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Proceedings of the Chemical Society, Vol. 7, No. 96 |
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Proceedings of the Chemical Society, London,
Volume 7,
Issue 96,
1891,
Page 53-74
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摘要:
Issued 3C/4/1891. PROCEEDINGS OF THE C'HEMICAL SOCIETY. No. 96. Session 1891-92. March 25th, 1891. Anniial General Meeting. Dr. Russell, F.R.S., President, in the Chair. The President delivered an address, of which the followirig is an abstract :-The number of Fellows is 1786, of whom 32 are honorary f0r.eig.n members. One foreign member, Dr. Heinrich Will, and 1'7 Fellows have died during the year :-Di*. M. Bechler, W. Blythe, €3. B. BrAdy, F.R.S , C. I. Burton, W. Lnnt Carpenter, Prof. T. Carnelley, J. B. Hutcheson, J. A. Hill, Robert MacCalniont, E. C. Nicholson, T. R. Ugilvie, C. P. Phillips, H. Poland, H. Smith, W. C. Stevens, F. 0. Landell and K. is. Walker. The following 13 Fellows have withdrawn:-A. Bain, E. N. Butt, J. Barker, R.Carruthers, VT.H. Glazier, J. Hall, A. E. John-son, E. A. Parnell, W. E. Porter, W. R. Reffell, J. Stokes, A. Taylor, and R. C. Tresider. 28 Fellows have been removed from the list on accozznt of arrears:-B. Akroyd, H. J. Alford, P. H. Cathcark, F. W. Dupr6, A. F. Damon, H. Eccles, W. T. Elliott, J. W. Ellis, M. P. Gosset, E. Ernest Graves, T. P.Qarwin, T. Hart, W. H. Hyatt, F. El. Lowe, H. A. B. Leipncr, T. Muskett, F. Nettlefold, C. O'Keefe, I;. Peckitt, G. F. Rodwell, V. P. Richards, A. H. F. Kuppell, A. E. Simpson, IV. P. K. Stock, c'. A. Smith, P. C. Thomas, Dr. W. H. Wilson aid M'. A. Wren. 114 Ft.llows have been elected during the year, being 31 fewer than last year. The financial state of the Society is not quite SO satisfactory, said the President, as it has been for some years past, the receipts from subscriptions being $177 less than last year.This fallingoff is to be 54 accounted for, partly by the accidental circumstance that there were 11fewer life compositions thnn last year, but chiefly by the fact that no fewer than 26 candidates had been blackballed. The same number of papers, viz. 72, have been printed in the Transactions as last year, but they occupy no fewer than 1051 pages. instead of 772 pages in the previouq year. There bas been a con-siderable increase in the number of abstracts, 2341 appearing this year., and occupying 1527 pages, whereas last year the number was 2131, which occupied 1252 pages. Hence the cost of the Journal has been greater this year by $413.All the new and valuable works on chemiutry have been added to the Library as t)hey were published. The time had again come round for the award of the Longstaff medal, given everythird year to the Fellow of the Society who, in the opinion of the Council, had done the most to promote chemical science by research. This instruction was not always easy to carry out ; but, the unanimous dccision arrived at on this occasion to award the medal to Professor Japp would certainlg, he thought, b3 regarded by the Fellows generally as eminently satisfactory. All who follvwed the higher development of organic chemistry knew how valuable were the carefully thou ght-out papers which Professor Japp had communicated to the Society.It was a matter of regret that he was unavoidably prevented attending the meeting to receivc the medal in person. The great event of the year had undoubtedly been the celebration of the Jubilee on February 24th and 25th ; it was the intention of the Council to issue in a separate form a full account of the proceedings on these occasions. With reference to the reception held at Gold- smiths’ Hall on the evening of the 24th by the President and Council, the Goldsmiths’ Company had not only lent their Hall for the occasion, but with that liberality for which the great City Companies were so noted, “recognising that the occasion was of quite an excep- tional character,” had expressed their wish to relieve the Society from the expense attending the preFaration and me of the Hall.The suggestion made in his previous address that a subject catalogue of the Joixrnal from its commencement might be published as a fit memorial of the Jubilee had, he thought rightly, been abandoned, as it appeared that the labour and expense involved would be greater than tlle result Konld justify. It seemed appropriate to the occasion to briefly chronicle the changes which had occurred in the constitution and government of the Society since its fnundation. Little or no alteration of bye-laws or plan of working tbe Society occurred during the early years. In 1852 the number of Vice-Presidents, which was then four, was increased by adding all past Presidents ; but, it was not until 1866 that any other change worth recording took place.In that year a new form of nomination paper was introduced, and this seems to be the first indication of any feeling having arisen that undesirable people were seeking and obtaining admission into the Society : this question had from time to time caused more discussion among the Fellows than any other relating to the government of the Society. As chemistry became of more public importance, a, very natural impression gained ground that, since all the more distinguished chemists of the day belonged to the Society, therefore every Fellow must be a thorough chemist. This misconception on the part of the public had had a n.ost mischievous effect. In 1867 the matter was very fully discussed, and was ultimately referred by the Coiincil to a committee consisting of Mr.Crookes, Dr. Miller, Dr. Odling, Mr. Wanklyn and Dr. Williamson. The report of this committee was adopted and sent to all the Fellows, and it stated the case so fully that it appeared well to republish it on the present occazioii. This committee decided not to recommend ”any alteration in the bye-law relating to the election of Fellows which would have the effect of contiring the Fellowship of the Society to strictly scientific men.’’ But with a view to increase the security against the election of undesirable candidates, they recommended that the number of signatures attached to a certific:tte be five instead of three, three instead of one to be from personal knowledge. The reconimendations were adopted, and appear to have met the requirements of the case, as the agitation ceased.In 1877, another similar outbreak took place, but on this occasion the feeling tha,t it was practically impossible for the Society to itisist on all its Fellows being trained and competent chemists became so strong that ultimately it was decided to found the present Institute of Chemistry. Now, after the lapse of 14 years, a discussion is again raised, but the collateral circumstances are very different, as, through the existence of the Institute, all who desire to be stamped as educated chemists have the opportunity of obtaining such recapition. It was, however, necessary to arrive at a clear understanding as t,o who we desire to attract, and who we desire to exciiide from our Society. Speaking for himself, said tlie President, he should wish to see the entrance made easy for all who have any real interest in our science, even if they be only amateur chemists, provided that socially there be no objection to their admission ; he would entirely abandon the idea that amount of chemical knowledge is to detsmine the suitability of a candidate.It was practically impossible by any hard-and-fast rules to exclude undesirable pwsons, and the historr of tlie Society went to show that the only effectivc method was for the Fellows themselves to realise that it rested with them to recomniend only proper persons. What had been the history of the Society during the past 14 years as showing whether the means at disposal had been effective in securing the prosperity of the Society ? Without a shadow of doubt, the Society never stood so high both in the scient,ific and external world as at the present time; his experience during the past two years had shown him how widely the Society was known, and in how f'nvourable a light it is regarded at home and abroad.If the feeling be cnltivated and generally acknowledged that the body of Fellows expect and require that all should act honestly and lionourably towards one another, t'here will be very few improper persons gaining admission. On learning that any Fellow is acfing in any way wrongly or dishonourably towards the Society, the first thing in future will be to ascertain, by reference to the Proceedings, who are the five Fellows who certified that the said Fellow was a proper person to join the Society. Nothing is more powerful than public opinion, and if it be felt that such a spirit should guide all elections, far more good will accrue to the Society than any law can effect which can be invented or enforced.Dr. Gilbert prorosPd a vote of thanks to the President, coupled with tile request that he aliow his address to be printed ; the motion was seconded by Mr. Carteighe Both sperkers referred in most appre- ciative terms t.0 Dr. Russell's services to the Society, especially on the occasion of the Jubilee celebration. Dr. Teed supported the motion, which was carried by acclamation. The President having acknowledged the vote, Professor Thorpe, the Treasnrer, gave an account of the financial psition of the Society.The receipts from Fellows had been 323459 16s. Od. ; from sale of the Journal ~€3839s. 4u'.; and by dividends on invested capital $363 0s. 6d. The expenses on account of the Journal had been $2724 0s. 10d.; on account Gf the Library $300 18s. 9d. ; on account of the Proceedings $183 7s. lOd.-the tol a1 expen- diture being &3790 4s. 9d. The balance at the bank was $1798 17s. 7d. ; and $ti00 had been invested in Metropolitan Board of Works 39 per cent. stock. Professor Attfield proposed that the thanks of the Fellows be tendered to the Treasurer. Dr. Atkinson, in seconding the vote, Z~mented the loss of income during the year, and referred to the smaller expenditure out of the Research Fund, and the excessive balance at the bank.Dr. Stevenson advocated a larger expenditure on the Libiaary. Mr. Friswell followed Dr. Atkinson it1 lamenting the diminution in income 57 and its cause, and also referred to the disproportix borne hg the life composition fee t80the annual subscription. Nr. Cassall asked that increased facilities of using the Library miqht he granted to Fellows. The President said that every effort was made by the Library Committee to obtain book:;, and that if Dr. Stevenson and others who complained of deficiencies would point out what was required, the Library Committee would most certainly pay the utlmost attention to their recommendations. The Library would be open at any reasonable and rational time.[Dr. Thorne subsequently stated that the statistics of attendance on evenings other than those when meetings took place in the buildings were such as to indicate that there was no great desire to use the Library in the evenings.] It so happened that a considerable sum had been voted out of the Research Fund at a time just outside the financial year, so tlrat actually the expenditure was greater than appeared. The Treasurer, in acknowledging the vote of thanks, mid that the large balance would very soon disappear, as a number of heavy pay- ments had to be made. He took occasion to gratefully ackmowlcdge the service which Mr. Tutton had rendered him in keeping the Society's accounts, and finally proposed that thanks be given to the Auditors, Messrs.H. Crompton, R. H. Uavies and B. Dyer. This proposal was seconded by Dr. Collie and adopted. Mr. Dyer having replied. Professor Ramsay moved a vote of thanks to the Officers and Council, which was seconded by Mr. Friswell, and acknowledged by Dr. Armstrong. BIr. Warington finally proposed that thanks be tendemd to thc Editor, Sub-Editor, Abstractors and Librarian. Dr. Clowes sesonded the motion. Mr. Groves and Dr. Tborne replied. Scrutators having been appointed, a balloi was taken, and as result the following were declared elected as Officers and C'ouncil for the ensuing session. Pre.fident : Dr. A. Crum Brown, F.R.S. Vice-Presidents who have-filled the ofice of Presidend : Sir F.A. Abcl, K.C.B., D.C.L., F.R.S.; W. Crookes, F.R.S.; E. Frankland, D.C.L., F.R.S. ; J. H. Gilbert, Ph.D., F.R..S. ; J. H. Gladstonc, Ph.L)., F.R.S.; A. W. Hofmann, D.C.L., F.R.S.; H. Muller, Ph.D., F.R.S.; W. Odling, M.B., F.R.S. ; W. H. Perkin, Ph.D., F.R.S. ; Sir Lyoii Playfair, Ph.D., K.C.B., F.R.S. ; Sir H. E. Roscoe, LL.D., F.R.S. ; W. J. Russell, Ph.D., F.R.S. ; A. W. Williamson, LL.D., F.R.S. 'irice-Presidertts : G. Carey Foster, F.R.S. ; W. N. Hartley, F.R.S. ; John Pattinson ; J. Emerson Reynolds, M.D., F.R,.S.; William A. Tilden, F.R.S. ; Robert Warington, F.R.S. 8ecretaiies : H. E. Armstrong, Ph.D., F.R.S. ; J. Millar Thornson, F.R.S.E. Foreign Secretary : Raphael Meldola, F.R.S. Treasurey .