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Proceedings of the Chemical Society, Vol. 17, No. 232 |
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Proceedings of the Chemical Society, London,
Volume 17,
Issue 232,
1901,
Page 19-34
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摘要:
PROCEEDINGS OF THE C H E M I C A IJ S 0 C I E T -Y. EDITED BY THE XECREFA RIEL?. Vol. 17. No. 232. February 7th, 1901. Professor THORPE, C.B., F.R.S., President, in the Chair. Messrs. R. M. Caven and J. E. Harrison were formally admitted Fellows of the Society. The following certificates were read for the first time :-William Carrick Anderson, 2, Florentine Gardens, Hillhead, Glasgom ; George Stanfield Blake, Purley Lodge, Purley, near Croydon ; Edward Richards Bolton, 7, Leazes Terrace, Newcastle-on-Tyne ; William Carter, 7, Victoria Street, Clitheroe ; Henry Drysdale Dakin, 9, Beech Grove Terrace, Leeds ; John Hanley, 4, Guion Road, Lither- land, Liverpool ;John Ansted Harrison, 47, London Road, Neath, Glamorganshire ;Henry Herbert Higgs, 26, Anglesey Street, Lozells, Birmingham ;Albert John Murphy, Preston House, Leeds ; Arthur Theodore Neil, 21, South Grove, Highgate, N.;William Robertson, 41, Rosenau Road, Battersea Park, S.W. ; Samuel Fenton Stell, 20, Henry Street, Keighley ; George Edward Welch, 88, Caledonian Road, Leeds ;Adam Storer Wylie, 93, Manchester Street, Oldham. THE ADDRESS TO THE KING. The PRESIDENTread the following Address, which the Council that afternoon had resolved to present to his Majesty the King. He moved that the Fellows of the Society should join with the Council in paying respect to the memory of the illustrious Queen they had so recently lost and in offering their homage to the new Sovereign. This was seconded by the TREASURERand carried unanimously, the Fellows all standing, 20 TO HIS IlOST GRACIOUS VII.MAJESTYKINGEDWARD May it please your Majesty.WE, the President, Council, and Fellows of the Chemical Society, beg leave to approach your Majesty with expressions of deep sympathy in the grievous loss which your Majesty and the Empire liave sustained through the death of our revered Sovereign, Queen Victoria, during whose beneficent reign tlre science of Chemistry, for the promotion of which her Majesty granted the Society a Royal Charter, has made immense progress. We recall with gratitude the leading part which your illustrious Father, the Prince Consort, took in securing the extension of scientific knowledge in this country, and especially the great assistance he rendered in the foundation, in the year 1845, of the Royal College of Chemistry (since developed into the Rqd College of Science), of which College he became the President.We desire respectfully to congratulate your Majesty on your accession to the Throne, and most heartily to wish your Majesty a long, happy, and prosperous reign. We venture to express the hope that your reign may be marked by discoveries in the science we represent not less brilliant than those which have characterised the reign of her late Majesty. Signed on behalf of the Chemical Society, T. E.THORPE, President. W. A. TILDEN, Treasurev. WYNDHAM R. DUNSTAN, Honorary ALEXANDER SCOTT, }#ecretarie&. R. MELDOLA, Foreign Secretary. THE DAY AND HOUR OF MEETING.Mr. F. J. LLOYDasked whether the President could give any infor-mation as to the reasons which had led the Council to issue its recent circular requesting the views of the Fellows on a proposal to change the day and hour of the Ordinary Meetings of the Society. The PREBIDENT,in reply, said that he was glad to take advantage of the opportunity which Mr. Lloyd had afforded him to state the atti- tude of the Council on the question. The expediency of an alteration in the day and hour of meeting had been mooted on more than one occasion, though no action was taken till the question was formally raised at a recent meeting of Council. The Secretaries were thereupon 21 directed to issue with the Journal” for this month the circular and card referred to, with the view of eliciting the opinions of the Fellows upon the subject. With respect to Mr.Lloyd’s question as to the reasons for the in- quiry, he might remind the Fellows that a great change had come over the social life of London during the fifty or sixty years of the Society’s existence. A great number of what used to