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Proceedings of the Chemical Society, Vol. 19, No. 273 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 273,
1903,
Page 279-294
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摘要:
/ssuecl 3 1/12/03 PROCEEDINGS OF IHE CHEMICAL SOCIETY. VOl. 19. No. 273. Wednesday, December 16th, 1903. Professor W. A. TILDEN,D.Sc., F.R.S.,President, in the Chair. Messra. E. F. Armstrong, H. J. W. Bliss, E. R. Hughes, B. Ingram, arid C. Miiller were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Alick Cole Benson, 33, Perham Road, West Kensington. Robert Gawler, M.Sc., 3, South View !Verrace, Leeds. Leo Frank Guttmann, Ph.D., 18, Aberdare Gardens, N.W. Cyril Douglas McCourt, 52, Victoria, Road, Clapham, S.W, Benjamin L. Murray, 19, University Place, New York. Thomas Stewart Patterson, Ph.D., Lyddon Hall, Leeds. Alfred Shrubsole, 9 1, Holyhead Road, Coventry. Samuel John Smith, 41, Grafton Street, Dublin.Alfred Tingle, Ph.D., B.Sc., Shantung, China. Of the following papers, those marked * mere read : “165. “The relative strengths of the alkaline hydroxides and of ammonia as measured by their action on cotarnine.” By J. J. Dobbie, A. Lauder, and C. K. Tinkler. The authors have shown (Trans., 1903, 83,598) that in aqueous solution, cotarnine has the “ammonium hydroxide ” form, whereas in ethereal or chloroform solution it exists as a ‘‘ carbinol.” 280 These two forms are distinguished by having widely different and very characteristic absorption spectra (Zoc. cit., Plate I,carbinol form ; Plate 11, ammonium hydroxide form). When cotarnine in aqueous solution is acted on by sodium hydr- oxide or any other soluble base, it is converted into the carbinol form.The proportion of the cotarnine which undergoes this change depends on the amount of sodium hydroxide present, the change being practically complete when a milligram-molecule of cotarnine is dissolved in one litre of normal sodium hydroxide solution. After the addition of any given quantity of sodium hydroxide, a state of equilibrium is estab- lished almost instantaneously, and no further change takes place in moderately dilute solutions, even after several hours, provided that the temperature is kept constant. Each additiohal quantity of sodium hydroxide causes a further transformation of ‘‘ ammonium hydroxide ” into “curbinol ”form. This change can be followed through all its phases by photographing the spectra of the solution after each addition of sodium hydroxide, the spectra obtained being in reality those of mixtures of the two modifications (Zoc.cit., Plate 111, Figs. 17-24), the relative amounts of which can be determined by comparing these photographs with a standard series obtained by photographing the spectra of solutions prepared by mixing the two forms of cotarnine in definite proportions. It is possible, therefore, to estimate the amount of change which any given quantity of sodium hydroxide produces in an aqueous solution of cotarnine, and to obtain a curve representing the effect of successive additions of the alkali. The action of ammonia and of the hydroxides of lithium, sodium, potassium, barium, and calcium has been examined in this way.The curves for the first three hydroxides are nearly identical, from which it is inferred that, so far as their action on cotarnine is con-cerned, they have practically the same strength; those of the last two agree with one another but differ slightly from the others, indicating a slight inferiority of strength, especially for the more concentrated solutions. The curve for ammonia, which differs widely from those of the alkaline hydroxides, indicates that this base is much weaker than the latter substances. DISCUSSION. Mr. W. C. REYNOLDSexpressed the hope that Prof. Dobhie would be able to investigate, in this connection, the parent bases, hydrastine and narcotine, from which hydrastinine and cotarnine are derived by oxida- tion.In the case of hydrastine, he had noticed the existence of two modifications, one variety melting at about 131-132’ and the other at 281 a temperature somewhat above 140”. If either variety was dissolved in alcohol or acetone and the solvent removed at the temperature of the water-batb, the lesJ fusible variety was obtained ; but if the solution