-T.E. Thorpe, B.Sc., F.R.S. Ordinai-y Members of Coiincil : E.Atkinson, Ph.D. ; Henry Bassett; ; Korman Collie, Ph.D. ; John Ferguson, M.A. ; E. Kinch; M. M. P. Nuir ; F. J. M. Page ; W. H. Perkin, jun., F.R.S. ; S. U. Pickering, M.A. ; Boverton Redwood ; Thomas Purdie, B.Sc. ; John A. Voelcker, Ph.D. The meeting then proceeded to consider the alterations in the bye- laws proposed by the Council. The first alteration having been read to the meeting, Xr. Lloyd asked the President what would be his ruling with reference to any new proposal made at the meeting to alter the bye- laws. The President said that he could not allow any proposal to alter the bye-laws of which notice had not previously been given to the Fellows to be put at that meeting.Although there was no express provision to that eflect either in the charter or bye-laws, it was nianifestly inexpedient to adopt any other course, and such ruling would be in accordance with the practice of the Society hitherto. Mr. Lloyd stated that the movement in which he and others had taken part had for its object to exclude those who were personally objectionable, and to effect this they desired to place the nomination of Fellows in the hands of the Council. He therefore moved as an amendment that the whole eubjcct of the alterations in bye-laws be postponed. The President having ruled this amendment out of order, after a few remarks from other speakers, a vote was taken, and the following alteration in the bje-laws was carried, there being only five dissentient s. '' That in the case of candidates resident abroad unable to obtain the before-mentioned number [five] of signatures, the Council shall have power to accept a certificate, signed from personal know- ledge by one Fellow of the Society, and to recommend its pre- sentation for ballot." Subsequently the following were also put to the meeting and carried all bat unanimously.2. That the following notice be printed at the head of the Form of Recommendation :-'' The atbention of the candidate in whose favour this certifjcate is 59 made out is specially directed to the fact that, if elected, he wil be required to sign the following obligation prior to his sdmis- sion into the Society :-“ Obligation.-I, the undersigned, do hereby engage that I will endeavour to promote the interests and welfare of the Chemical Society, that I will observe its laws, and to the utmost of my power maintain its dignity, as long as I shall continue a Fellow thereof.3. That Bye-law XI1 be altered so that it read as follows :-“ An Annual General Meeting of the Society shall be held on the 30th day of March, or on some day in March near that time, and at such an hour as tfie Council may determine, for the elec- tion of Officers, &c.” April 2nd, 1891. Mr. W. Crookes, F.R.S., Vice-president, in the Chair. Certificates were read for the first time in favour of T. St. John Uel bin, 12, Bolton Mansions, South Kensington ; James Lane Notter, Leigh Grange, Woolstone, Southampton ; Frederick Tetley, 3, Mann-ville Terrace, Horton Road, Bradford.The following papers were read :-1. “ Citraconffuorescein.” By J. T. Hewitt, B.A., B.Sc. With the object of further comynricg citraconic with maleic anhydride, the latter having been shown by Lunge and Burckhardt to be capable of yielding a ilaorescein, the author has submitted citraconic anhydride to the action of resorcinol in presence of sulph-uric acid, and finds that, like mnleic anhydride, it yields the corre- sponding fluorescein. Citraconfluorescein is readily soluble in alcohol and glacial acetic acid, and fairly soluble in water ; the aqueous solu- tion is of a yellowish-brown colour, and exhibits a green fluorescence less vivid than that of ordinary fluoibescein.2. “ Ethylic thiacetacetate.” By C. T. Sprague, B.Sc., Ph.D. The author describes a series of experiments made with the object of determining the constitution of the etbylic thiacetacetate which Hiibner obtained by the action of sulphur monochloride, S2C12, on ethylic acetacetate, and which, after his death, was studied by Buchka. The same snbstance has since been prepared by Deliole by the action of siilphiir dichloride, SCI,, on ethylic acetacetate ; by Schonbrodt by the action of sulphur on the copper derivative of st.hylic acetacetahe ; and by Michaelis and Phillips from thionyl chloride and ethglic acetacetate. Buchka proposed the formula S(CH.Ac*CO,Et),, but an alternative formula S(O*C:CH*CO,Eb), was suggested by Deliole.After describing the preparation of tfhe substance, the author dis- cusses tphe discrepant statements made by different observers as to it,smelting point. He then describes at length the product,s of the interaction of hydrazines and ethylic thiacet,acetate, and shows that it behaves towards phenylhydrazine, &c., in the same manner as ethylic acetacetate: in the first, instance, a pyrazolone sulphide is formed from two molecules of the hydraaine and one of the thiacetate ; the sulphides are in the next instance converted by further action of t,he hydrazine into pyrazolone disulphides and bisphenylmethylpyr- azolone or the homologous substances ; and, finally, the pyrazoione disulphides and the hydrazine interact to form hydrogen siilphide and hydrazones of the pyrazole series.The results afford further proof of the correctness of Buchka’s formula. 3. “ The function of chlorine in acid chlorides as exemplified by sulphuryl chloride.” By Henry E. Armstrong. A large number of experiments carried out during recent years in the author’s laboratory show that sulphui-yl chloride, SO,CI,, acts 011 benzenoid compounds, if at all: uniformly in the rernarkable manner first pointed out in the case of phenol by Dubois in 1867 (Zeits. f. Ghemie, p. 705), and in several other cases by subsequent observers, simply as a chiorinatitt,g agent. Sulphuryl chloride is in many respects a remarkable compound: it is very easily produced by the direct union of sulphur dioxide and chlorine in presence of a catalyst, such as camphor, charcoal or acetic acid, but little heat being evolved in its formation; it is a highly mobile liquid of low boiling point; and it is acted on with extreme slowness by water and alkaline solutions.It is, in fact, a surprisingly inert substance, possessed of properties by no means such as are usually regarded as characteristic of acid chlorides. The author questions whether after all the chlorine in acid chlorides is possessed of special activity. Probably our ideas on the subjecb are based too much on the consideration of the properties of the most familiar of acid chlorides, acetic or acet’yl chloride; benmic cbloride, it is well known, is a far less active substance, and many other acid chlorides are but slowly attacked by water.It would appear that in sulphuryl chloride the chlorine is but loosely held, and that it is easily withdrawn by a compound having an sfflnity for chlorine : naphthalene, for example. On slightly warming a mixture of this hydrocarbon and sulphuryl chloride, SO2 is at once evolved, and the