be called the ‘ resident ’ Fellows now lived in suburbs which were extending in all directions more and more widely. Moreover, the facilities or reaching town had been so enormously increased that it seemed worth while inquir- ing whether a rearrangement of the day and hour of meeting would render it possible for the country Fellows to atlend the meetings of the Society in greater numbers than at present.He (the President) thought it would thus be seen that the Counci had good prim&facie grounds for testing the opinion of the general body of Fellows. He might add that more than half of the cards issued had been returned, and of these a very large majority were in favour of the suggested alteration. No exact analysis had as yet been made, but the Fellows might be interested to know that those in favour of the change were in the ratio of about four or five to one. Of the ‘resident Fellows about two to two and a-half to one were in its favour. He expresseda wish that the remaining cards should be returned as quickly as possible so that the Council might have the opportunity of considering the replies, and of dealing with the matter, if necessary, at the Annual General Meeting.A ballot for the election of Fellows was held and the following were subsequently declared duly elected :-Andrew Charles A itken, Thomas Stewart Barrie, John Cardew Bedwell, B.Sc., Herbert Jolin Bult, Merrick W. Burrows, M.Sc., Robert Waley Cohen, B.A., Herbert H. Cousins, M.A., Gilbert Howard Daniel, B.Sc., Robert Dodd, Frederick G. Donnan, M.A., Ph.D., John Alfred Emery, Reginald W. Ferguson, Henry Edward Haddon, Arthur Houldershaw, Bernard Farmborougb Howard, Edward Hughes, Robert Salmon Hutton, M.Sc., Stephen Archigenes Ionides, Major J. L. T. Jones, I.M.S., Robert Henry Jones, M.Sc., H. T. G. van der Linde, Nicholas Henry Martin, James Menzies, William Meredith, James Moir, M.A., B.Yc., Arthur W.Nunn, Theodore Henry Page, Thomas Slater Price, Ph.D., D.Sc., Lionel Guy Radcliffe, William Cecil Ramsden, Herbert Kilburn Scott, Harry Metcalfe Smith, John Talbot, B.A., B.Sc., Albert Edward Thomas, B.Sc., Major-Gen. .J. Waterhouse, William A. Wsylsncl, J. S. Wilson, M.D., C.M. Of the following papers, those marked * were read :--. 22 +8, “The action of hydrogen bromide on carbohydrates.” ByH. J. H. Fenton and Mildred Gostling. It was previously shown by the authors (Frans., 1898, 73,554, and 1899, 75,423) that bromomethylfurfuraldehyde results when hy- .drogeo bromide acts upon lzvulose, sorbose, inulin, or cane sugar, and it was shown that the formation of this substance is characteristic of ketohexoses or of substances which give rise to them on hydrolysis.The experiments have now been extended, using a higher temperature and chloroform as the solvent. Under these conditions, all forms of ceZZuZose give large yields of bromomethylfurfuraldehyde, and the results appear conclusively to prove that cellulose must contain a grouping or nucleus similar to that in It~vulose. An account was also given of the behaviour of several other carbohydrates under similar conditions. “9. “The ketonic constitution of cellulose.” By C. F. Cross and E. J. Bevan. Having received a private communication of the results obtained by Fenton and Gostling, which are described in the preceding note, it has been deemed opportune to state fully the experimental evidence available for the solution of the problem of the constitution of cellulose.For the view that cellulose is a near analogue of starch, that is, a polyanhydride of dextrose, the evidence is slender, resting mainly (1) on the well established empirical formula (C,H,005)12and (2) on the somewhat superficial study of the products of ultimate hydrolysis by Rraconnot (Ann., 1819, [ii], 12, 172) and Flechsig (Zeit.Physiol. Chem., 1883, 7, 523). The later evidence comprises the following items: (a) The tetr-acetate (Cross and Bevan) appears to be an ester of the unresolved cellulose (anhydride) with a formula C,H,O*( OAc),, from which may be deducedias probable, the ketonic formula CO:(CHOH),:CH2for the cellulose unit; (b) Will and Lenze have shown (Bein., 1898, 31,68) that the ketoses yield nitric esters with two ester groups less than the corresponding aldoses, two hydroxyl groups being condensed by in- ternal reaction, Cellulose giving a trinitrate (C,) with yields less than