was allowed to evaporate spontaneously, or if a concentrated hot solution was cooled and then allowed to crystallise, the more fusible variety was obtained. The less fusible variety was always produced by the fractional precipitation by ammonia of the hydrastine salts. Moreover, if the temperature when in the neighbourhood of the melting point was raised very slowly (about lo per half hour), the crystals appeared to change from the more fusible to the lees fusible modification.The crystals which melted at 131-132”, when heated in the ordinary manner, did not soften until the temperature was considerably above 140°, and then melted somewhat indefinitely. Under similar conditions, both varieties seemed to have the same specific rotation in solution. Similar changes were not observed in the case of the allied a1 kaloid, narcot ine. “166. Peroxglaminesulphonates and hydroxylaminetrisulphonatesL( (sulphazilates and metasulphazilates).” By T. Haga. By oxidising potassium hydroxylaminedisulphonate,Fremy obtained the salts which he called sulphazilate and metasulphazilate. Claus re-named the former ‘‘ oxysulphazotate,” and formulated its constitu-0 tion as (SO,K),N/-)N(SO,K) ;the latter be called ‘‘trioxyazoate,” OV giving it the formula O:N(S03K),,H20.Raschig changed these whilst Hantzsch and Semple have re-named the sulphazilate ‘(nitroxy-disulphonate I’ with the formula, O*N:(S03E)2, and have gone back to Claus’s formula for the metasulphazilate. The author has found that (1) potassium sulphazilate interacts with normal potassium sulphite, (SO,K),NO*OX(SO,K), +E*SO,K = (SO,K),NOK + (SO,K)ON(SO,K),, to form normal potassium hydroxyl- aminedisulphonate and potassium metasulphazilate ;(2) the sulphazilate decomposes spontaneously into the metasulphazilate, hydroxylamine- disulphonate, and much nitrous acid, the last being preserved as nitrite when potassium hydroxide is present : 2(S0,K),N20, +H20= B(SO,K),NO +(SO,K),NOH +NO,H ; (3) potassium metasulphazilate 282 is decomposed quantitatively into sulphate and normal aminedisul- phonate (iminosulphate) by sodium amalgam or by the zinc-copper couple, KO*SO,*O*N(SO,K),+ 2Na =KO*SO,*ONa+ TJaN(SO,K),; and (4)the ultimate products of its hydrolysis, when heated with hydro- chloric acid, are hydroxylamine and sulphuric acid.The molecular magnitude of sodium hydroxylaminetrisulphonate and also of the 2/3-normal sodium hyciroxylaminedisulphonate,as deter- mined by Loewenherz’s method, is in each case that which contains only one atom of nitrogen. The constitution of the sulphazilates is therefore that expressed by the name, potassium peroxylaminesul- phonate, and the formula, (S03K)2NO*ON(S0,K)2,and of the meta- sul phazilates that expressed by the name and formula, potassium hydroxylaminetrisulphonate, (S03K),N*O*(S0,K).The sulphazilates are oxime peroxides or peroximes, being produced by oxidising hydroxylaminedisulphonates with a variety of reagents (including ozone), even in the cold ; they behave as oxidising agents, becoming again reduced to hydroxylaminedisulphonates, 2(S03K),NOH [(SO,K),NO],. A metasulphazilate is the only known case of a triacylated hydroxylamine. Having, as a hydroxylaminetrisulphonate, one of its sulphonate radicles in union with oxygen, it is clearly one-third sulphatic, yet without being actually a sulphate.It is a mixed oxide or anhydride of two acid salts, one being the acid sulphate and the other the 2/3 normal hydroxylaminedisulphonate, (SO,K)O iH--+.-H$;N(SO,K),, ..__._...__._...... The inorganic mixed anhydride most closely analogous to a hydroxyl-aminetrisulphonate is Pelouze’s salt, potassium hyponitrososulphate, (SO,K)*O*(N,OK),the two salts agreeing in being stable in presence of caustic alkali and in not yielding barium sulphate with a soluble barium salt, whilst giving rise to a sulphate with sodium amalgam or zinc. To understand this behaviour, it is only necessary to assume that the rnetasulphazilate ionises into three metallic kstions and a complex trivalent anion which includes within itself the sulphate radicle. Dunstan and Goulding have shown that zinc and acid reduce trialkylhydroxylamines to trialkylamines, so that if, as has hitherto been supposed, metasulphazilates were oxamines, they should reduce to aminetrisulphonates (nitrilosulphates) and not to aminedisulphonates and sulphates.The author concludes that the nitrogen of the sulph- azilates and metasulphazilates is exclusively tri-and not quinque-valent, as suggested by the earlier investigators oE these salts. There is so much difference between the properties of a peroxyl-xminesulphonate and those of the bl uish-violet substance produced by the action of sulphur dioxide on a solution of nitrososulphuric acid in 253 sulphuric acid that it is improbable that Sabatier’s suggestion will prove correct as to the latter compound being the acid of Fremy’s bluish-violet salt.Potassium hydroxylaminetrisulphonate is shown to have 3/2 mola. of water of crystallisation, whereas Claus, who stated that the salt contained one mol. of water, was perhaps unaware that some of its water of crystallisation becomes fixed by hydrolysis during the drying. Sodium, ammonium, and hydroxy-lead hydroxylaminetrisulphonates have been prepared for the first time. “167. ‘6 Peroxglaminesulphonic acid.” By E.Divers. In support of Sabatier’s assumption that the bluish-violet colour caused by the action of sulphur dioxide on sulphuric acid containing nitrososulphuric acid is due to the formation of the unknown acid of Fremy’s bluish-violet potassium salt (sulphazilate or peroxylamine- sulphonate), it is pointed out that the difference in properties observed by Haga (preceding note) is hardly greater than that between the behaviour of nitrous acid in the respective forms of nitrososulphuric acid and potassium nitrite.Sabatier’s observations are shown to be quite consistent with the view that the acid is peroxylaminesulphonic acid, that is, a peroxide and a compound of trivalent nitrogen. “168. (6 Constitution of nitric peroxide.’’ By E. Divers. Haga’s examination of Fremy’s sulplrmxilate has established that it is peroxylcminesulphonate, a trivalent nitrogen compound and a perox-ide. It is a sulphonated nitric peroxide, as suggested by Hantzsch and Semple, and when decomposed by water, gives a complex anhydro- sulphate (hydroxylaminetrisulphonate),on the one hand, and, on the other, nitrous acid and sulphonated nitrous acid (hydroxylamine-disulphonate), equivalent respectively to the nitric and nitrow acids which are yielded by nitric peroxide.Dinitric peroxide is therefore a true peroxide, lzitrosyl peroxide, (NO),O,. Mononitric peroxide must therefore be regarded as O:N*O, formu-lated with a univalent oxygen atom, and not with its nitrogen atom in the quadrivalent condition, O:N:O, as suggested by Piloty and Schwerin (Bey.,1901, 34,1884 and 2354). For it seems appropriate to consider the constitution of the two forms of nitric peroxide to be the same, the only difference being the presence in the one form of the bivalent double atom of oxygen, and in the other form of a single univalent oxygen atom.A true peroxide is correctly defined as a compound in which some or all of the oxygen is exerting on the rest of the corn- pound only half its usual valency. Piloty and Schwerin's porphy-rexide, (C,H,N,):NO (Zoc. cit.), is to be regarded as being such a peroxide. 169. ''Halogen derivatives of diphenyl and dihgdroxgdiphenyl." By J. C. Cain. The author has already shown that only a small amount of 3 :3'-di-chloro-4:4'-dihydroxydiphenyl is obtained by boiling the correspond- ing diazonium salt with water (Trans., 1903, 83, 688), and now describes a method for preparing the substance by chlorinating 4 :4'-dihydroxydiphenyl. The following compounds are described : 3 :3'-dicl~Zol.odiphe~lyl, white needles, m.p. 29O, b. p. 298O ; 3 :4 :3' :4'-tetruc~~Zorodip~~nyI, white needlep, m. p. 172O, b. p. 230' under 50 mm. pressure ; 4 :4'-di-bromo-3 : 3'-dichZorodiphenyI, white needles, m. p. 176-li7' ;4 : 4'-di-iodo-3 :S'-dichZorodiprllenyl, pale yellow needle.., m. p. 162', b. p. 275' under 10 mm. pressure ; 4 : 4'dicyano-3 : 3'-dicfLZorodiphenyl, white needles, ni. p. 152-153' ;3 :3'-dichZorodipJienyZ-4: 4-dicarboxyZic acid, white needles, m. p. 287-288". 3-ch!oi*o-4:4'-dihyds.ox~dip?~nyZ, white needles, m. p. 2 15'. 3 :3' :5(?)-TricMoro-4:4'-dihydroxydi-phenyl, white needles, m. p. 179'. 