naphthalene is rapidly converted into tctmchloride. The SO, radicle in the chloride being all but destitute of " residiial affinity," the cornpound has but little tendency to act as a whole. The view that, the activity of acid chlorides is conditioned by the oxygen rather than the chlorine is strongly supported by Wagner mid Saytzeff's observations, and the later ones of Pam low (AnnaZerL, 188, L04) on the action of zinc orgnnometallic: compounds on acid chlorides, which, there can be little doubt, attack the oxygen and not the chlorine : R*COCl + ZnMe, = R-CMeCl(O*ZfiMe). Perhaps also the activity even of so powerful an agent as chloro- sulphonic acid, SO,HCl, should be ascribed less to the chlorine than to the oxygenated radicle ; this view is borne out by the fact that the analogous compound S0,EtCl is a very inert substance.Both these compounds act, in the main, as sulphonnting agexts, and may perhap8 be regarded as mere forms of SO,. It would almost seem that on very slight provocation they become resolved into SO, and either HCl or EtC1, and that in the case of SO,HCl the formation of acid cnloride (sulphochloride), which is so frequently observed, is effected indirectly by the conjoint action of hydrogen chloride and SO,, an interaction taking place analogous to that by which acetic chloride is formed by the conjoint action of hydrogen chloride and phosphoric anhydride on acetic acid.Pyrosulphiiryl chloride, S,O,Cl,, which is an extremely active snb-stance, although not rapidly acted on by water, also acts as a chlor-inating agent, behaving much as if it consisted of SO, and SO,Cl, ; in some cases it gives rise to the formation of a very large proportion of sulphochloride, which probably is a direct product of its action. There is no reason to suppose, however, that even in this chloride the chlorine is specially active. A detailed description will be given later on of a long series of observations on the action of the various sulphurjl compounds above referred to.4. "The act,iou of nitric acid on the ligno-celluloses." By C. F. Cross and E. J. Bevan. Dilute nitric acid attacks the ligno-celluloses when heated with them at GO". The products are in the first instance a bright jellow derivative of the fibre substauce (lignone) and nitrous acid. By the further interaction of these, a characteristic decomposition is deter-mined, large quantities of nitrous oxide (N,O) being evolved together with carbonic anhydride, only a small proportion of nitric oxide 62 being formed. A sensible quantity of hydrogen cyanide is also produced, the proportion being increased by increase of temperature.These observations point, to the entrance of the NOH residue into the lignone molecule and its interaction with nitrous acid according I Ito the equation C:NOH + NOH.0 = N,O + H,O + CO, the final I I result being the displacement of 2H by 0. The action is probably general for compounds containing the NOH residue-hydroximes and nitrolic acids-and the aiithors suggest that attention should be paid to the gaseous products formed by the interaction of nitric acid arid carbon compounds as calculat,ed to elucidate their mechanism. The investigation, of which this is a preliminary note, is procecd-ing. The Chairman, Mr. CROOKES,gave a short verbal account of obser-vations which he had made on t.he rolatilisation of metals in ~vacuo under the influence of an electric discharge.April 16th, 1891. Professor A. Crum Brown, F.R.S., President, in the Chair. Messrs. J. C. Aylzznd, J. E. Marsh, G. A. Pingstone and G. H. Robertson were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. William Duncan, 10, Plough and Harrow Road, Edgbaston, Birming- ham ; Alfred John Gregory, The Bays, Knights Hill, West Norwood, S.E. ; John Kiiowles, Northwich, Cheshire ; Frank H. Leeds, 29, Bouverie Road, Stoke Newington, N. ; Etobert Andrew Scott Macfie, Rowton Hall, Chester ; Frank 0. Solomon, North-Eastern County School ; Dr. Otto Carl Weber, Rectory Road, Crumpsall, Manchester Seward W. Williams, East Orange, New Jersey, U.S.A. The following papers were read :-5.“ Studies on the formation of substitution derivatives.” By H. Gordon, M.A. The following notes relate to a part of a series of investigations undertaken by tlie author, in the laboratory of the Central Institu- tion, with the object of throwing further light on the laws which govern substitution in the case of benzenoid compounds. It was skated by Armstrong in 1875 (J. Chum. Soc., UO), that whenpara- br~tnodiorthonitrophenolwas warmed with bromine, it underwent isomeric change into orthoh.omorthoparadinitropheno1. Several other Cttses, in which perhaps a similar change takes place, were briefly discussed in the same paper. The author, at Dr. Armstrong's sugges- tion, has 1evised these observations, and, while confirmiiig the main result, is able to correct and explain others.l'he netion of bromine on dio,.thonitrfphenol.-The action of bromine on an acetic acid solution of diorthonitrophenol was found to give, at ortJinary temperatures, the normal product, namely, parabrdmodiortho- nitrophenol. On the other hand, when the mixture was heated for a short time at loo", the product consisted of a mixture of the two isomers, parabromodiorthonitrophenol and o).thobToi,rorthoparadinitro-phenol. This mixed product by continued heating at 100"with small quantities of bromine was gradually converted into odhob~onzortlio- paradinitrophenol. Parubromodiorthonitrophenol is therefore com- pletely converted by the action of heat and bromine into the isomeric ort hobromort hoparadin itrophenol.In connection with the above facts, it is of interest to note that, whereas Korner (Gaz. China. Itul., 1874, 327-397) found that on nitrating crude bromophenol, pzrabromodinitrophenol WAS obtained, Hiibner and Brenken (Be?.., 6, 170) obtained orthobwmodinitrophenol. At the time, Armstrong suggested that these facts might be explained by assuming that HIibner and Brenken had carried out the nitration in such a way as to condition isomeric change. Some experiments were made with the view to aseertain whether nitric acid would bring about this change, and it was found that hy heating an acetic acid solution of ~~ara~~omodiorthonitrophenolwith a few drops of nitric acid at 100J for a short time, the whole was converted into the isomeric o?-thob~omodiorthonitrophenol.At this point it was thought important to ascertain whether similar changes could be brought about in the corresponding chloro-com- pounds. Some diEculty was encountered iii preparing the para- chlorodinitrophenol from diorthonitrophenol, as it was found that chlorine had no action on the phenol dissolved in acetic acid at lo@",even in the presence of iodine. The chlorination was effected by passing chlorine into a solution of diorthmitrophenol in antimony pentachloride heated to about 105". Only the normal product, para- chlorodinitrophenol, was obtained. Action of bromine on parachl orodiortho ttitropheno 1.