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Proceedings of the Chemical Society, Vol. 21, No. 292 |
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Proceedings of the Chemical Society, London,
Volume 21,
Issue 292,
1905,
Page 83-98
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摘要:
Issued 27/3/05 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 21. No. 292. Wednesday, March 15th, 1905. Professor W. A. TILDEN, D.Sc., F.R.S., President, in the Chair. Messrs. A. G. Levy, F. L. Pyman, G. W. Monier-Williams, and W. H. Woodcock were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Frank Standish Findon, M.A., B.Sc., 41, Great Percy Street;, Holford Square, W.C. Edwin Morris, 12, Dragon View, Harrogate. Frank ghedden, B.Sc., 5, Belvedere Road, Walsall. George Devenish Thomas, B.Sc., 8, Hubert Terrace, Dover. The PRESIDENTannounced that Professor Percy Frankland had pre-sented to the Society the eudiometer made and used by the late Sir Edward Frankland for the analysis of ethyl in 1849 ;that Pro- fessor Retzius, of Stockholm, had presented an engraving of Berzelius ; and that Mr.Oscar Guttmann had presented a bronze medal struck in honour of Roger Bacon in Paris in 1818. The Council, on behalf of the Society, had expressed their thanks for these gifts. Of the following papers, those marked * were read : “36. “The velocity of olrime formation in certain ketones.” By Alfred Walter Stewart. With the object of gaining confirmation of the results already obtained in the case of the addition of sodium hydrogen sulphite to various ketones (this vol., p. 13), the author has investigated the rates of formation of the corresponding series of oximes. Solutions of the ketones were allowed to interact with a hydroxylamine sulphate solution for a fixed time, and the amount of free hydroxylamine was then estimated by warming with iodine solution and sodium phosphate and titrating with standard thiosulphate.The principal results are shown in the following table : After 10 20 30 minutes. Percentage of oxime. Acetone.. . ... ... 45.1 A 49.7 \ 50.0 Methyl ethyl ketone ... 36.6 39.2 39.2 Methyl isopropyl ketone 31 *4 31.5 32.0 Pinacolin ... ... 12.9 17.0 24.5 The resnlts are generally in agreement with those already found for the addition of sodium hydrogen sulphite to ketonic compounds, and since chemically the two reactions belong to different types, it seems probable that the hindrance to the reactions in the case of ketones containing many methyl groups near the carbonyl is due to stereochemical and not to purely chemical causes.“37. “ The ultra-violet absorption spectra of certain enol-keto- tautomerides. Part 11.” By Edward Charles Cyril Baly and Cecil Henry Desch. In the first part of this investigation (Fmns., 1904, 85, 1029), the ultra-violet absorption spectra of acetylacetone and ethyl acetoacetate and of certain of their derivatives were described. Evidence was then brought forward in support of the view that the absorption band exhibited by these substances is due to the equilibrium existing between the two possible tautomeric forms. Neither of the two modifications when in a pure state gives an absorption band, but when the two are present together in mutual equilibrium, that is to say, when a number of molecules are changing from one form into the other, a very decided absorption band is developed.The oscilla- tion frequency of the light absorbed was further shown to be inde- pendent of the mass of the atom in the so-called labile condition. The conclusions drawn in the first paper are now shown to be fully confirmed by an investigation into the absorption spectra of benzoyl-acetone, ethyl benzoylacetate, ethyl ace tyls uccinate, ethyl diace tyl- succinate, ethyl oxaloacetate, ethyl acetonedicarboxylate, and ethyl benzoylsucciiiate, together with certain of their derivatives. These results favour the view that the absorption band is clue to the change of linking taking place when one tautomeric form passes into the other.It is possible to account for the formation of the absorption band by adopting the physical conception of the atoms as a system of electrons, and in this way the formation of the bands is placed in the same category as other spectral phenomena. Some light is thrown on the dissociation of salts in solution by these results, and it appears probable that dissolved salts are not dissociated into independent ions, but that the two parts of the molecule are merely drawn apart to a certain extent by the action of the solvent. When the two parts are sufficiently