the theoretical (for the simple ester reaction) conforms with this general character of the ketoses and their anhydrides ; (c) Faber and Tollens (Bey.,1899,32, 2595), in a recent study of the oxycelluloses, have identified in the soluble products of the oxidation tartaric and oxalic acids and a dibasic acid containing five atoms of carbon.Sac-charic acid was vaot fog-nzecl. Further, the oxycelluloses digested with cnlcium hydroxide yield dioxy butyric and isosaccharic acids. Acids 23 with the normal six carbon chain are again conspicuously absent; (d) Brown and Morris (Trans., 1893, 63, 604) have established that cane-sugar is a first product of chlorophyllic assimilation and starch is probably only a derived overflow product. Further, that cane sugar, amongst the soluble carbohydrates, has a maximum nutritive value when tested in relation to chlorophyllic assimilation (Trans., 1890, 57, 484).A similar observation, but more directly with laevulose in relation to cellulose production, was made by A. Brown (Trans., 1886, 49, 432). On the above grounds, the authors had previously concluded that cellulose is not a polyaldose (anhydride), but is of ketonic constitution. Fenton and Gostling, by condensing cellulose to methylfurfural as a main reaction, have opened an entirely new direction of experimental attack, the first result of which is at least to render the polyaldose view of its constitution questionable.Their results directly suggest that lEvulose or other ketose is the raw material for cellulose elaboration and also offer a simple explanation of the origin of unsaturated compounds such as the furfural deriva- tives which are constituents of the lignone complex. It also further weakens the evidence upon which all furfural yielding constituents of plants have been assumed to be pentoses or pentosanes. DISCUSSION. BROWN,Dr. HORACE whilst fully admitting that a considerable amount of evidence can now be brought forward in favour of the ketonic constitution OF cellulose, expressed a doubt whether the small amounts of the bromo-derivative of methylfurfural obtained by Mr.Penton from purified starches would justify the conclusion that starch contains the carbonyl group. More evidence is required of the specific nature of the reaction, and also of the absolute freedom of the starch from traces of ‘‘ starch cellulose.” He was unable to add anything to the physiological evidence put forward by Dr. Morris and himself some years ago, and which certainly did appear to lend some countenance to the view that in the plant economy laevulose has some genetic con-nection with cellulose rather than with starch. Mr. FENTONsaid that although he and his colleague were at present concerned chiefly in demonstrating a ketonic grouping or nucleus in cellulose, he considered it not at all improbable that such a grouping exists, as a fraction of the whole, in the complex molecule of starch. The product of hydrolysis of the portion containing such a grouping may very conceivably have been overlooked in the methods of’identifi- cation hitherto employed.24 *lo. “Note on a method for comparing the affinity values of acids.” By H. J. H. Fenton and H. 0. Jones. In a former communication (Trfcns., 1901, 79, 92), the autshors described a simple method for coinparing the affinity values of acids based upon the decompositions of the hydrazone of oxalacetic acid. This substance when heated with pure water yields the hydrazone of pyruvic acid and carbon dioxide : From 83 to 90 per cer,t.is decomposed in this manner, the slight differences observed in different specimens depending on their purity. But in presence of acids of sufficient concentration an entirely different change occurs ;water is lost and Wislicenus’ pyrazolone carboxylic acid is formed without evolution of any carbon dioxide : CH,CO*OH CH,*COIH IC:N-Npll = b:N*NPh + H,O. I60,H CO,H With acids of insufficient concentration both changes occur simul- taneously, the amount of carbon dioxide evolved being less as the concentration of the acid increases. Making exactly parallel experi- ments with different acids, it was shown that the volumes of carbon dioxide obtained are in the inverse order of the affinity-values of tbe acids.In order to explain the nature of this influence, the authors suggest that the uadissociated molecule of the hydrazone tends