--Various ex-periments were carried out under diff went conditions to ascertain whether any isomeric change could be effected by the action of bromine on parachlorodinitrophenol, but in every case with negative results, the normal product, parachlorortliobromo~thonitrophenol, being formed in every case, and no isomer.The resnlt appeared to be in opposition to results published by Ling (J.Cltem. Soc., 1887, 769), who stated that the action of bromine at 100" on parachlor-ort,honitrophenol is to form pttrabromorthoch1ororthonitrophenol. Ling, however, on repeating his expel-iments (J. Chem. Soc., 1889, 588), found that his former stirtenlent was incorrect, and that no isonier-ic change had taken place. The author considers that the probable explanation of the isomeric change observed in the case of bromodinitruphenol is that the bromine first conzhines with the nitro- cornpound, and that, at the moment of breaking up, the bromine and NO, change places ; in the case of the chlorine compound, a similar change does not take place, probably because the chlorine is more firmly held than bromine.Action of sulphuric ucid on oythopnra dichlorophen olorthosulphorb ic rccilZ.-In the paper to which reference has already been made, Arm- strong indicates that possibly, by the combined action of heat and sulpliuric acid, orthopwradicblorophenolsulphonicacid could be con- verted into the isomeric diorthochloroparaphenolsulphoriic acid. As this would be a very remarkable change, the experiments were re-peated under a great variety of conditions of tenipcratnre, &c., but in no case was such a change found to take place.Armstrong was no doubt misled by the prcsence of some diorthochlorophenol in his orthoparadichlorophenol, prepared by the action of chlorine on phenol, which gives rise to both dichlorophenols. It appeared possible that, although no isomeric change took place in the case of dichlorophenol, yet it might occur in the case of the corresponding dibromophenol. The results tended to show that this was not the case ; but as several secondary reactions set in, snch 9s the formation of tribroinophenol, &c., this reaction was not further investigated. The clilorirm,ion uird brom iiialioiz of phenol.-Phenol, when chlor- inated in the ordinary manner, yields a mixture of para- and ortho- chlorophenol (Peterson and Bahr-Predani).As shown by Dubois in 1867, phenol may alho be chlorinated by means of SOZCl2,but it was not known whether the product in this case was a mixture of the two isomers; the author has therefore exanlined it, and finds it to be a mixture similar to that obtained by means of chlorine alone. Further, he has investigated the action of brcjmine on phenol under the conditions described by Hiibner and Brenken (Ber., 6, 170), and finds that the product is practically pure pnrabromophenol. If it be assumed that the initial action of chlorine and bromine on phenol is to form an additive compound, which then becomes resolved into hydrogen chloride or bromide and the mono-substituted phenol, it would appear that, at the moment of change, the resulting ortho-compound, in the case cf bromine, at once undergoss conversion into the 65 para-derivative ; but in the case of chlorine this change only partially takes place, owing to the chlorine being more firmly held.The sdphonation of the nitrophenols. -0rt honitrophenol and paranitrophenol, accor.ling to experiments published by Armstrong (J. Chent. SOC.,1871, 175), are both readily acted on by SO,HC1 : the former yields the well-known sulpho-acid ; the product from the latter, however, is decomposed by water and is not identical with the siilpho-acid ~ubseqiiently obtained by Post. It was to be supposed that the product obtained by Armstrong was the sulphate, and this the author finds to be the case.It is scarcely probable that the initial action is different in the two cases ; it is more likely that the sulphate formed from the orthonitrophenol at once under- goes isomeric change, and that, owing to its greater stability, such a change does not. occur in the case of paranitrophenol. The author did not succeed in obtaining any sulpho-acid by heating at 100" the sulphate from the paranitrophenol. On adding S0,HCI (2 mols.) to paranitrophenol (1mol.) and heating at loo", however, a not in- considerable amount of snlpho-acid was formed, although much of the material was carbonised. There can be little doubt, therefore, that the paranitrophenol- sulpbonic acid is formed by the sulphonation of tlie prcviously formed sirlphate.Metanitrophend closely resembles the para-compound in being readily converted into the sulphat,e, but not into the sulpho-acid even by the action of heat. The author is engaged in further investigating the action of sulphonating agents on metanitrophenol. T)ISCUSSION. Nr. A. R. LINGsaid that anfortunately he had made a mis-statement in his work on isomeric change (Trans., 1887, 789), and he wished to thank Mr. Gordon for pointirg it out ; he had, however, corrected it in a subsequent communication (Trans., 1889, 588). In the latter paper, he had recorded a case of isomeric change (when orthochloroparabromuphenol is nitrated), similar to that observed by HCibner and Rrenkeu, cited by the author. Referring to the actic? of SO,Cl, on phenol and its derivatives, Mr.Ling said that he agreed with the author that this agent yielded the same mixture of mono-chloro-derivatives as chlorine alone ; he remembered, moreover, having once made an experiment to prepare dichlorophenol from S02Cl:,and phenol, and finding that the reaction apparently stopped at the formation of the mono-derivative ; this was the more remark- able as parabrornophenol may readily be chlorinated by SO,Cl, (cf. Trans., 1889, 587). His experience of the difficulty of obtaining chloro-derivatives of $he nitrophenols by acting on the latter with chlorine was the same as Mr. Gordon's, and on this account he preferred to prepare the chloronitrophenols by nitrating the chloro-derivatives. On other points, including the tendency of the bromonitro-derivatives to undergo isomeric change, and the apparent absence of this property in the case of the chloronitro-derivatives, their results were in com-plete accord. 