 6‘ The aflinity constants of aniline and its derivatives.” ByRobert Crosbie Farmer and Frederick John Warth. The affinity constants of aniline and its deiivatives are best deter-mined through the hydrolytic dissociatiou of their salts. For this purpose, the met>hod of distribution between two solvents, previously employed by one of the authors (Farmer, Tvans., 1901,79,863),has been applied to these compounds. The advantages of the method are, mainly, its applicability to (1) sparingly soluble organic compounds, (2) strongly coloured solutione, (3j solutions in which a slight decom- position interferes with titrations, (4) salts which are hydrolped to the extent of nearly 100 per cent. in solution. Comparative experiments showed that the sulphates of aniline and the toluidines were in all instances hydrolped to a greater extent than the corresponding hydrochloride?, but the relative difference decreased in dilute solution.o-Nitroaniline showed pra~t~ically no tendency to form a hydro-chloride in aqueous solution, and p-nitroaniline was a much weaker base than the meta-isomeride. The nitroanilines exhibited no acidic properties when examined by the same method in presence of caustic potash. The substituents arranged themselves in the following order as regards their influence on the affinity constant of aniline, the nitro- group being the most electronegative : NO,, CO,H, aN:N*C,H,, Br, C1, CH,, OCH,. a-and p-Naphthglamines were somewhat weaker bases than aniline.Acetanilide and aceto-o-toluidide showed practically no basic properties. p-Nitrosomethylaniline possessed easily measur- able acidic properties in addition to its basic properties, but p-nitroso-dimethylaniline showed no tendency to form salts with alkalis. 206. The attractive force of crystals for like molecules in saturated solutions.” By Edward Sonstadt. The author describes the preparatiou of saturated solutions in pairs or in sets, in which to one or more of the solutions is added a quantity of the crystals of the dissolved salt, the flasks or other containing vessels being left together in a cellar in which the temperature varies 245 only slowly. The added crystals draw from the solution in which they are deposited a certain portion of the salt, so that the supernatant liquid contains, after a time, an appreciably smaller proportion of the dissolved salt than the solutions contained in the other vessels, to which no crystals had been added.The det)erminations were made either by evaporating a weighed portion of each of the solutions and weighing the residue, or by taking the density of the solutions by a specific gravity bottle. 207. “The Grignard reaction applied to the esters of hydroxy-acids.” By Percy Faradag Frankland and Douglas Frank Twiss. By actiag on dimethyl tartrate with magiesium phenyl bromide aud treating the product with dilute sulphuric acid, the authors have obtained a compound crystallising in small, white needles (m. p. 14 So), which is presumably aa88-tetraphenylerythrito1, (C,H,)2C(OH)*CH(oH)*C~(OH)*C~oH)(c6H~)2.It is powerfully dextrorotatory, a 4.327 per cent. solutiou in ethyl alcohol giving [a]go+ 182.8’. The compound is isomeric with the already known benzofnpinacone (tetraphenylerythritol, m. p. 235O), C,M5-CH(OH)*C(OH)(C,H,)*C(OH)((?,H,)*CH(OH)*C,H,,obtained by Kauff maim (Chem. Centr., 1898, I, 1232) by the electrolytic reduction of beuzil or benzoh, and which is, of course, inactive. The authors, who are promeding with the investigation, are making this preliminary communication in consequence of the incidental description by Acree (Ber., 1904, 37, 2753) of the action of magnesium phenyl bromide on inactive methyl mandelate with production of triphenylglycol.208. “Note on the addition of hydrogen cyanide to unsaturated compounds.” By Arthur Lapworth. Knoevenagel has recentiy stated (Bet-., 1904, 87, 4065) that mesityl oxide unites cearly quantitatively with pure hydrogen cyanide, and in proof he cites the yield of mesitylic acid obtained by adding potassium hydroxide to the mixture after eight days and then boiling. As potassium cyanide, in presence of potassium hydroxide, rapidly converts mesityl oxide into mesitylic acid, Knoevenagel’s experi- ment throws no light on the subject. Experiments at looo with hydrogen cyanide dissolved in alcohol are apt to be misleading, as after some hours at this temperature the solution is often faiatly alkaline, and is much more reactive than before heating.The author has never obtained an appreciable amount of additive product when hydrocyanic acid free from all trace of basic 246 impurity was warmed with an up-unsaturated ketone ;nevertheless, the views which he has put forward as to the mechanism of such pro- cesses are altogether opposed to the assumption that pure hydrogen cyanide is devoid of additive properties in any instance where addition occurs in presence of a base or a metallic cyanide (compare Knoe-venagel, Zoc. cit., p. 4067). Alkylidenecyanoncetic acids react very readily with hydrogen cyanide in presence of bases or metallic cyanides; the products vary with the precise conditions imposed, but with care it is easy to obtain nearly quantitative yields of compounds derived from the type CHX(CN)*CH(CN)*CO,H, and from which alky lsucci nic acids are produced by acid hydrolysis.For example, phenylsuccinic acid may rapidly be synthesised from benzaldehyde, potassium chloroacetate, and potassium cyanide. The study of this reaction as applied to both fatty and aromatic aldehydes is in progress. Alkylidenemalonic acids do not appear to be capable of uniting with hydrogen cyanide, WISLICENUS MEMORIAL LECTURE. The Wislicenus Memorial Lecture will be delivered by Professor W. H. Perkin, F.R.S., on Wednesday, January 25th, at 8.30 p.m. At the next Ordinary Meeting, on Wednesday, December 14th, at 5.30 p.m., the following papers will be communicated :-Hydrolysis of arnmonium salts.” Ry V. H. Veley. “The viscosity of liquid mixtures. Part 11.’’ Ey A. E. Dunstan. ‘‘The diazo-reaction in the diphenyl series. Part 11. Ethoxy-benzidine.” By J. C. Cain. 6‘ The sulphate and the phosphate of the dimercurainmonium series.” By P. C. R8y. “A method for t,he direct production of certain aminoaxo-com-pounds.” By R. Meldola and L. Eynon. R. CLAY ANY SONS, LTD., BREAD ST. HILL, E.C., AND BUNOAY, SUFFOLK

ISSN:0369-8718    

DOI:10.1039/PL9042000239

出版商:RSC    

年代:1904

数据来源: RSC