170. ('Notes on some natural colouring matters." ByA. G.Perkin and E. Phipps. The flowers of the Prunus spinosa contain both quercetin ancl kampherol, whereas in the violet (uioka odowta) and white clover (trijbZium repens) quercetin alone has been detected.From the Japanese dyestuff "Fukugi " (botanical origin unknown), a new colour- ing matter, C17H120G,has been isolated, forming yellow, prismatic needles (m. p. 288-290c), the general properties of which indicate that it is closely allied to luteolin. On bromination, it yields the compound CI7Hl0O6Br2(yellow needles, m. p. 280°), and, when fused with caustic alkali, phloroglucinol and protocatechuic acid are obtained. Morintetraethyl ether, C,,H,O,(OEt), (yellow, prismatic needles, m. p. 126-1 28'), closely resembles the corresponding methyl deriv- ative and forms the colourless acetyl compound, C,,H,O,(OEt),*C,H,O (needles, m. p.121-123'). When brominated in the presence of alcohol, myricetin yields a mixture of tetrabromomyricetin and tetra-bromomyricetin ethyl ether, C1,H,Br,O7*OEt (colourless needles melting completely at 146'). Cryoscopic determinations of the molecular weight of its acetyl derivative icdicate that hesperitin has the formula CI6HI4OG,and not 285 C32H28012,as previously suspected by the formation of the alkali salts, C,2H,70,2K and C,,H,,012Na (Trans., 1898, 31, 103I). BenxoyL curcumin (yellow needles, m. p. 176-178O) in a similar manner gave results in harmony with Ciamician and Silber’s formula, C,1H200,, (Ber., 1897, 30, 192) for curcumin. 171. (‘The estimation of methyl alcohol in presence of ethyl alcohol.” By T.E. Thorpe and J. Holmes. The authors described a method of estimating the amount of methyl alcohol in mixtures of methyl and ethyl alcohols base3 on the different modes of action of a mixture of potassium dichromate and sulphuric acid on the two alcohols. The method differs from that already described by Dupr6,in 1876, in which the amount of acetic acid formed is taken as a measure of the amount of ethyl alcohol present, in that the amount of carbon dioxide evolved is weighed. The authors described how their method is applicable to the case of the methylated spirit of commerce, and to the detection and determina- tion of metbylated spirit in tinctures and medicinal preparations suspected to contain it. 172. Separation and estimation of silver cyanide and silver chloride.” By R.H. A. Plimmer. Freshly precipitated silver cyanide, although insoluble in cold dilute nitric acid, readily dissolves in the boiling acid, evolving the theoretical quantity of hydrogen cyanide, so that the gas, when passed into silver nitrate solution, produces an amount of silver cyanide equal in weight to the sample originally employed. In this way, silver cyanide may be quantitatively separated from silver chloride. When the cyanide has been dried at looo, the hard lumps produced offer a greater resistance to the solvent, and if the boiling is prolonged the acid, ou becoming more concentrated, oxidises a small proportion of the hydrogen cyanide. 173. (6 Estimation of hydroxyl radicies.” By H.Hibbert and J. J. Sudborough. In attempting to determine hydroxyl groups by Tschugaeff’s method (Ber., 1902, 35,3912), the authors have not succeeded in obtaining satisfactory results, owing to the following causes : (1) moisture gradually penetrates through the india-rubber, even although this is coated with collodion. (2) The vapour pressure of ether varies so enormously with slight alterations of tempsrature. (3) Grignard’s magnesium methyl iodide solution slowly absorbs atmospheric oxygen. 286 The following method is free from the foregoing objections; dry amyl ether is used as the medium instead of ordinary ether, and the operation is carried out in an ordinary bottle provided with a double bored india-rubber stopper, so that the bottle may be attached to (1) a Lunge’s nitrometer filled with dry mercury, (2) a glass tube pro-vided with a stopcock, so that the air in the apparatus may be replaced by dry nitrogen. The amyl ether solution of the hydroxyl compound is placed in the bottle and a solution of Grignard’c; magnesium methyl iodide in the same solvent is introduced in a small tube; when a constant temperature has been attained, the two solutions are mixed.Satisfactory results have been obtained with a-and P-naphthols, resorcinol, o-nitrophenol, acetoxime, deoxybeozoin and chloral hydrate. Quinol gives somewhat low results, probably owing to the fact that it is only sparingly soluble in amyl ether. 