6." Compounds of dextrose with the oxides of nickel, chromium and iron." By Alfred C. Chapman. The author describes compounds of dextrose with the oxides of nickel, chromium and iron respectively. The nickel compound was prepared by adding a solution of nickel hydrate in strong aqueous ammoriia to a concentrated solution of dextrose in 90 per cent. alcohol. It is a green, aniorphous substance, insoluble in water and alcohol, of the formula C6Hlz06'2Ni0*3 H20. To prepare the chromium compound, an exccss of dextrose is dissnlved in an aqueous solution of chromic chloride, and this solution is poured into an excess of cold strnng ammonia.The precipitated liydrate partly redissolves on standing, and the purple solution so obtained gives, on gouring it into 90 per cent, alcohol, a lilac-coloured precipitate of the chromium dextrosate. The dry compound is a, slate-coloured, amorphous substance, insoluble in water and alcohol. Its composition appears to be represented hy the forinula (:,H',,O6.Cr20,*4H2O. The compound of dextrose with ferric oxide is prepzred by adding a slight excess of ammonia to a solution of ferric chloride in which an excess of dextrose has been dissolved. The red precipitate which at first forms soon redissolves on standing, giving a deep red solution.If this liqnid be poured into $0 per cent. alcohol, a red, flocculcmt precipitate of the dextrosate 0:' iron at once forms. The moist compound dissolves easily in water, giving a red solution which is decomposed on boiling, but is not decomposed by ammonia, potassic ferrocyanide or potassic thiocyanate. The dry compound is an orange-red, amorphous substance, insoluble in water and alcohol. It has the formula 2~6H,,0,.3Fe20,.3H~o. DISCUSSION. Remarks were made b7 several speakers with reference to the possible influence on the composition of such substances as described by the author of variations in the proportions of the interacting compounds, their stability in aqueous flolution and their behaviour towards polarised light. Dr.TEED,referring to the circumstance that the ordinary iron reactions were not manifest in the case of the cornpound of iron oxide with glucose until after the addition of chlor- 67 hydric acid, pointed out that the thiocyanate coloration ordinarily regarded as characteristic of ferric salts was also only developed in presence of certaiv acids, especially chlorhydric acid. The PREsmEh”r, referring to the tendency of chromium t,o form basic salts, pointed out that the formula of the chromium compound would be analogous to those of the zinc and nickel compounds if it were written C6H,206*2(Cr0.HO)*3H20; the iron compound, however, did not, appear to have an analogous composition. The author, in reply, after describing the behavioui- of the com-pounds when boiled with water, said that he had not yet conipletcd their examination.7. “ A rapid method of estimating nitrates in potable waters.” ByG. Harrow, Ph.D. The method depends on the reduction of nitric to nitrous acid by means of zinc-dust and chlorhydric acid, in a, very dilute solution, in presence of a-uaphthylnmine and sulphuric acid, the estimation being made by comparing the depth of the pink azo-coloration developed in the solution with that arising on similar treatment of standard nitrate solutions. A beaker containing 50 C.C. of the water is placed on a sheet of white paper side by side with other beakers holding 50 C.C.of standard solutions containing 1.0, 0.1 and 0.01 of nitrogen a6 nitrate per 100,000.and to each is added 10 C.C. of a test solution, prepwcd ’by dissolving 1 gram of a-naphthylamine, 1gram of sulphanilic acid and 25 C.C.of chlorhydric acid in abontl 200 C.C. water, boiling with a small quant’ity of animal charcoal, filtering and making up to 500 C.C. A very small quantity of zinc- dust--$ to 8 milligrams-is added to each beaker. If nitrate be present in the water, a more or less intense pink oolour is developed, which may be compared, at the end of 15 minutes, with that arising in the Ptandard solutions. By diluting the water until the tint produced is judged to be of the same intensity a8s that of one of the standards-prefernbly the most dilute-a first approximation is arrived at; and the water, having been diluted to the extent indi- cated by the results, a fresh experiment is made with this diluted water.When nitrites are present, the amount is estimated in n similar manner prior to the addition of zinc-dust, and due allowance is subsequently made. The author quotes a considerable number of comparisons with the Criim method, which show that very satisfac- tory results are obtainable. DiscusSION. Mr. WARINGTONsaid that he looked doubtfully on the method pro-posed, as nitrous acid was not the only product of the action of zinc. 68 The result would be accurate only if the conditions were precisely the same in the so1utionr;r compared. The author was right in making a final experiment in which the solutions to be compared were of the same strength.Quantitative analysis by means of colour-depths is perfectly safe only when, as in the old Nesslerising method, the final comparison is between solutions of equal strength. In not a few cases the depth of tint produced is not uniformly proportional to the quantity of substances present, very dilute solutions generally giving a weaker tint in proport:on to their strength than strong solutions ; this is, for instance, the case in the well-known interaction of meta-phenplenediamine and nitrous acid. The speaker also questioned whether. the method was more rapid than the indigo method. Professor P. F. FRANKLANDsuggested that probably in presence of the nephthylamine, which would tend to destroy the nitrous acid as it was formed, the reduction of the nitrate would be confined to the production of nitrous acid.8. “ The ‘gravivolumeter,’ an instrument by means of which the observed volume of a single gas gives directly the weight of the gas : a preliminary note.” By Francis R. Japp, I?.R.S. An apparatus for esecting tliis object has been described by Lunge (Ber., 23,448; see also Bey., 24, 735) ; but his me’thod labours under the disadvantage of requiring for each‘gas a separate apparatus with a special graduation. Thus Lunge’s apparatus for measuring nitrogen is a “ gas-volumeber,” with divisions of 0.798 C.C. (further subdivided into tenths), each of which divisions will contain a milli-gram of nitrogen under standard conditions. The reduction to standard state is effected mechauically by means of the “ regulator ” attached to his gas-volumeter.The author desires to point out how a gas-apparatus may be con- structed, by means of which, with an ordinary graduation in cubic centimptres, any required single gas may, without observation of temperature or pressure, and