摘要:

Ismed 3/1/1893. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 117. Session 1892-93. _-EXTRAMEETrNG.-December 13th, 1892. Mr. w. Crookes, F.R.S., Vice-president, in the Chair. Stas Memorial Lecture. In opening the proceedings, the Chairman said:-“We are met to-night at an Extraordinary Meeting to do honour to the memory of one of the greatest chemists of this century, I might almost say, one of the greatest chemists ever known to the world. This day is the first anniversary of his death, and it is a very happy thought on the part of the Council of the Chemical Society to hold a meeting on the occasion, in order that you may hear an account given of his labours. I had the very great advantage of being, I mighf say, a personal friend of Stas. I have been in his laboratory and seen his arrangements and apparatus, and there witnessed, among other things, a large mass of chloride of potassium, which took him years to prepare, with which he had made the most refined experi- ments without detecting the slightest trace of sodium.I think that fact alone a most wonderful evidence of his marvellous skill.” Dr. Armstrong said, before reading the paper, he desired to state that it was a matter of great regret that it was impossible for Professor Mallet to be present. The Society were none the lees much indebted to him, not only for having done what was asked of him, but more particularly for the example he had set. Last year, when a discussion arose as to the steps to be taken to secure ap-propriate notices of their eminent deceased foreign members Stas and Kopp, the suggestion was made that it would be very desirable to take advantage of these and similar oppoitunities, not merely to give accounts of the work that our foreign members bad done, but inasmuch as the foreign members are always men of great distinc- 204 tion and, as a rule, moreover, men who have lived a considerable number of pears after they have accomplished their life work, that such notices should, as far as possible, take the form of critical monographs of the subjects with which they have principally dealt. It seemed that in this way the Society would he doing educational work of very considerable service to its fellows and to chemists generally.The matter was presented to Professor Mallet in this light, and there could be no doubt that he had responded in the most liberal manner possible to the appeal made to him ; moreover, it was he who had suggested that a special meeting should be held on the anniverswy of Stas’ death.The delivery that evening of the first memorial lecture, therefore, was a, very important step in the Society’s kistory. It had been arranged that the work of Kopp should be dealt with in a similar spirit by the Treasurer, Professor Thorpe, in February next, on the anniversary of Kopp’s death. Furthermore, it was pro- JWjed-and he hoped that in Mag next the proposal would be carried illto execution-that,, in like manner, on the anniversary of his death, the work of Von Rofmann should be commemorated: At present the plan was iiot fullv developed, but, it was somewhat as follows :-In ordei.to deal with the subject from an English point of view, as our German confrzres in Berlin were also engaged in the preparation of a similar accoiint, it was proposed that Lord Playfair, who was in-t,irnnteIy associated in early days with chemical science in this country, shonId recount his recollections of the state of chemistry at and prior to the time of HoEmann’s arrival in England; that Sir Predk. Sbel should follow with an account of the work done at the Royal College of Chemistry under Hofmann, compiling this witJh the assistance of the remaining friends and pupils of Rofmann ; and that the rise and progress of the coal-tar colour industry and its connexion with the Hofmann school should be sketched by Dr. Perkin, who, he was glad to say, had consented to make his cnntribution to a large extent autobiographical.Whether it would be possible also to in- clude in this memorial notice an analysis of the chief chemical work of Hofmann was not yet decided, this task being one of no slight difficulty and magnitude. The following paper was read :-81. “Jean Servais Stas and the measurement of the relative masses of the atoms of the chemical elements.” By J. W. Mallet. The story of t.he life of Stas is first briefly told, and reference is then made to his researches in other directi.ons than that of his specia.lly chosen investigation of atomic weights ; in order to fairly consider the contributions to knowledge in this latter direction which me owe tG Stas, Professor Mallet next notices the succession of funds- mental ideas which have gradually led up to the question, What is the mass of an atom of a particular element ? This historical snrvey is followed by a lengthy section on the early history of investigations as to the atomic weights of the elements up to the year 1820; after which, reference is made to determinations carried out from the time of BwzeJius to that of Stas, a list, in chronological order, of the various published investigations being given.Stas’ work is then considered, the nature of the several general questions of fundamental importance in regard to matter as studied hy the chemist, which he endeavoured to settle, being pointed out.These general questions are as follows:-1. Is the mass, or weight, of an atom of a given element an abso-In tely constant qnnntity, so that chemical analysis, properly con-ducted, must always produce, from each substance examined, strictly the snme relative quantities of the same constituents separated ? 