separated to allow of the inter- change of parts between adjacent molecules, then the condition known as ionisation exists. lt is possible to have degrees of dissociation without any evidence such as is required by the electrolytic dissocia- tion hypothesis; such degrees of dissociation no doubt occur in the case of organic compounds, which react apparently by means of ions, but the solutions of which present no evidences of the presence of the ions.The aliphatic tautomeric compounds in solution present also a type of dissociation without the presence of ions. The labile atom is only drawn away from the rest of the molecule sufficiently to allow an inter- change to occur between two different parts of the same molecule. The labile atom is a potential ion. Four grades of dissociation may be recognised. DISCUSSION. Sir W. RAMSAYremarked that the late Prof Fitzgerald used to contend that the positive and negative ions could not be regarded as entirely independent entities, but must have some physical connection with each other.The “ Faraday ” tube spoken of by Mr. Baly may be taken as such a connection. If it be asked how far it is possible to stretch a ‘‘ Faraday ” tube, when one atom, positively charged, may be taken as independent of a negatively charged atom with which it was originally in union, the answer is that the atoms, formerly partners, may be separated by air, glass, or any material. Thus if an experi-ment suggested by Prof. Ostmald be conceived, in which the + and-ions of a solution of potassium chloride are present in diff ereiit vessels, physicists would contend that the ‘‘Faraday ” tube joining them would exist however far the ions be removed one from the other."38. '' Esterification constants of substituted acrylic acids." By John Joseph Sudborough and David James Roberts. The esterification constants of some 22 substituted acrylic and allied acids with methyl alcohol have been determined at 15'. The following compounds were examined : crotonic, cinnamic, ccllocinnamic, P-chlorocrotonic, P-chloroisocrotonic, a-chlorocrotonic, me thy1 hydrogen fnmarate, inethyl hydrogen maleate, atropic, a-phenylcinnnmic, a-phenylallocinnamic, a-bromocinnamic, a-bromoallocinnamic, P-bromo- cinnamic, p-bromoallocinnamic, a-chlorocinnamic, a-chlorocdlocinnainic, P-chlorocinnamic, P-chloroallocinnamic, furf urylacrylic, and aUof ur- f urylacrylic, n-butyric, hydrocinnamic, and phenylpropiolic acids.The results indicate that a substituted acrylic acid is esterified much less readily than the corresponding saturated acid, and somewhat more readily than the corresponding acetglenic acid, R*CH,*CH,*CO,H > R.CH:CH*CO,H > R*CiC*CO,H. The effect of introducing substituents into acrylic acid is to lower the rate of esterification. This effect is the most marked when the substituent is in the a-position with respect to carboxyl. A com-parison of the constants for pairs of stereoisomeric acids, for example, H.IC;'*Y and Y.S*H X*C*CO,H X*C*CO,H ' shows that the acid with CO,H and Y in &-position is esterified much less readily than when these substituents are in the trams- position.A similar relationship appears to hold good for pairs of acids, Y-CH:CH*CO,.H, with the exception of cinnamic and all& cinnamic acids, which have exactly the same esterification constant. No general relationships have been established hitherto between the pairs of acids, X=$Y Y0E.XandH-C-CO,H H*C-CO,H "39. a-Chlorocinnamic acids.'' By John Joseph Sudborongh and Thomas Campbell James. The action of alkalis on cinnamic acid dichloride and its methyl ester has been studied. The product is a mixture of a-chloro- and a-chloroallo-cinnamic acids, and the relative amounts of the two vary but little with the temperature or with the alkali. Even when the acid dichloride is acted on at low temperatures, the amount of a-chloro-acid (m, p.137") is considerable, and is raised to only a very small extent by substituting the methyl ester for the acid dichloride. Cinnamic acid dichloride does not show the same tendency to eliminate carbon 87 dioxide as was observed with the dibromide, and hence the amount of chlorocinnamene is practically nil unless the reaction proceeds at a high temperature. The velocities with which a-bromo-, a-chloro-, a-bromoallo-, and a-chloroallo-cinnamic acids are acted on by aqueous potassium hydroxide have been determined. The methyl ester, chloride, amide, anilide, p-toluidide, and a-naph- thalide of the a-chloro-acid and the chloride and amide of the a-chloro- do-acid have been prepared. Phenylpropiolic acid may be