without calculation, be measured under such conditions that each cubic centimetre represents a milligram of the gas. The form of the apparatus is, with slight modifications, that of Lunge’s gas-volumeter (Uer., 23,440) ; the method of employing the regulator is, however, different. The apparatus consists of two gas burettes of, sap, 50 C.C. capacity each. One of these is the gas measuring tube; the other performs the function of the “regulator ” in Lunge’s gas-volumeter, and may be termed the ‘‘regulator tube.” Both are connected, as in Lnnge’a gas volumeter, by means of stout flexible tubing and a T-piece, with the same movable reservoir of mercury.Both are moistened intern- 69 ally with a drop of water, in order that the gases they contain may be saturated with aqueous vapour. The 25 C.C. division of the regulator tube is taken as the starting point in calculating what the author terms the “gravivolumetric values ” of the different gases to be measured. Thus in the case of nitrogen he calculates to what volume 25 C.C.of “standard-dry ” iiitrogen must be brought in order that 1 C.C. would correspond with 1milligram of the gas : that is to say, 25 C.C. of standard-dry nitrogen O*OOI256 x 25 = 0.0314 gram ; and, therefore, these 31.4 milligrams of nitrogen must be brought to the volume of 31.4 C.C. The division 31.4 on the regulator tube is marked N,.Corresponding points are in like manner determined for tlhe various other gases which it is desired to measure, and these points are similarly marked 02,COz,&c., as tho case may be, on the regulator tube. Finally, the thermometer and barometer are read (a process which is only necessary once €01. all in setting the regulatcr) ; the volume which 25 C.C.of standard-dry air would occupy if measured moist at the observed temperature and pressure is calculated; and this calculated volume of air is admitted into the regulator tube and the tap closed. The instrument is now ready for use.Suppose it is desired to ascertain the weight of a quant’ity of nitrogen contained in the measuring tube. The mercury reservoir is lowered until the mercury in the regulator tube stands at the nitrogeil mark, 31.4, at the same time adjusting the regulator tube itself, by raising or lowering it bodily, so that the mercury level in the measuring tube and the regulator tube may be the same. Under these circumsta?zces each cubic centiqnetre of gas in the measuring tube repre-sents a milligyam of nitrogen. For since in the regulator tube 25 C.C. of standard-dry air have been made to occupy the volume of 31.4 c.c., and as the gases in the two tubes are under the same conditions as regards temperature, pressure and saturation with aqueous vapour, therefore, in the measuring tube, every 25 C.C.of standard-dry nitro- gen has also been made to occupy the volume of 31.4 C.C.But 25 C.C. of standard-dry nitrogen weigh, as we have seen, 31.4 milligrams ; so that the problem is solved, and the cubic centimetres and tenths of cubic centimetres give directly the weight of the gas in milligrams and tenths of milligrams. The various other single (i.e., unmixed) gases may be weighed in like manner by bringing the mercury in the regulator tube to the “ gravivolumetrlc mark ” of the gas in question, and adjusting the levels as before. An exception would be made in the case of hydro-gen, which would be brought to such a volume that the cubic centi- metre would contain a tenth of a milligram.Lastly, if the mercury in the regulator tube be brought to the 70 mark 25, a gas or mixture of gases in the measuring tube will have the volume which it would occupy in the standard-dry state. In this form the instrument is merely a gas-volumeter, as described by Lunge, and may be emplojed for ordinary gas analyses. The “ grarivolunieter ” is thus designed to fulfil a variety of pur-poses for which Lunge employs a number of different gas-volumeters. Whether it will fulfil these purposes equally well remains to be seen. The theoretical principle is unimpeachable ; but there are doubtless practical difficulties to be overcome before the “ gravivolumeter ” can rank as a working laboratory appliance. Very likely the foregoing (merely provisional) dimensions of the regulator would have to be increased in order to give sufficient accuracy of adjustment.The author proposes to have +he instrument constructed in various forms, so as to ascertain the most suitable. He anticipates that it will, at all events, give results sufficiently accurate for technical purposes. Meanwhile he desires, by this preliminary note, to place on record this principle of gas analysis, which he believes to be new-the principle of measuring the various single gases at such a volume that each cubic centimetre contains a milligram of the gas. Mr. DE MOSENTHALexhibited one of Lipmann’s “ coloured ” photo-graphic negatives. 9. “ The action of acetic acid on phenylthiocarbimide.” By J.C. Cain and J. B. Cohen, Ph.D., Owens College, Manchesi’er. The authors have repeated the experiments of Hofmann, and show that the product of the action of pnre glacial acetic acid on phenyl-thiocarbimide is not diacetanilide as stated by Hofmann; but that two compounds are formed, viz. : diphenylurea and acetanilide. The proportion of these products depends upon the temperature at which the mixture is heated. At a lower temperature, diphenylurea is mainly formed, and at R higher temperature, acetanilide. The action, which appears to take place in two stages, may be ex- pressed by the following equations :-I. 2C,jH,NCS + 6C,H,O, = (C,jH,NH),CO + 3(C,H,0),0 + 2H,S + GOz. 2. (C,H,NH),CO + 2CZH40, = 2CsH,NH, + (C2HSO)ZO + CO,. These interactions are independent of the presence of water.10. “ The action of aluminium chloride on benzenoid acid chlorides.” By R. E. Hughes, Jesus College, Oxford. At Mr. Marsh’s suggestion, the author has examined the action of 71 aluminium chloride on cinnamic and hydrocinnamic chlorides in the expectation that pentamethylene derivative3 might result from the occurrence of an internal condensation analogous to the exterrial condensation which attends the formation of acetophenone from acetyl chloride and benzene, thus- coC,H,*CH.CH*COCl = C,H,<CH> CH + HCl. The experiments have, however, afforded negative yesults. The chloride was either dissolved in or mixed with (in the case of hydro-cinnamic chloride) light petroleum, and aluminium chloride was then added ; action set in at 80-90" in the case of cinnamic.and at about 50" and more briskly in the case of hydrocinnamic, chloride. The chief product in either case was an ill-characterised substance, the nature of which remains to be determined. Bohh