2. Assuming that the atomic weights of the various elements are severally fixed arid immutable, are they represented by numbers which are commensurable, i.e., are the atomic weights of all the other elements integer midtipies of that of hydrogen ? 3. If we assume the atomic weights of the elements to hare con- stant, valiies and to be represented by commensurable numbers, does not this indicate that, all or most of the elements are, in reality, com- pound forms of matter-that, in short, we are as much called on to beliere in the iinity and unlimited interconvertibility of matter as in the unity and interconvertibility of energy ? 4.Do experiments with substances raised to extremely high tem- geratures justify the belief that the elements may be dissociated into simpler forms of matter ? The rigour with which Stas investigated the methods of analysis, and t<he requirements he discovered and applied with a degree of patience and skill never before used in chemical investigation having bcen somewhat fully reierred to, attention is directed to the results arrived at in the course of his elaborate researches- The titles of his memoirs are given, together with a very lengthy list of the works and papers of other authors dealing with atomic w(4ght determinations.Professor Mallet then discmses, at considerable length, the objects to be aimed at, and the methods to be pursued in future investiga- tions. 1. Attention is directed to the fact that Stas himself expressed the earnest wish that some other chemist, of sufficiently well established scientific authority, would take the trouble to check, by repetition, some one, at least, of his fundamental results. 2. It is eminently desirahle that the work which Stas did for a few of the elements be extended to the entire list of those known-to rare as well as to common elements.3. Certain of the elements particularly call for a, more searching and exact investigation of their atomic weights-tellurium is a, prominent example ; cobalt and mercury are others : of these, the former may be expected to hzve a weight intermediate between those of iron and nickel. 4. It is desirable, then, in cases, such as that of iron, for example, in which the accepted value has been determined by study of a, single change, should also be determined by cther and independent methods. 5. It is eminently desirable that an attempt be made to directly determine the ratio between the atomic weight of hydrogen and that of each of the halogens, without in any way bringing in the atomic weight of oxygen. 6. The uncertainty as regards the elements of the yttriiim group, and, in a less degree, those of the didymium group, requires clear- ing up.7. It would be well to submit to experiment, by means as refined as those employed by Stas, the question of the absolute exactness of the well-known law oE “ multiples.’’ 8. Further enquiry into the close approach of so maqy atomic weights to the integer multiples called for by Prout’s hypothesis is requi red. 9. It is necessary that the apparent periodic relationships among the elements should be discussed, not merely, as heretofore, with the aid oE roughly approximate atomic weights, but with exact weights, and, therefore, that more precise determinations of the numbers we would discuss should be made. In the final section of the paper, the methods which it is desirable shall be pursued in the determination of atomic weights are discussed in detail, under the following heads :-1.Selection of analytical or synthetical processes. 2. Use of pure materials. 3. Vigilance in regard to extraneous or accidental causes of error. 4. Choice as to the quantities of materials to be used. 5. Practical precautions as to accuracy in manipulation. 6. Precautions in regard to weighingd. 7. Measurements by volume of liquids or gases. 8. Calculation of results. 