prepared by heating the a-chloro-acid with 20 per cent.aqueous caustic potash (2.5 mols.) at 100' for 8 hours; the yield is about 50 per cent. of the theoretical amount, as carbon dioxide is evolved and an oil formed. "40. ''Diortho-substituted benzoic acid. Part VI. Conversion of methyl into ethyl esters." By John Joseph Sudborough and Thomas Huws Davies. Purdie has shown that methyl esters of aliphatic acids are readily transformed into the corresponding ethyl esters by means of ethyl alcohol and a small amount of sodium or sodium ethoxide. The methyl esters of substituted benzoic acids can be transformed in a similar manner provided the two ortho-positions with respect to the carb- methoxy-group are not occupied. Thus, the methyl esters of p-nitro-, m-nitro-, 3 :5-dinitro-, 3 :5-dibromo-, 3 :5-dibromo-4-amino-, and 3 :4:5-tribromo-benzoic acids have been converted into the corre-sponding ethyl esters, and the ethyl esters of m-nitro-, p-nitro-, 3 :5-dinitro-, p-bromo-, 3 :5-dibromo-4-amino-,3 :4:5-tribromo-benzoic acids have been converted into the corresponding methyl esters by means of methyl alcohol and a sniall amount of sodium methoxide.Methyl 2 :6-dibromobenzoate, methyl 2 :4:6-tribromobenzoate, methyl 2 :4:6-trinitrobenzoate, and ethyl 2 :4:6-tribromo-3-amino-benzoate could not be transformed in this way. DISCUSSION. Dr. CAINsaid that he was rather of the opinion that in the o-substi- tuted compounds described by the author a linking might occur between an oxygen and a bromine atom, the former becoming tetradic and the latter triadic, thus hindering or even altogether preventing the formation of an additive compound. 88 "11."Simple method for the estimation of acetyl groups." ByJohn Joseph Sudborough and Walter Thomas. The acetyl derivative (0.5-1.0 gram) is added to a 10 per cent. w,lution of pure benzenesulphonic acid and the mixture subjected to steam distillation until the distillate is no longer acid. With 0-acetyl derivatives, this usually takes 1-2 hours if the steam is passed though somewhat rapidly. The distilIate is then neutralised by means of standard barium hydroxide, using phenolphthalein as indicator. Satisfactory results bave been obtained with acetyl-a-naphthol, diacetylquinol, triacetylpyrogallol, hexa-acetylmannitol, and triacetylgallic acid.AT-Acetyl groups may be estimated in a similar manner, but the operation takes somewhat longer, especially in the case of mono- or di-acetyltribromoaniline, the retardation being due to the influence of the ortho-substituents. Good results have been obtained with acet- anilide, mono- and di-aceto-o-toluiciides, the corresponding p-compounds, diacetyl-$-cumidine, arid the a cetyl derivatives of a-and P-naphthyl- amines. It is essential that the benzenesulphonic acid should be pure. The purification is readily accomplished by dissolving the barium salt in hot water, blowing steam through the solution until the distillate is neutral, allowing the barium salt to crystallise, and decompocing it with the theoretical amount of sulphuric acid.Naphthalene-a- and -P-sulphonic acids may be used instead of the benzenesulphonic acid. "42. '' Gynocardin, a new cyanogenetic glucoside." By Frederick Belding Power and Frederic Herbert Lees. The cyanogenetic glucoside, gy?tocnrdin, the isolation of which from the seeds of Gynocavdia odorata (R. Br.)has previously been recorded (Power and Gornall, Proc., 1904, 20, 137), has now been further studied by the present authors. Gynocardia seeds in contact with water afforded an amount of hydrogen cyanide equivalent to 0.44 per cent. of the entire seed or 0-63 per cent. of the kernels. The yield of crystalline glucoside was about 5 per cent. of the weight of the seeds.Gynocardin separates from water in colourless, glistening, prismatic needles containing liH20,which it loses at 115'. The anhydrous substance has the formula C13H190!3N,melts at 162-163', and has [a]:" + 72.5' in aqueous solution. 