6i174. Diortho-substituted benzoic acids.Part V. Formation of salts from diortho-substituted benzoic acids and organic bases.” BY J. J. Sudborough and W. Roberts. Since the publication of Part IV (I’rccns., 1899, 75, SSO), E. Fischer has shown (Bey., 1900, 33,345, 1967) that diortho-substituted tertiary bases of the type of dimethylmesidine are incapable of form-ing quaternary ammonium salts. The authors have prepared several mono-and diortho-substituted tertiary amines, and find that these are capable of combining with strong diortho-substituted benzoic acids, for example, s-trinitrobenzoic and 2 : 4: 6-tribromo-3-aminobenzoic acids, but will not unite with feeble acids like 2 : 4 :6-trimethylbenzoic and o-toluic acids. In addition to the ordinary normal salts (1 mol. acid + 1 mol.base), acid salts of the type (2 mols. acid + lmol. ba5e) derived from monobasic acids and monoacidic bases have been obtained. Many of these salts can be analysed by direct titration in alcoholic solution with standard barium hydroxide solution, using phenolphthalein a.s the indicator. 175. cis-7r-Camphanates of d-and I-hydrindamines.” By‘I F. S. Kipping. cis-?r-Camphanic acid gives with dl-hydrindamine two isomeric salts melting at 173’ and 193O respectively, but which have the same specific rotation in aqueous solution (Trans., 1900, ’7’7, 903). Having recently succeeded in resolving the dl-base (Trans., 1903, 83,873), the author examined the cis-r-camphanates of the d-and of the I-base, partly to prove that the compounds previously described are really partially racemic, and partly to ascertain whether each of the optically active bases gives isomeric salts.d-Hydrindamine cis-r-camphanate, obtained by cornbining the acid with the base from pure d-hydrindamino d-bromocamphorsulphonate, crystallises from water and alcohol in long needles and melts at about 181' ;when fractionally crystallised from aqueous alcohol, the final mother liquors yield fractions which melt very indefinitely at 170-175O; the specific rotation of various fractions of this salt, examined in 2 per cent, methyl alcoholic solution, varied from [a], -7.8' to -17.8'. I-Hydrindamine cis-lr-camphanate, prepared from the base contained in pure I-hydrindamine d-bromocamphorsulphonate, closely resembles the salt of the d-base, but the original preparation melts indefinitely at 186-191O ; when crystallised fractionally from aqueous alcohol, it yields portions melting as low as 180-184O.The specific rotation of fractions of this salt, determined in 2 per cent, methyl alcoholic solu- tions, varied from [a],,-6O to + 7". These observations seem to justify the conclusion that each base gives two isomeric salts, which, when the dl-base is used, combine in pairs to form the two partially racemic compounds previously described. The whole of the cis-?r-camphanic acid used in these and in previous experiments was collected and crystallised fractionally from alcohol ; the first and last fractions crystallised in identical forms, namely, characteristic hexagonal plates (Tram., 1S96, 69, 943), melted simul- taneously, and had the same specific rotation in alcoholic solution.176. Resolution of dl-methylhydrindamine." ByG. Tattersall. In resolving dl-methylhydrindsmine into its enantiomorphously related components by the use of d-bromocamphorsulphonic acid (7;-ans., 1903, 83, 91d), the yield of salts of the d-and I-bases was always small, and the author, at Dr. Kipping's suggestion, attempted to find a more satisfactory process for the resolution of this dl-base. Experiments then showed that d-tartaric acid, used so as to form the hydrogen tartrates of the base, effected an excellent separation of the d-and I-bases by crystallising the salt at the ordinary tempera- ture.The most sparingly soluble fractions contained the hydrogen tartrate of the d-base. The purification of the bases was effected by converting the first fractions, containing chiefly the d-base (about one- third of the whole), and the last fractions separately into the d-bromo- camphorsulphonates, and finally fractionating from water. d-Methplhydrindarnine hydrogen tartrate, C10H13N,C4HG06,2H,O, crystdlises from water in long, glassy prisms; it melts at 153-155O 288 with slight decomposition. In aqueous solution, it has a specific rotation [ u]. + 33' and molecular rotation [MI,, + 99'. I-,Wethy Zhydhdarnine hydrogen tartrate C,,H ,,N, C4H606,crystal-lises from water in aggregates of small, glassy prisms; it melts at 197' with slight decomposition.In aqueous solution, its speci6c rotation is [a],-5' and its molecular rotation [MI, -14.8". 