only to lose water, giving the pyrazolonederivative, but that the negative ionCOPH -CN,HPh -CH,CO, is unstable and tends to lose carbon dioxide. Upon this hypothesis any circumstance tending to prevent ionisation should favour the production of the pyrazolone derivative, and the presence therefore of a sufficient concentration of hydrogen ions should cause the change to take place in this direction more or less completely. Other explanations might, of course, be offered, referring, for example, to the dehydrating influence of acids or to the ‘basic’ character of the pyrazolone ring, and it was therefore considered advisable to make further experiments in order to ascertain whether other conditions went in harmony with the ionisation hypothesis.The investigations had reference to the influence of (a) salts, (b) non-electrolytes, (c) acids in presence of their own salts, and (d) solvents other than water. In all the experiments the conditions were made exactly parallel, about 0.1 gram of the hydrazone being heated to 100’ with 7.5 C.C. of the liquid to be examined in the manner previously described. The solutions examined and results obtained were as follows :-Weight-in Weight Corrected grams in of volrime of 100 C.C. hydrazone. :arbon dioxide. 1. Pure water ........................ 0.0998 8.31 C.C. 2. Sodium sulphate (cryst.) ......0*1000 9.75 )) 3. Cane sugar ........................ 0.1005 5‘12 :, 4. Urea .............................. 0’1000 8.31 ), ))5. Sulphuric acid.. ................... 0.1003 2’60 6. Sulphuric acid and sodiuni 0~1000 7.12 ,,sulphate ....................... 7. Acetic acid ......................... 0~1001 7-07 ,, 8. Acetic acid and scdium acetate (cryst.).......................... 0 -1002 8-31 ,) 9. Amy1 alcohol .................... 0.0989 3.53 )) 10. Toluene ............................ OV1078 2.29 ,, 11. Nitrobenzene .................... 0.1026 2.29 ,) Bases likewise have practically no influence ; thus 0.1001 gram hydrazone heated with a quantity of soda representing slightly less than 1 equivalent gave 8.58 C.C.(corr.) of carbon dioxide. The conclusions which may be drawn from these experiments are : (a) The influence of salts, bases, and non-electrolytes is nil, the results being practically identical with that given by pure water. (b) The effect of a salt in presence of its own acid is greatly to diminish the influence of the acid, and (c) Solvents having different ionising powers give very different results, the amount of carbon dioxide evolved being greatest in the case of water, less in amyl alcohol, and least in toluene and nitrobenzene. With regard to the three last-named solvents,it maybe remarked that, although they were carefully dried, water is produced in the pyrazolone formation, hence it is not surprising that some action should take ,placein a solvent such as toluene, which when pure has presumably little or no ionising power.It is evident therefore that the results are, on the whole, well in harmony with the ionisation hypothesis, which certainly appears to offer. the most satisfactory explanation of the phenomena, although other explanations are, of course, possible. The purification of the hydrazone by recry stallisation is a trouble-some and wasteful process, but the crude substance answers perfectly, since the results required are only relative. It is advisable to employ the same sample for each set of observations and the substance should be freshly prepared. 26 DIscUSSWX. Dr. TEAVERSremarked that the evolution of carbon dioxide from the acid seemed to take place under conditions similar to those which obtained during the electrolysis of the salt of an acid, and to be de- pendent on the concentration of the negative ion, in one case in the solution generally, and in the other on the surface of the anode.It mould be interesting to know how the corresponding diphenylhydrazone would behave under similar conditions. Mr. FENTON,in reply, said that one example of a disubstituted hydrazine had been investigated, namely, benzylphenylhydrazine, but that the oxalacetic derivative was extremely unstable, and only the pyruvic derivative could be isolated. *11. Organic derivatives of phosphoryl chloride, and the space configuration of the valencies of phosphorus." By R. M.Caven, B.Sc. By the interaction of ethoxyphosphoryl chloride, OP*OC,H,:CI, with