89 aepta-acetl/Zyynocusg~in,Cl,H120,(C2H30)7N,forms needles melting at 118-119", and having [ aID+ 40.4' in chloroform. Gynocardin is readily hydrolysed at the ordinary temperature by gynocarduse, the enzyme isolated from the seeds, but with difficulty by boiling 5 per cent. hydrochloric or sulphuric acid, according to the equation : C,,HlgO,N + H20 = C6H1,0, + C6H,04 + HC". Among the products of hydrolysis by either acids or the enzyme, it has been possible to isolate only d-glucose and hydrogen cyanide, the third substance, C6H,04, readily undergoing secondary decomposition with the formation of amorphous matter.By its comparatively great stability towards acid hydrolysing agents, gynocardin diff ers in a marked manner from the four other known members of its class (com-pare Dunstan and Henry, Phil. Trans., 1901, 194, 515 ; 1902, 199, 399, and Proc. Roy. SOC.,1903, 72,285). Gynocardin is readily hydrolysed by barium hydroxide with the formation of crystalline barium gynocardinate, (Cl,H199,*C0,),Ba, and ammonia, according to the equation : C13HIgOgN + 2H20 = Cl,HlgO,*CO,H + NH,. Gynocas-dinic acid, C12H190,*C02H,forms a syrup which does not, reduce Fehling's solution and is dextrorotatory ; it is hydrolysed by acids in accordance with the equation : C,,H,,O,*CO,H + H20 = C6H1206+ C7H1,06.d-Glucose and an ucid are thus formed. The latter could be isolated in the form of its quinine salt, C20R2402N2,C7H1006, which crystallised in needles melting at 224' with decomposition. This salt, however, could only be separated in such small amount from the sugar which accompanied it that it, has been impossible to determine the constitu- tion of the acid C7Hlo0,. The foregoing results point, however, to the conclusion that ggno- cardin is the d-glucose ether of the cyanohydrin of either a trihydroxy-aldehyde, C,H4(OH)3*CHO, or a ketone, C,H,(OH),:CO, respectively. In accordance with this view, the constitution of gynocardin can be represented by one of the following formulae : C,H4(OH),=CH(CN)~O*c6Hl~05C,H,(OH),:C(CN)*O*C6Hl~05.or Gynocardin is devoid of any appreciable physiological action.43. '' Catechin and acacatechin. Supplementary note." By Arthur George Perkin. As previously found, catechin (from Gambier catechu), when dried at looo, melts at 175-177', and Clauser's etatement (Ber., 1903, 36, 101) that anhydrous catechin melts at 210' could not be substantiated. 90 Acacatechin, C,,H,,0,,3H20, dried over sulphuric acid, loses 1H20, and differs from catechin, C15H1400,4H20, which under these conditions evolves 3H20. Acaccctechin tetrarnethpl ether yields the acetyl com- pound, C,5H900(CH3),*C2H30(colourless needles, m. p. 135-1 37O), and on oxidation with potassium permanganate gives veratric acid and another substance, which is probably phloroglucinol dimethyl ethw.Catechin tetramethyl ether behaves similarly. With sulphuric or hydrochloric acid in the presence of acetic acid, catechin and acacate- chin give an orange-red anhydride having the same composition in both cases (C =63-26; H =3.89 ; and C =63.33 ; H =3.94 respec-tively), which is insoluble in alkaline solutions and the usual solvents, but which is not identical with the “catechuretin” of Kraut and Delden (Annalen, 1863, 128, 270) and Etti (Annalen, 1887, 186, 332). When oxidised with potassium ferricyanide in the presence of an alkali acetate, both catechins yield a new colouring matter, which dyes mordanted fabrics in orange-brown shades. ‘644.The action of ethyl dibromopropanetetracarboxylate on the disodium derivative of ethyl propanetetracarboxylate. A correction.” By William Henry Perkin, jun. A short time ago (Tmias., 1903, 83,780), T. W. I>. Gregory and the author published the results of a research on the above decomposition, and stated that the product of the reaction was ethyl hexamethylene-called the attention of the present author to the fact that this inter- pretation is incorrect, and that the substance actually formed is ethyl 224 nlethylerrzetetrccca/rboxplate, CH2 (C02Et)2C/\C(C0,Et)2* The substances described by Gregory and Perkin as hexamethylene derivatives are therefore in reality trimethylene compounds. ‘rhis remarkable formation of the trimethylene ring is discussed in the detailed paper.45. “Glutaconic acid and the conversion of glutaric acid into trimethylenedicarboxylic acid.” By William Henry Perkin, jun.,and Cleorge Tattersall. Glntamnic acid has hitherto only been obtained in one modification, although stereochemical theory indicates that the two modifications, 91 H*g*CH,*CO,H H*8*CH,*CO,Hand )H*C*CO,H CO,H-C*H cis. trans. corresponding with fumaric and maleic acids, should exist. Ordinary glutaconic acid (m. p. 134') is the cis-modification, since it yields an anhydride which, under reduced pressure, distils without decomposition and on hydrolysis yields the same acid (compare Buchner, Bey., 1890, 23,706). The authors have been engaged in a series of investigations with the object of preparing the unknown or trccrrzs-modification of glutaconic acid, but without success.When glutaconic acid is distilled, it decomposes partially into vinylacetic acid, CH,:CH*CH,*CO,H, and carbon dioxide, but when heated with water