chlorides afforded a small amount of the aluminium salt of the corresponding acid in the form of a microcrystalline powder, insoluble in alcohol, benzene, ether and petroleum, slightly soluble in a warm solution of sodium carbonate. The author incidentally describes the following hydrocinnamic derivatives. Hydrocinnamic chloride, C6H5*CH2*CH2*C0C1,boils at 117-119", under 13 mm. pressure; the author specially points out that the properties of this c.hloride are strikingly similar to those of benzoic chloride and characteristically different from thorn of cinnamic chloride, which, unlike most acid chlorides, is a remarkably inert substance, being only very slowly decomposed by water or caustic alkalis.Hydrocinnnmide crystallises from hot alcohol, in which it is readily soluble, in stellate groups of needles melting at 82'; it is readily soluble in hot water. I€ydrocinnnrnaniZide crystallises from hot alcohol in faintly yellow plates melting at 92". It is noted that benzoic and cinnamic acids may be readily separ- ated by treating the the mixture with phosphorus pentachloride and distilling the product under reduced pressure ; the portion passing over below 95" under 10 mm. pressure contains the benzoic chloride.72 ADDITION8 TO THE LIBRARY. Donations. Kurzes Lehrbuch der organischen Chemie, yon A. Bernthsen. 2te Aufl. Braunschweig 1890. From the Author. Sugar Analysis, by F. G. Wiechmann. New York and London 1890. From the Pnblishers. Geological and Natural History Survey of Canada :-List of Canadian Hepaticm, by W. H. Pearson, Montreal 1890. Catalogue of Canadian Plants. Part V. Acrogens, by J. Macoun. Montreal 1890. B’rom the Director of the Survey. Transactions of the Sanitary Institute. Vol. X, 1888-9. London 1890. From the Institute. United States Geological Survey :-Monographs, Vol. I. Lake Bonneville, by G, K. Gilbdrt. 4to. Washing ton 189 0. Mineral Resources of the United States : Calendar, Year 1888, by D.T. Day. Washington 1890. Ninth Annual Report, 1b87-88, by J. W. Powell. Washington 1889. From the Director of the Survey. Prometlieus ; illustrirte Wochenschrift uber die Fortschritte der angewandten Naturwissenschaften herausgegeben von 0. N. Witt. I Jahrgang 1590. Prom Dr. Witt. Treatise on Chemistry, by H. E. Roscoe and C. Schorlemmor, Vol. 111. Organic Chemistry. Part 111. New Edition. London 2891. From the Authors. Norwegian North-Atlantic Expedition. Vol. SX. Zoology : Pycnogonidea, by G. 0. Sam. Chiistianin 1891, From the Xditorial Committee. Smithsoninn Institution :-Annual Report to July, 1888. Washington 1890. Report of the United States National Museum for the Year ending June 30th, 1888. From the Board of Regents.Biographisch-litterarisches Handworterbuch der wissenschaftlich-bcdeutenden Cliemiker, von C. Schnedlgr. Berlin 1891. Reports from the Laboratory of the Royal College of Pllysicinns, Edinburgh, edited by J. B. Tnke and L). N. Paton. Vol. 111. Edin-burgh and London 1891. Frorr the C?~llege. 73 Local Government Board: Report of the Medical Officer for 1889. London 1890. From the Medical Officer. Occasional Lectures and other Discourses on Agricultural Chemistry, by J. H. Gilbert. London 1890. From the Author. Proceedings of the Royal Physical Society of Edinburgh. Session 1889-90. Edinburgh 1891. From the Society. II. By Pzcrchase. Agronomie, Chimie Agricole et Physiologie, par M. Boussingau It. Tome VIII.Paris 1891. Les BactBries et leur r6le dans l’btiolage, l’anatomie et l’histologie pathologiques des malades infectieuses, par A. V. Cord et V. Babes. Troisihme 6dition. Deux volumes. Paris 1890. Lehrbuch der Mikrophotographie, von R. Neuhaus. Braunschweig 2890. Arbeibrsmethoden fur orpnisch-chemische Laboratorien von Lassar-Cohn. Hamburg und Leipzig 1890. Leqons sup l’Electricit6, par B. Gerard. Tome I. ThBorie de l’Electricit6 et du Magn6tisrne-Electrom6trie-Th6orie et construc- tion des G6nBrateurs et des Transformateurs 6lectriqnes. Paris et. Li6ge 1890. Kolorimetrie und quantitative Spectral-analyse in ihrer Anwen- dung in der Chemie, von G. Kriiss und H. Kruss. Hamburg und Leipzig 1890. Krystallographisch-chemische Tabellen, von A.Fock. LeipzEg 1890. Lehrbuch der physiologischen Chemie, von 0. Hammarsten. Aus der zweiten schwedische Auflage iiberaetzt vom Verfisser. Wies-baden 1890. Lehrbuch der allgemeinen Chemie, von W. Ostwald. 2te Aufl. Band I. Stochiometrie. Leipzig 1893. Kurze Anleitung zur technisch-chemischen Analyse, von L. Medicus. Tiibingen 1890. Analytische Methoden zur Nahrungsmittel-Un tersuchungen, von C. Virchow. Berlin 1890. Grundriss der allgemeinen Chemie, v011 W. Ostwald. Zweite Auflage. Leipzig 1890. Anleit ung zur Darstellung organischer Praparate, von S. Levy. Zweite Auflage. Stuttgart i890. Das Totalreflectometer und das Refractometer fur Chemiker, von C. Pulfrich. Leipzig 1890. Grundriss einer Histochemie der pflanzlichen Geaussmlttel, von H.Molisch. Jena 1890. Dictionary of Applied Chemistry, by T. E. Thorpe. Vol. 11. London 1691. 74 Text-Book of Phjsiological and Pathological Chemistry, by G. Runge. Translated from the 2nd German edition, by L. C. Wool-dridge. London 1890. Outlines of General Chemistry, by W. Ostwald. Translated by J. Walker. London 1890. Text-Book of Chemical Physiology and Pathology, by W. D. Halliburton. London 1891. Trait6 d’analyse chimique de R. D. Silva ; pabli6 par M. R.Engel. Paris 1891. Die Krystallanaly~e, oder die chemische Analyso durch Bco-bachtung der Krystailbildung mit Hiilfe des 3likroskops, von 0. Lehmann. Leipxig 1891. Confbrences faites au laboratoire de 31.Friedel. Second fascieule 1888-89: Conferences de 3131.C. ChabriB, G. Patein, V. Auger, A. BQhalet A. Combes. Paris 1891. Untersucliungen aus der Praxis der Garungsindustrie, von E. C. Hansen. Zweite Auflage. Heft I. Miinchen u. Leipzig 1890. Histoire de la Chemie, par R. Jagnaux. Deux tomes. Paris 1891. Chemistry in Space, from J. H. Van’t Hoff’s “ Dix Annkes dans 1’Histoire d’une Tlikorie.” Translated and edited by J, E. Marsh. London 1891. At the next meeting, on Majy 7th, there will be a Ballot for the election of Fello~is. The following papers mill be read :-“The act’ion of alkalis on the nitro-compounds of the paraffin series.” By Professor Dunstan and Alr. T. S. Dymond. “ The addition of the elements of alcohol to the ethereal salts cf unsaturated acids.” By Professor Purdie and W. hlarshall. “ Note on the azo-derivatives of /3-naphthylamine.” By Professor Meldola, P.R.S., and Frank Hughes. HIRXIBON AND 80N8, PRINTERS IR’ ORDIHAXT TO HER MAJESTY, ST. MARTIX’S LANY.
ISSN:0369-8718
DOI:10.1039/PL8910700053
出版商:RSC
年代:1891
数据来源: RSC
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