two equivalents of aniline in ethereal solution, a chlorine atom is replaced and ethoxyanilidophosphomjl chloride, OP*OC,H,*NHC,H,*Cl, results, This compound crystallises from ether in truncated pyramids, m. p. 61-62". The remaining chlorine atom ma.y be displaced by the action of p-toluidine, when the edql ester of ~nilido-p-toluidop~osp~~oric acid, OP*OC,H,*NHC,H,*NHC,H,CH,, is obtained. This substance crystallises from dilute alcohol in needles, m. p. 116". p-Toluidine and aniline may be made to react in reverse order. Thus ethoxy-p-toluidophosp~~orylchloride was obtained crystallised in oblique prisms, m. p. 74" ;and the ethyl ester of p-toluidoanilidoplos-pJboric acid mas found to crystallise from dilute alcohol in needles, m.p. 116-117". The ethyl esters obtained by these reverse processes present similar physical and microscopic characters, and an intimate mixture of the two products melts at 116-117'. Thus the two compounds /OC,H, (1) /OC,H, (1)OP-NHC,H, (2) and OP--NHC6H4CH, (2) \NHC,H,CH, (3) \NHC,H, (3) are identical, and from this it appears that the two chlorine atoms in the compound OP*OC,H,*CI, are similarly situated with regard to the rest of the molecule. The only alternative to this would be the supposition that, the two chlorine atoms being differently situated, aniline and 27-toluidine possess the power of appreciating this difference, and exercise a different pre- 27 dilection when reacting with the substance.This supposition, how- ever, can hardly be entertained. The chlorine atom replaced by the ethoxy-group might;, however, differ in relative position from the other two chlorine atoms. To determine whether this is so, aniline and p-toluidine were made to react directly with phosphoryl chloride, and the follow- ing compounds were obtained : ccniZidopl~osp~~o1.yl chloride, OP*NHC,H,:Cl,, prisms, m. p. 79' ;anilido-p-to2zcido2,J~osp~orylchloride, OP-N HC,H,*NHC,H,CH,*Cl, very fine needles, m. p. 133-134' ; p-tolzcidopl~osp~~orylchloride, OP*NHC,H,CH,:Cl,, plates, m. p. 106" ; p-toZzcidoanilido~~~os~J~or~lchlovide, OP NHC,H,CH,*NHC,H5 CI, very fine needles, u.p. 133'. The two substances /NHC,H, (1) /NHc6H4CH3 )OP--NHCGH,CH, (2) and OP--NHC,H, (2) \Cl (3) \Cl (3) present similar characteristics, and when mixed together melt at 133-134'.They are therefore identical. It would seem then that the first and second chlorine atoms to be replaced are similarly situated, and therefore that all three chlorine atoms occupy similar positions within the molecule of phosphoryl chloride. The supposition that the chlorine atom which was at first replaced by the ethoxy-group refuses to react with bases, and is the particular atom which remains in tact in these latter compounds, need scarcely be considered. The above conclusion concerning the similarity of the chlorine atoms, if ultimately established, should be an important factor in settling the configuration of the phosphorus atom./R1A tri-derivative, such as OP/-RI', in which the points of attachment \,I11 of the three radicles are similarly situated in space with reference to the rest of the molecule, does not contain a plane of symmetry. It should therefore be capable of existing in right- and left-handed forms in which the phosphorus atom is the centre of optical activity. Ex-periments are now in progress to determine this point, and the fact that one of the elements is doubly bound to the phosphorus atom lends additional interest to the investigation, which was commenced at the suggestion of Dr. Kipping. 28 *12. ‘‘a-Rydroxycamphorcarboxylic acid.” By A. Lapworth and E. M. Chapman. An account was given of experiments begun with the view of preparing a-bromohomocamphoric acid, an object which has been achieved in another way (Trccns., 1900, 77, 1063).A method for preparing camphorquinone in large quantities, and free from camphoric anhydride, was described. Camphorquinone-p-bromophenyZ~ydraxo?ze,C,,H,,0:N,H*C6H4Br, is eminently suited for the detection of the quinone in small quantities ; it is very sparingly soluble in nearly all organic media, and melts at 215-216’. It appears to exist only as the ketonic modification (Betti, Rer., 1899, 32,1995). Camphorquinonesemicnrbaxone,C,,H,,O:N,H*CONH,, which is nearly colourless at ordinary temperatures, turns yellow at 210°, melts and decomposes at 228-229O. When camphorquinone is treated with hydrogen cyanide at -loo, a nearly colourless mass is produced, which probably consists of stereo--isomeric forms of a-dihydroxycyanocamphor,C8HI4< C(OH)CN OneIco of these was isolated in the form of six-sided plates, which decom- posed when heated, and melted at 197-19S0, approximately the melting point of camphorquinone; it had all the properties of an a-hydroxpitrile, and when dissolved in fuming sulphuric acid was con- verted into a~ydroxyca~nphorca~boxylic C(OH)CONH,anzide, C,H,,< Ico which forms large, brilliant crystals melting, somewhat indefinitely, at 235-240O.Ia-Hydroxgcamphorca1.60x?