at 180°, the decomposition takes place in another direction, and crotonic acid (m. p. 72') results. p-Hydroxyglzcturic mid, CO,H*CH,*CH(OH)*CH,*CO,H, dis-on tillation, yields a mixture of cis-glutaconic acid and its anhydride, and, when treated successively with phosphorus pentachloride and alcohol, it is converted into ethyl P-chlorogluturccte, C0,Et CH,*CHCl*CH,*CO,Et, which, when digested with diethylaniline and subsequently hydrolysed, regenerates cis-glutaconic acid. Ethyl a-bronzoglutarate, C0,Et *CHBrG H2*CH,*CO,Et, is obtained from glutaric acid by bromination and subsequent esterification.When this ester is digested with diethylaniline and subsequently hydrolysed, or when simply hydrolysed with alcoholic potash, it yields trans- FH*CO,Htrimethylenedicarboxplicacid (m. p. 175O), CH,< CH*CO,H (compare Bowtell and Perkin, Proc., 1899, 15, 241). Ethyl a-iodoglutarate, obtained from the bromo-ester by digesting with potassium iodide, hehaves in exactly the same manner. 46. ''The transformations of highly substituted nitroamino-benzenes." By Kennedy Joseph Previte Orton and Alice Emily Smith. The s-trisubstituted nitroaminobenzenes do not undergo the isomeric change into nitroanilines characteristic of less substituted nitroamino- benzenes, since the ortho- and para-positions in the benzene nucleus relative to the amino-group are occupied.In some cases, for example, 1-nitroamino-s-tribromobenzene,a nitroaniline is produced by displace-ment of a bromine atom by the nitro-group under the same conditions in which the isomeric change is effected, namely, in aceti,c acid soiutions 92 in the presence of sulphuric acid (Tmns., 1902, 81,490, 806). In other cases, a more complex decomposition takes place. For example, s-trichloronitroaminobenzene, which is obtained from s-trichloroaniline, yields s-trichlorobenzenediazonium salt, ammonia, and s-ts.ichlorophengZ-6rwhzo-2 :3 :6-tric?~Zorobenxoquinone, C,H,Cl,-N:C,HCl,:O, the two latter being in molecular proportions.The iminoquinone crystallises from petroleum in red crystals melting at 143";on reduction, it is con- verted into 2 ; 4 :6 :2 :3 : 6 -I~exacl~loro-4-l~~drox~~i~~~enyZa~~~ne, C6K,Cl,*NH*C,HC1,*OH, which crystallises in long, colourless needles melting at 186". When hydrolysed by sulphuric acid, the iminobenzoquinone is converted into molecular proportions of s-trichloroaniline and 2 :3 :6-trichlorobenzo-quinone. Since in all cases the acetic acid solutions of nitroaminobenzenes, on treatment with sulphuric acid, yield magenta, purple, or indigo-blue solutions from which are obtained on dilution nitroanilines or sub-stituted pheiiyliminoquinones, according as the ortho- and para-posi- tions with respect to the imino-group are occupied by other groups, it seems probable that analogous compounds, possibly quinone derivatives, are always present in these solutions ; from these intermediary sub- stances are produced, on the one hand, the nitroanilines, or, on the other, the iminoquinone derivatives.47. '' An asymmetric synthesis of quadrivalent sulphur." By Samuel Smiles. The I-menthyl ester of methylethylthetine bromide was prepared from I-menthyl bromoacetate and methyl ethyl sulphide. It was found that (a)the product yields an inactive methylethylthetine on saponi-fication with silver oxide or with cold concentrated hydrochloric acid ; (b) that the molecular rotatory power of the product lies nearly half- way between those of the dimethyl and diethyl derivatives, and that this relation is also shown by the corresponding platinichlorides ; (c) that the platinichloride of dl-methylethylthetine I-menthyl ester bromide, when prepared from I-menthol and the acid bromide of dl-methylethylthetine, has the same rotatory power as the platini- chloride made from the product of asymmetric synthesis.Hence it is concluded that the two isomeric d-and I-methylethyl- thetine I-menthyl ester bromides are produced in equal amount from the interaction of methyl ethyl sulphide and I-menthyl bromoacetate. 1-Menthyl bromoacetate, a colourless oil boiling at 144-1 45O/ 12 mm., has a sp. gr. 1.208 at 25'/4O and [.ED-61.98" and [MI:" -171.68" ; when dissolved in alcohol (c= 12*21), [a]:" is -62.24O and [MI,.