177. u Isomeric salts of d-and Z-methylhydrindamines with d-chloro- camphorsulphonic acid." By G. Tattersall. In a recent communication (Tattersall and Kipping, Trans.,1903, 433, 918), the formation of isomeric salts by the combination of d-and I-methylhydrindamines with d-bromocamphorsulphonic acid has been described, and similar experiments have now been made with the same bases and d-chlorocamphorsulphonic acid. The salt of each base was made from carefully purified material and subjected to prolonged fractional crystallisation ;the end fractions were then examined. In the cases of both the d-and Z-bases, the melting points of the successive fractions gradually fell from the first to the last fractions, this behaviour being also observed with the d-bromocamp horsulp honate.The chlorocamphorsulphonates differ, however, from the bromo- camphorsulphonates in their optical behaviour. With the former acid, the specific rotations of the last fractions are higher than those of the first fractions, whereas with the latter acid the opposite was the case. The statement is true for both aqueous and chloroform solutions. The results obtained are summarised in the following table : l-Metl~y d-chloroccimphorsulphoizate.Z~~ydrirtdammine [ alD* x-\ in. p. In chloroform. In water. First fraction 239' + 3.3' + 34.2' Last ,, 231-233' 8.0 35% d-Methylhydrindmnilze d-c~lorocan~pho"Sul~)honate.I: a ID. < 7 m. p. In chloroform. In water. First fraction 24'7' +56' + 60' Last ,, 225-230' 63 63 Both salts crystallise in auhydrous needles. Similar results were obtained with hjdrindamine d-chlorocamphor- sulphonates (Kipping, Trans.,1903, 83,902), but in this case it was found impossible to isolate the isomeride of higher specific rotation. 289 178. The four optically isomeric I-menthylamines and their salts.” By F. Tutin and F. S. Kipping. THE principal object of this research was to ascertain whether I-menthylamine would give, with d-bromocamphorsulphonic acid, isomeric salts analogous to those obtained by combining this acid with the optically active hydrindamines (TTccnS., 1903, 83, S73) and methylhydrindamines (Zoc.cit., p. 918); for this purpose, it was first necessary to obtain the E-menthylamine free from optical isomerides. An examination of the menthylamine prepared by reducing the oxime of “Z-menthone ” showed that the crude basic product was a mixture of four optically isomeric active bases, land that the menthylamine obtained by heating ‘6 I-menthone ” with ammonium formate was like- wise composed of these four isomerides. The explanation of these facts is afforded by a consideration of the optical configuration of I-menthone-a ketone which readily undergoes partial racemisation-and also of the reactions by means of which it is tranFformed into the base. Since the four isomerides in question are derivatives of I-menthoue (--) and of iso-E-menthone (+ -), they are distinguished as Z-menthylamine, neo-Z-menthylamine, iso-Z-menthylamine (d-menthyl- amine in the literature), and isoneo-Z-menthy lamine respectively.Z-Menthylamine combines with J-bromocamphorsulphonic acid giving a mixture of isomeric salts. One of these compounds can be obtained in a pure condition by repeated fractional crystallisation from water ;it melts at about 226’ and has a specific rotation [a],+43.7’ in aqueous, and [aID+48.7’ in chloroform solution. The isomeric salt cannot be obtained in R pure condition, but its presence is con-clusively proved by the fact that the more readily soluble fractions melt at about 221O and have a specific rotation [a]. + 38.8’ in aqueous, and [a],+42.8’ in chloroform solution.For the separation of the four isomeric E-menthylamines in the crude base, their hydrochlorides, d-bromocamphorsulphonates, and d-camphorsulphonates were fractionally crystallised, and also their formyl derivatives ;E-menthylamine is thus isolated without difficulty, but for the separation of the other three isomerides, fractional crystallisation of their benzoyl derivatives was found to give the best results. The following compounds are described :- 200 I-Base. neo.2-Base. iso-&Base. isoneo-'-Base. in. p. [a],. m. 1'. [aIn. In. p. [a]=. In. p. [u]~. d-Bromocamphorsulphonate. 