/Zic acid, CSH14<C(oH)Co2H, is formedco an heating the nitrile with strong hydrobromic acid for some time. It is sparingly soluble in water, and crystallises in brilliant needles or prisms which melt and decompose at 207-20S0, becoming con-verted into Manasse’s hydrocamphor (Bey., 1897,30, 659).The acid is converted into carbon dioxide and camphorquinone by lead per- oxide and acetic acid, and is slowly decomposed when heated with alkalis, being, perhaps, converted into &a-homocamphanic acid (Trans., C(OAc)CO,H1900, 77,1067). a-Acetoxycamphorccwboxy2ic acid,CsH1,< I Yco melts at 85-86O. It was pointed out that these compounds must contain the carboxyl group in the position in which it occurs in camphor. “13. “The bacterial decomposition of formic acid.” By W.C. C. Pakes and W.H.Jollyman. The authors, as the result of various observations, were led to analyse the gases produced from sodium formate in solution by certain bacteria.These experiments show that hydrogen and carbon dioxide are evolved, sodium hydrogen carbonate remaining in the medium in which the sodium formate was dissolved. The total amount of carbon dioxide, that is, the amount evolved as a gas and that in combination, was found to be equal in volume to the amount of hydrogen evolved. It is therefore possible to express the reaction by R very simple equation, either H*CO,Na + H,O =NaHCO, + H, or H*CO,H =CO, + H,. One of the chief reasons why the addition of sodium formate to media containing dextrose is of such advantage is that the alkali formed from the decom- position of the sodium formate neutralises the acids produced by the decomposition of the sugar ;the fact that the medium continues to be neutral or alkaline allows the bacteria to grow for a longer period than when the medium becomes increasingly acid.Many bacteria had no action upon the formate, and it was found fhat none of the more commonly occurring yeasts had any action upon the salt. 14. “Preparation of substituted amides from the corresponding sodamide.” By A. W.Titherley, M.Sc., Ph.D. The behaviour of sodamide derivatives of the type R*CO*NHNawith various halogen organic compounds was investigated, when the marked difference observed between the aliphatic and aromatic derivatives suggested a dissimilarity in their constitution. (a) With alkyl haloids. In presence of benzene there is no action ; alcohol, if present, takes part in the reaction, giving the amide and an ether, thus: CH3*CO*NHNa + C,H,OH +C,H,T =CH,CO-NH, +NaI + C,H,OC,H,.Sodiobenzamide in sealed tubes at 140’ readily gives alkyl derivatives, C,H,CO *NHR, in absence of alcohol, whilst sodacet- smide under similar conditions undergoes complex decomposition, giving only a small quantity of the alkylacetamide. (b) With acid chlorides in presence of benzene, sodiobenzamide behaves normally, giving diamidex, C,H,CO*NH* COR, but sodacetamide does not give regular results. With acetyl chloride, diacetamide is Formed, but with benzoyl chloride a complex change takes place, di- benzamide, tribenzamide, acetamide, diacetarnide, benzonitrile, and benzoic anhydride being formed, but no acetyl benzamide.c) With halogen esters, sodiobenzamide behaves normally, but gives only small yields of direct condensation products. Ethyl 30 hippurate was synthesised by the action of ethyl bromacetate on sodio- benzamide. Sodacetamide gives unsatisfactory results. (d) With bromamides, symmetrical disubstituted acyl hydrazines were expected, in accordance with the equation R*CO*NHNa+ ROC0*NHBr= R *CO*NH*NH-CO *R+ NaBr ; but no trace of these substances was obt,ained, as both aliphatic and aromatic derivatives. immediately undergo molecular rearrangement, giving alkyl acyl