-172.4". Dinzethylthetine l-mentlhJ estei- bi*onzicZe, (CH,),S Br*CH2*C0,*Cl,H,,. melts at S7-90" with decomposition; in absolute alcohol, it has [MI, -157.9", and in 50 per cent. alcohol [ fw], -162*7', and in acetone solution [MIL,-159.2"; the chloride has [MI,-162.0' approximately ; the hydroxide is an oil which slowly decomposes into menthol and dimethplthetine. The platin&hloride melts at 177' and in epichloro- hydrin gives [MID -371.3'. dl-Methylethylthetine l-me?tthyl ester bi-omide, CH,*SBr(C2H5)*CH2*C02*CloH19, melts at 80-S3° and in alcoholic solution has [&I],-162.7". Its platilaichloride melts at 173-1 74" and has [ AXID -351 .Oo in epichlorohy drin. Dietlqlthetine 1-menthy2 ester bromide, (C2H,),SBr*CH,*C0,*C,,Hl,.melts at 73-74' and has [ MIu -169.0" in alcoholic solution. The pkatinichloride melts at 148-149', and a solution in epichlorohydrin gave [MI, -331.9". 48. '' Tne action of a-halogen ketones on alkyl sulphides. ' By Samuel Smiles. It' has been found that certain a-halogen-substituted ketones interact with alkyl sulphides forming the halides of sulphine bases. The reaction is by no means general, for bromodiphenacyl, C,H, CO*CHBr * ca,*CooC,H,, a-bromocamphor, and certain other ketones do not act in this manner. Further, the activity of the bromine cannot be entirely due to the proximity of an acid radicle to the CH,*Br group, for phenylbromo- ismethylsulphone, CH2Br*S02*C6H,, without action on the alkyl sulphides.This behaviour of the a-halogen ketones is interesting when compared with that of the a-halogen-substituted'acidswhich also contain the group CH,Br*CO,and react in a similar manner. Monochloroacetone and methyl sulphide yield ciceionyklimethyl-sulphine cldoride, (CH,),SBr*CH,*CO*CH,,a colourless, uncrystallisable syrup which is very solttble in water ; the platinichloride consists of pale yellow needles melting at 185°-1S60. o-Bromoacetophenone and methyl sulphide unite to give a theoretical yield of di~aeth~Zphenac~lsulphii2ebromide, (CH,),S Br*CH,-CO*C,H,, which forms long, colourless needles, melting at 148" ; it is soluble in hot water or alcohol, but very sparingly so in acetone. The hydroxide crystallises from chloroform in colourless leaflets which melt at 59-60" ; it dissolves readily in water, giving strongly alkaline solu- tions.The plutiiaicltZos.ide is thrown down from the aqueous solution of the chloride as a pale buff-coloured precipitate which, when pure, melts at 196-197' with decomposition. On mixing saturated alcoholic 94 solutions of picric acid and the bromide, the picrate is precipitated in sparingly soluble needles (m. p. 151-152"). The dichrontcitc!is insoluble in water and melts at 168-169O. Dieth~~henacylsulp?~inebromide forms colourless needles (m. p. 88-89') which are very soluble in water and alcohol, but sparingly so in acetone and ethyl acetate ; the platinichloride, a pale buff-coloured powder insoluble in most organic media, melts at 146-147' with decomposition.The picrate crystallises from hot alcohol in the form of bright yellow needles and melts at 125-1 26". D ~c6ntylphenccc?/szclphina bromide is a colourless, crystalline substance which is soluble in water or alcohol and melts at 60-61'; the pZati7zichZoride, melting at 138-139°, is soluble in warm ethyl acetate. Dimethyl sulphide and bromodeoxybenzoin give di?nethyldesyZszLZp?~inebromide, (CH,),S*CHBr(C6H5)*CO*C6H5; this substance crystallises from warm ethyl acetate in colourless prisms which melt and decompose at 110' ;the plalinkhloride dissolves in warm acetone and crystallises therefrom in buff -coloured needles which melt at 162'; the picrate forms yellow needles melting at 190'. (For other desyl derivatives, compare Fvam., 1900, 77,1178.) 49.cL Pinene isonitrosocyanide and its derivatives." ByWilliam Augnstus Tilden and Harry Burrows. A brief description of the cyanide and some of its reactions has been given in the '(Preliminary notice of some new derivatives of pinene and other terpenes " by the same authors (Proc.,1902,18, 161). Pinene isonitrosocyanide is shown to be a nitrile from which has been obtained, by the action of stxong sulphuric acid, an amide of corresponding cbnstitution. Pinene isonitrosocarboxylamide, C,,H,,( :NOH).CO*NH,, forms prisms which melt at 220'. It yields a methyl ether, which forms large, colourless prisms melting at 145O and a benzoyl deriva- tive melting at 197'. Pinene isonitrosocarboxylic acid, corresponding with the amide, has not been obtained, but hydrolysis with hydrochloric acid yields an oily acid volatile in steam, which is probably the ketonic acid, O:C,,H,,*CO,H.By the continued action of sulphuric acid on the amide, an isomeric change is induced, the product having the properties of the lactam in which the oximegroup, C:N-OH, has been converted into a carbonyl group, while an imino-group enters into the ring, thus :-CO*NH-. From this compound, by boiling with cawtic potash, the correspond- ing acid has been obtained. The amide crystallises in prisms, which melt at 209* and contain 1 molecule of water of crystallisation. The acid also contains water of crystallisation and melts at 220'. The silver and other salts of this acid have been prepared and analysed.When heated with hydrochloric acid, the acid is converted into an amino-acid, which forms a stable, crystalline hydrochloride. In the formation of thiscompound, it is believed that the ring is opened and, by the assumption of the elements of water, the group -CO*NH- i5 converted into -CO,H and NH,-. 