226' i43.2" iO-i5" 1 -166" +65" --d-Camphorsulphonate......... 158 -5'3 188 +11*8" 177 +21'7 --Renzoyl derivative ........... 166 -61.9 125 -17'4 121 +2!2'7 101" -3.8" The specific rotations of the salts mere determined in aqueous solutions, those of the benzoyl derivatives in chloroform. 179. '' Preparation of the tetra-alkyl derivatives of stannimethane." By W.J. Pope and S. J. Peachey. The preparation of the mixed tetra-alkylstannimethanesby the action of a zinc alkyl upon a trialkylstannimethyl iodide is difficult to carry out owing to the occurrence of secondary reactions, which greatly diminish the yield of the desired product. The authors have found that the magnesium alkyl iodides, bromides, and chlorides prepared by the method given by Grignard react vigorously with stannic chloride or with the mono-, di-, and tri-alkylstannimethane halogen derivatives, giving rise to the corresponding tetra-alkyl- stannimethanes. After treating the product with water, the tetra- alkyl derivative is readily separated in a state of purity by fractional distillation of the ethereal solution.Tetraethylstannimethane, SnEt,, is prepared by adding stannic chloride (1 mol.), dissolved in light petroleum, to the ethereal solu-tion of magnesium ethyl bromide (4.5 mols.), washing with dilute acetic acid and distilling the ethereal solution ;it boils at 180-181' under '758 mm. pressure. Dimethyldiethylstannimethane, SnMe,Et,, may be prepared either by the action of magnesium methyl iodide on diethylstannimethylene chloride, bromide, or iodide, or by that of magnesium ethyl bromide on dimethylstannimethylene chloride, bromide, or iodide in ethereal solution.After treating with water and distilling the ethereal solu- tion, the substance is obtained as a colourless liquid identical with that prepared by Frankland's method. Trimethylethylstannimethane, SnMe,Et, is obtained by treating trimethylstannimethyl bromide or iodide with the calculated quantity of magnesium ethyl bromide in ethereal solution, washing with dilute acetic acid, and fractionally distilling the ethereal solution ;it boils at 107-108 under 768 mm. pressure. Trimethylpropylstannimethane,SnMesPla, is similarly prepared by the action of magnesium propyl bromide or iodide on trimethylstanni-methyl bromide and forms a colourless liquid boiling at 129' under 764 mm.pressure. Triethylpropylstannimethane, SnEt,Pra, from triethylstannimethyl bromide, boils at 195' under 764 mm. pressure. Dimethylet h ylpropy 1s tan nime thane, SnMe2EtPra, prepared by the action of propyl rriagnesium bromide or iodide on dimethylethylstanni- methyl bromide, boils at 153' under 762 mm. pressure. Methylethyldipropylstannimethane, SnMeEtPra2, obtained from methylethylstannimethylene iodide and magnesium propyl bromide, is a colourless liquid boiling at 183-184' under 758 mm. pressure. Tetraphenylstannimethane, SnPh,, is conveniently prepared by the action of stannic chloride on mixgnesium phenyl bromide. The further study of the mixed alkylstannimethanes, prepared by aid of the above reaction, is being continued, together with the examination of the action of the magnesium alkyl salts on silicon tetrachloride.180.'I Optically active esters of p-ketonic and ,&aldehydic acids. Part IV. Condensation of aldehydes with menthyl acetoacetate." By A. C. 0. Hann and A. Lapworth. Menthyl acetoacetate condenses readily with aldehydes in presence OF bases, and the following products have been obtained. Dimenthyl ethyliclenebisacetoacetcde, CHM~(C:HAC*CO~*C~~H~~)~,pro-duced when acetaldehyde is used, forms fine needles melting at 194-196' and has [a]),-24.9' in benzene, a very slight mutarotation being noticed. Menthyl n-propylideneacetoacetate,CHEt: CAc*CO,*CloHlg, is formed at the ordinary temperature, crystallises in glistening, elongated plates or needles, melts at 84-38', and has [a]D-34'9'. It condenses with menthyl acetoacetate to form dimenthpl n-propylidenebisacetoacetate, CHEt(CHAc*C02*CloHlg),, which melts at 801-207' and has [a], -26.9'.Binzenthyl n-but~liclenebisacetonce€ute,CHPr~(CHAc*CO2*Cl0H,,),, melts at about 184' and has [a].