ureas, NHR*CO*NH*COR.. It, was found that the sodium atom could be best replaced by alkyl radicles by heating with potassium alkyl sulphates ; for example : With sodamide, amines are formed thus : NaNH, + KRSO, = R*NH,-I-KNaSO,.With sodium organic amides, substituted amides are formed : CH,*CO*NHNa+ KRSO, = CH,*CO *NHR + KNaSO,. On treatment with sodamide, the remaining hydrogen atom in the group CONHR may be replaced by sodium, and this similarly replaced by an alkyl group. The stages are : R-CO-NH, 4R*C@*NHNa-R*CO*NHRI-+ E*CO*NNaRI-+ R*CO*NRIRrl, where R' and R1' may be similar or dissimilar radicles. Several new monalkyl amides and mixed dinlkyl amides have been thus prepared, and their behavioul-, with dry hydrochloric acid and sodamide respectively, studied. The hydrochlorides of the monalkyl amides contain base and acid in the proportion of 1 mol. : 1 mol.(com- pare acetamide hydrochloride), and in the aliphatic group are solid, crystalline, very easily fusible, fairly stable substances ; in the aromatic group, thick viscid liquids, which dissociate readily. Acetetiiylamide hydrochloride, CH,*CO *NHC,H,,HCl, melts at 60" ; and ucet-n-propglanzide ?qdo.ocliZoride,CH,. CO *NHC,H,,HCI, melts at 47"; acetisobutylamide, CH,*C'ONH-C,H,P, is a liquid boiling at 225-227', is miscible with water, but is readily separated as an oil by adding alkali ; its hydrochloride melts at 107". Benx-n-poyplamicle, C,H,*CO *NHC,H7,crystallises in cubic-shaped crystals melting at 84.5", and boiling at 294-2959 Benzbutylamide, C,H,*CO *NHC,H,, melt,s at 57", and boils with slight decompositiou at 295-296'.Acet~~etl~ylethylamide, CH,*CO*N(CII,)C,H,, boils at ISOo ; and 6enxmethylethyZamide, C,H,*CO.N(CH,)C,H,, boils at 280'. Both are liquids. The sodium derivatives, R*CO*NNaR', are white powders, appreciably soluble in benzene. In the aliphatic series they dissolve unchanged in alcohol, and the solution: give, with alcoholic silver nitrate, orange precipitates-The aromatic sodium alkyl amides are decomposed by alcohol. The author discussed the tautomerism of the amides and expressed the view that in the aliphatic group the sodium compounds are true sodamide derivatives of the type R*CO*NHNa, whilst in the aromatic group they are partly sodium salts of the imidohydroxy-formula, NHR-CeONa, and partly R*CO*NHNa. Two series of silver derivatives have been obtained, one white, presumably R*C<tfg, and the other 0orange, R*CqNHAg, which are capable of passing into each other and are very unstable. The formula of benzamide itself in aqueous solution is probably NHC,H,*CeOH, and that of acetamide, CH,*CO *N€I,.15. “Note on two molecular compounds of acetamide.” By A.W. Titherleg, M.Sc., Ph.D. Acetamide sodium bromide, 2CH,* CONH,,NaBr, and acetamide sodium iodide, 2CH,* CONH,,NaI, are well defined crystalline compounds analogous to the hydrochloride, 2CH3*CONH,,HC1. They were obtained as bye-products in certain reactions, and may be prepared by direct union of the constituents in the presence of alcohol. On concen-tration or cooling theyseparate as needles which begin to dissociate below their melting points and are very deliquescent.On quickly heating, 2CH,*CONH,,NaBr melts at 144O with separation of NaBr, and 2CH,*CONH2,NaT melts at 110’ with separation of NaI. Molecular compounds with other haloid compounds of potassium and sodium do not appear to exist. 16. “Diacetamide; a new method of preparation.” By A. W. Titherley, M.Sc., Ph.D. Diacetamide may be readily prepared by the direct action of acetyl chloride (in benzene solution) on acetamide, SCH,CONH, + CH3COC1= (CH,CO),NH + 2(CH3*CONH,)HCI. After filtering off the insoluble acetamide hydrochloride and removing the benzene by distillation, the residue is fractionated. No previous account appears to have been given of this reaction. Neither acetyl nor benzoyl chloride has any action on benzamide, but the benzoyl chloride gradually decomposes acetamide, witb formation of benzoic acid, benzoic anhydride and acetonitrile. 