50. Some interactions of metallic cyanides with organic bases." By Robert de Jersey Fleming Struthers. Phenylhydrazine heated with mercuric cyanide effervesces and deposits reduced mercury. This result might be indicated by the following obvious and simple equation : HgC,N, + C,H5*NH*NH,=Hg + 2HCN +N, + C,H,, but in reality the reaction is complicated by the formation of the intermediate compound HgC,N,,BC,H,*NH*NH,. This sub- stance is a white, lustrous, crystalline solid sparingly soluble in water or alcohol ; it melts acd decomposes with effervescence at about 110" according to the equation : 3(Hgc,N,,ZC,H,*NH*NH,) =3Hg + 6HCN +4N2+4C6H6+NH, +C6HI,*NH2+C6H,*NH*NH,.Phenylhydrazine, when heated with cuprous cyanide, effervesces, but in other respects the action is different from that which obtains in the case of the mercury compound. An intermediate compound, CuCN,C,H,*NH*NH,, was isolated in the form of brilliant scales with a silvery metallic lustre. This substance becomes rapidly discoloured at the ordinary temperature, evolves nitrogen, and ultimately acquires a deep coppery lustre. This evolution of gas mas proved to be due not to spontaneous decomposition, bul to an action of atmospheric oxygen.When heated to a somewhat higher temperature than that required for the mercury salt, the copper derivative decomposes, thus : ZCuCN,C,H,*NH.NH, =ZUCK+KH3+N, +C,H, +C,H,*NH,. From the above reaction, it seemed possible that cuprous cyanide might exert a catalytic action on phenylhydrazine. This proved to be the case, quite a small quantity of the cyanide under proper conditions of temperature sufficing to liberate nearly the theoretical yield of nitrogen from a large excess of phenylhydrazine, the actual amount being some thirty times as much as would have been the case had there been no catalysis. The action is probably due to the alternate decomposition and regeneration of the compound CuCN,C6H5*NH*NH,.The cyanides of mercury, copper, and silver were also found to form definite additive compounds with pyridine, aniline, quinoline, and other similar bases. ADDlTIONS TO THE LIBRARY. I. Donations. Lewkowitsch, Julius, Clhemische Technologie und Analyse der Ole, Fette und Wachse. 2 Biinde. pp. xv+45S, x+768. ill. Braun-schweig 1905. (Becd. 16/2/05.> From the Author. 11. By Puvclmse. avogadro, Amedeo, und Ampere, Andre Marie. Die Grundlagen der Molekulartheorie. Abhandlungen von A. Avogadro und A. M. Ampere, 1811 und 1514. (Ostwald’s KZc~ssiker,No. 8.) Leipzig 1889. (Recd. 28/2/05.) Becher, Johann Joachim. Chymischer Rosen-Garten, samt einer Vorrede und kurtz-gefasst en Lebens-Beschreibung Herrn D.Bochers von Friederich Roth-Scholtzen. pp. 96. Nuremberg 1717. (Recd. 713/05,) Burton, W. K. Practical guide to photographic and photo-mechanical printing, Second edition, pp. xvii +415. ill. London 1892. (Recd. 17/2/C5.) Butterfield, W. J. htkinson. The chemistry of gas manufacture. 9 practical handbook on the production, purification, and testing of illuminating and fuel gas, and on the bye-products of gas manufacture. Volume I. Materials and processes. pp. x + 257. ill. London 1904. (Recd. 17/2/05.) Cannizzaro, Stanislao. Abriss eines Lehrganges der theoretischen Chemie vorgetragen an der K. Universitat Genua, 1858. Uebersetzt von Arthur Miolati. Herausgegeben von Lothar Meyer. (Ostwald’s KZussiker, No. 30.) Leipzig 1891.(Recd. 28/2/05.) Dalton, John, und Wollaston, William Hyde. Die Grundlagen der Atomtheorie. Abhandlungen von J. Dalton und W. H. Wollaston, 1803-1808. Herausgegeben von W. Ostwald. (Ostwald’s KZassikes., No. 3.) Leipzig 1902. (Red 28/2/05.) Davy, Humphry. Electrochemische Untersuchungen. Herausgege-ben von W. Ostwald. (Ostwald’s Klassiker, No, 45.) Leipzig 1893. (Recd. 28/2/05.) Forster, John Reinhold. An introduction to mineralogy : or, an accurate classification of fossils and minerals, viz. earths, stones, salts, inflammables, and metallic substances. To which are added : I. 9discourse on the generation of mineral bodies. 