-16.8'. Dirnenthyl isobutylidene- bisucetoacetate, CHPr~(CHhc*C02~CloHlg), melts at 193-202' ; in benzene solution, it has [~]),-42*6', changing slowly to [aID -46.0'. Xenthyl benxylideneacetoacetate, CHPh: CAc*CO,*CloHI,, crystallises in well-formed, glistening plates melting at 133-1 34' ;in benzene solution, Q]~-10.0. With menthyl acetoacetate, it yields ntenthpl benxylidene bisncetocccetate , CHPh(CHAc*CO, ClOHI9),, which melts at 203-206' and has [aIL,-30-4O.292 The formula usually ascribed to the monoalkylidene derivatives of P-ketonic esters does not readily account for the abnormally low values of their rotatory powers. The statement that tertiary bases are not effective in bringing about the condensation of aldehydes with P-ketonic esters is incorrect ; the very feeble tertiary bases, pyridine, quinoline, or dimethylaniline are useless, but trimethylamine and tripropylamine may be employed, although these are not so rapid in their action as the still more powerful secondary bases, such as diethylamine or piperidine. 181. ''Estimation of the adulterant in citronella oil." By M.K.Bamber. A mixture of 2 C.C. of pure cocoanut oil free from acid and 2 C.C. of the citronella oil under examination is shaken for one minute with 20 C.G.of 83 per cent. alcohol (sp. gr. 0.8273 at 30') in the graduated tube (see Figure), this vessel being then rotated in a centrifugal machine for 0.5 to 1.0 minute. The volume of cocoanut oil, which now contains the impurity originally present in the citronella oil, is ascertained, and this reading minus 2 C.C. represents the adulterant. For example, 2.45 C.C. of residual oil represent 0.45 C.C. of impurity in the 2 C.C. of citronella oil or an adulteration of 22.5 per cent,. A staudard oil should be tested occasionally against the unknown samples in order to eliminate errors arising from the use of alcohol of different strengths. In this way, the adulterant is separated and estimated in 3 or 4 minutes, the test being conducted at 29-30'.293 ADDITIONS TO THE LIBRARY. 11. By Purchase. Kohut, Adolph. JuFtus von Liebig. Sein Leben und Wirken. pp. 394. ill. Giessen 1904. Posner, Theodor. Lghrbuch der synthetiscben Methoden der organ- ischen Chemie. pp. xxxii +436. Leipzig 1903. Schucht, Ludwig. Die Fabrikation des Superphosphat s mit Beriick- sichtigung der anderen gebrauchlichen Diingemittel. Handbuch fur den Diingerchemiker im Betriebe und im Laborntorium. 2 Aufl. pp. 336. ill. Braunschweig 1903. Weber, Carl Otto. The chemistry of india-rubber, inzluding the theory of vulcanisation. pp. xii + 314. ill. London 1902. 111. Pamphlets. Cross, C. F., Bevan, E. J., Beadle, Clayton, and Sindall, R.W.C.B.S. Units and standard paper tests. An essay towards establishing a normal system of paper testing. pp. 25. London 1903. Golding, John. A domesticated microbe. (From the PYOC. Notting-hum Nuturalist’s Societ?y, 1903.) London Essence Co. Half yearly report. Nos. 1 and 2. London 1903. Rideal, Samuel, and Walker, T. Ainslie. Standardisation of dis-infectants. (From the Journal of the Smtitai-y Institute, 24,3.) Schaer, Ed. Ueber die Verwendung des Chloralhydrates bei Drogen-und Nahrungsmittel-priif ungen toxikologisc h-chemischen Uritersuchungen und technischen Expertisen. (From the Berichte der Deutschen, Pharmaceutischern Gesellschaft, 1903, Hft. 6.) Wells, Henry M. Cylinder oil and cylinder lubrication, Part I. (From the Engineer, July 17 and 31, August 7 and 14, 1903.) 294 At the next meeting, January 20th, 1904, at 5.30 pm., the following papers will be communicated :-“The chemical reactions of nickel carbonyl.Part I.” By J. Dewar and H. 0. Jones. 6‘ The chemical reactions of nickel carbonyl. Part IT. Reaction with aromatic hydrocarbons in presence of aluminium chloride. Synthesis of aldehydes and anthracene derivatives.” By J. Demar and H. 0. Jones. ‘4 Optically active asymmetric nitrogen compounds, d-and Z-phenyl- methylethylamine salts.” By H. 0. Jones. _. -R. CLAY AhD SONS, LTD., BREAD 5T. HILL, E.C., ASD CS;hQAY, BUFFVLY.
ISSN:0369-8718
DOI:10.1039/PL9031900279
出版商:RSC
年代:1903
数据来源: RSC
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