32 17."Organic derivatives of silicon." By F. S. Kipping an6 L.L. Lleyd. Experiments on the preparation of enantiomorphously related silicon compounds were commenced nearly three years ago, and a short ac-count of this work has already appeared (hoe., 1899, 15,174); the much more important object, the separation of the isomerides, has not yet been attained. When silicon tetrachloride is treated in dilute ethereal solution with one m~lecular proportion of a phenol or alcohol, it is decomposed in accordance with the equation SiC1, + RI.08 =SiCI:; ORT+ HC1, and by submitting the product to a similar.treatment, a second group, and then a third may be introduced, SiCl,* OR' +RLt*OH=SiCl,(O R1)(ORII)+H C1 SiCl,(OR')(OR") +R"I*OH=SiCl(OR1)(OR")(ORrlT)+HCl. Amido-compounds may be used in the above reactions in the place of alcohols or phenols with similar results. Phenox~methoxysilicon dichloride, SiCl,(OPh)(OMe) (b. p. 2 16O), and phenoxyrnethoxyethoxysiliconchloride, SiCl(OPh)(OMe)(O tit) (b. p. 241*), are colourless, oily liquids readily decomposed by water ;methoxyethoxy-silicon dichloride, SiCl,(OMe)(OEt), and metJLoxyethoxyisobutox~silicorP chloride, SiCl(OMe)(OEt)(OBufi), boiling at 128" and 160' respectively, have similar properties. The principle on which the above reactions are bitsed, namely, the interaction of halogen compounds and hydroxylic or amido-derivatives, is evidently capable of general application, and its use for the prepara- tion of enantiomorphously related compounds is being investigated by one of us in the case of dements other than silicon.18. (6 Iaomeric hydrindamine camphor-mulphonates. Racemisa-tion of a-bromocamphor." By F.S.Kipping. In examining the salt formed by the conibiriatiou of d-1-hydrindamine with d-camphor-r-sulphonic acid (obtained by the reduction of a-bromocamphorsulphonic acid) in order to try and isolate isomeric salts analogous to those obtained from the bromo-acid (Tram.,1900, 77, 861), it was found that although the salt at first seemed to be homogeneous, it could be resolved into fractions having different specific rotations.This difference in optical properties is due to the fact that the crude d-camphor-7r-sulphonic acid contains a very small quantity of the eriantiomorphouslp related isomeride, and as the latter can hxdly have been produced during the reduction of the bromocarnphorsulphonic acid, it follows that a-bromocamphor undergoes partial racemisatioe during sulphona tion, This change is one of considerable complexity, and necessitates the transference of part of one of the closed chains in bromocamphor from one position to another, as in the case of the optical inversion of cam-phor (Kipping and Pope, Trans., 1897, 71, 958). Except for the separation already referred to, the salt of d-Z-hydrind- amine with camphor-rr-sulphonic acid undergoes no change on frac-tional crystallisation, and gives a molecular rotation practically identical with that of ammonium d-camphor-rr-sulphonate ;it is, there- fore, a partial29 externally compensated salt of the type dAZB,dAdB ; it crystallises from water in large transparent rhomboidal prisms con- taining water of crystallisation, and melts at about 19F.19. ‘‘Tetramethylene carbinol.” By W. H. Perkin, jun. When the chloride of tetramethylenecarboxylic acid is reduced in moist ethereal solution with sodium, it is converted into tetramethylene carbinol, QH2’yH2 ,a colourless oil boiling at 143-144O aiidCH,*CK*CH,OH having an odour resembling that of isoamyl alcohol. The determina- tions of the density, refraction and magnetic rotation of this sub- stance are given in the etailed paper.ANNIVERSARY DINNER. It has been decided by the Council to arrange for a Dinner of the Fellows of the Society and their friends on Wednesday, March 27th, 1901, the day preceding that fixed for the Annual General Meeting. Further particulars will shortly be announced, 34 At the next meeting, on Thursday, February 21.4, the following papers will be communicated : “Isomeric hydrindamine mandelates and phenylchloracethydrind- amides.” By F. 8.Kipping and H. Hall. “Isomeric benzylhydrindamine bromocamphorsulphonates and some salts of d-Z-hydrindarnine.” By F. S. Kipping and H. Hall. “Condensation of phenols with esters of the acetylene series. IV. Benzo-y-pyrone and its homologues.” By X. Ruhemann and H. W, Bausor. ‘‘Constitution of bromocamphoric anhydride and camphanic acid .” By A. Lapworth and W. IT. Lenton. ‘‘The action of acetylchlor- and acetylbrom-aminobenzenes on amines and phenylhydrazine.” By F. D. Chattaway and K. J. P. Orton.
ISSN:0369-8718
DOI:10.1039/PL9011700019
出版商:RSC
年代:1901
数据来源: RSC
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