11. Dr. Lehman’s tables on the affinities of salts. 111. Tables on the specific gravities of mineral bodies.IV. A view of their respective powers as con- eluctors of electricity. pp. 96. London 1768. (Recd. 7/3/05.) 97 Guldberg, Cato Maximilian, und Waage, Peter. Untersuchungen uber die chemischen Affinitiiten. Abhandlungen aus den Jahren 1864, 1867, 1879. Uebersetzt und herausgegeben von R. Abegg. (Ostwald’s Klassiker, No. 104.) Leipzig 1899. (Reed. 28/2/05.) Hess, Germain Henri. Thermochemische Untersuchungen, 1839-1 842. Herausgegeben von W. Ostwald. (Ostwald’s Klassiker, No. 9.) Leipzig 1890. (Reed. 28/2/05.) Hoff, J. H. van’t. Die Gesetze des chemischen Gleichgewichtes fur den verdunnten, gasf ormigen oder gelosten Zustand. Uebersetzt und herausgegeben von Georg Bredig. (Ostwald’s KZczssiker, No. 110.) Leipzig 1900. (Recd.28/2/05.) Kolbe, H. Ueber den naturlichen Zusammenhang der organischen mit den unorganischen Verbindungen, die wissenschaftliche Grundlnge zu einer naturgemassen Classification der organischen chemischen Korper, 1859. Herausgegeben von Ernst von Meyer. (Ostwald’s Klassiker, No. 92.) Leipzig 1897. (Reed. 28/2/05.) Mendeldeff, D. The principle8 of chemistry. Translated from the Russian (seventh edition) by George Kamensky, and edited by Thomas H. Pope. 2 vols. pp. xxiii+639, viii+551. ill. London 1905. (Recd. 13/3/05.) Mitscherlich, Eilhard. Ueber das Verhaltniss zwischen der chemis- chen Zusammensetzung und der Krystallform arseniksaurer und phos- phorsaurer Salze, 1821. Uebersetzt aus dem Schwedischen. Heraus-gegeben von P. Groth.(Ostwald’s Klassiker, No. 94.) Leipzig 1898. (Recd. 2S/2/05.) Ostwald, W., und Luther, R. Hand- und Hulfsbuch zur Ausfuhrung physiko-chemischer Messungen. Zweite Auflage. pp. xii + 492. ill. Leipzig 1902. (Reed. 14/2/05.) Pasteur, L. Ueber die Asymmetrie bei naturlich vorkommenden organischen Verbindungen, 1860. Uebersetzt und herausgegeben von M. nnd A. Lsdenburg. (Ostwald’s Klccssikev, No. 28.) Leipzig 1891. (Reed. 28/2/05.> Perkin, F. Mollwo. Practical methods of electro-chemistry. pp, xii + 328. ill. London 1905. (Reed. 7/3/05.) Pisanelli, Baldassar. Trattato de’ Cibi, et del Bere, ove non solo si tratta delle virtti de’ cibi, che ordinariamente si mangiano, e de’ vini che si bevano, ma insieme s’ insegna il mod0 di corregger’ i diffetti che si trovono in essi, per mantener la sanith .. . Aggiontovi cli molte dotte, es belle annotationi dal Franc. Gallinn. pp. 238. Car-magnola 1589. (Reed. 7/3/05.) Porta, Giovanni Baptistn. De distillatione libri IX. Quibus cert a methodo, rnultipliciq’ ;artificio, penitioribus naturs arcanis detectis, cuiuslibet mixti in propria elementa resolutio, perfect& docetur. pp. 154. ill. Rome 1608. (12ecd. 7/3/05.) 98 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 Wednesday, March 20th, 1905 (the day fixed for the Annual General Meeting). The price of the tickets will be One Guinea each, including wine Tickets will be forwarded to Fellows on receipt of a remittance for the number required, addressed and made payable to the Assistant Secretary, Chemical Society, Burlington House, London, W.ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the election of Officers and other business will be held on Wednesday,March 29th, 1905, at half-past four o’clock in the afternoon. At the next Ordinary Meeting, on Thursday, April 6th, 1905, at 8 p.m., the following papers will be communicated : “The basic properties of oxygen at low temperatures. Additive compounds of the halogens with organic substances containing oxygen.” By D. McIntosh. “Note on the interaction of metallic cyanides and organic halides.” By N. V. Sidgwick.“The chemical dynamics of the reactions between sodium thio- sulphate and organic halogen compounds. Part 11. Halogen sub-stituted acetates.” By A. Slator. “ The chemical kinetics of reactions with inverse reactions. The decomposition of dimethylcarbamide,” By C. E. Fawsitt. “The tautomerism of acetyl thiocyannte.” By A. E. Dixon and J. Hawthorne. ‘‘A method of determining the specific gravity of soluble salts by displacement in their own mother liquor, and its application in the case of the alkaline ha,lides.” By J. Y. Buchanan. ‘‘The combination of mercaptans with unsaturated ketonic COM-pounds.” By S. Ruhemann. “A new formation of acetylcamphor.” By M. 0. Forster and Miss H. M. Judd. R. CLAY AND SOSS, LTD., BREAD RT. HILL, E.C., AND BUNQAY, 8UP’B’OI.K.
ISSN:0369-8718
DOI:10.1039/PL9052100083
出版商:RSC
年代:1905
数据来源: RSC
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