9. Advantage to be derived from the application of greater working force and ampler means than can be commanded by private indivi- duals to the determination of atomic weights. In this section, Pro- 207 fessor Mallet advocates the establishment of a laboratory in which a small corps of competent chemists should be engaged solely in revis-ing the whole list of atomic weights, with every precaution that could be devised to secure accuracy.10. Final form of statement of result. In this section, it is argued at length that all atomic masses should be expressed in terms of the mass of the hydrogen atom taken as unity. The adoption of any other basis tends to confuse the consideration of any natural relations between these constants, as has been pointed out by Stas himself in reference to the hypothesis of Prout ; numbers which,, on the basis of 0 = 16, come very near fo integers, ceaseto do so when H is taketi as unity, and 0 has its true value, as determined by experiment, assigncd to it.The paper will occupy fully 60 pages in the Society's Transactions. The Chairman in proposing that hoarty and sincere thanks be givcn to Professor Mallet for his paper, said the suggestions he had made were most valuable, and it was to be hoped they would stimulate the younger chemists to carry out investigations such as he had referred to. He could not help feeling that Stas was more honoured among the English-speaking races than on the Continent. On the occasion of his lamented death, 12 mouths ago, the scientific societies oE Belgium petitioned the Government to purchase his apparatus and some of hi3 piire materials, and as many of his works could not be purchased, either because they were out of print or had been published in an inaccessible form, that funds shoald be voted for t'he publication of R complete set of Stas's memoirs and papers.After a considerable delay, the answer of the Govemment. was to the effect that the schools were sufficiently supplied with apparatus and preparations. There was one memoir that Stas wrote that would be most valuable if it could be published, but he heard it was locked up in a Govern-ment Department. Stas was employed by the Government to investi- gate and determine the suitability of alloys of iron and other metals for the manufacture of heavy ordnance ; his ressarches on the sub-ject were most valuable, and he obtained some most important results : but hitherto all applications for permission to peruse his reports have been met with arefusal.I€they could be made public, they would undoubtedly be of great value, both scientifically and practically. Dr. R'ussell said that abont 25 years ago, when working on the atomic weights oE nickel and cobalt, he had the pleasure of seeing Stas in London, who took a very considerable interest in this work ; at that time he had met with certain difficulties in purifying nickel: Stas took considerable interest in the matter, and wrote out for him a paper of instructions recommending him to follow a certain course, and, only a month or so ago, he happened to come across this. Professor Dewar said that he was sure all must agree that one of the greatest services that could be rendered to the memory of Stas would be the complete publication of his memoirs. Resident as he had been in Belgium during a very interesting period of chemical history, he knew something of the support Stas gave to what, at the time, was a most revolutionary addition to chemical science.All present were aware that Kekul6 was Professor in Ghent during many years, and the speaker was sure that Ire would be the first to acknow- ledge that it was largely owing to Stns's influence and assistance as an authority in Belgium, not, only as a scientific man, but as a mem-ber of tho highest social and political circles, that he was so splendidly supported by the Belgian Government. Furthermore, when the early memoirs of Kiirner, that are now classic, in which he suggested the position theory as an addition to the benzene or ring theory of Kekul6, were first submitted io the Belgian Academy, it was really Stas who secured their publication, arid it was his encouragement of Korner's work that promoted the advent of the position theory in organic chemistry.To touch on the vast work of his life, and to attempt to criticise his researches, inakes an ordinary observer Feel exceedingly small. Xe always felt that, in comparison with modirn work, a paper by Stas was an oasis of intellectual fruitfulness in a desert of arid vapid publication. We were all alike; we were all equally to blame ; at home and abroad there was the same general tendency : the result being that our scientific literature is burdened by too many trivial, common-place productions, exhibiting no trace of any desire to cultivate originality or thoroughness.No chemist could read a paper by Stas without feeling himself an exceedingly small man. The noble inheritance left by Stas to chemists must live for ever, and it will always be a pleasure to any chemist wishing to cultivate his higher faculties, to read and study, atnd attempt to imitate his works. Professor Dewar then referred to the determinations of the atomic weight of manganese and of the molecular weight of triethylamine, which he had carried out in conjunction with Dr. Scott (cf. R.SOC. Proceedings, 1883, 35, 44,347). We were greatly indebted to Pro- fessor Mallet for the admirable r8sume' he had given, and for his friendly and critical remarks.He also, said Professor Dewar, was of opinion that the near approach in quite a number oP the atomic weights to whole numbers is still a, matter of very serious suggestive iiiterest, and he proceeded to call attention to the results obtained on taking into account the values that the lrrte Professor Dittmar found for the oxygen and hydrogen ratio, remarking that no man more 209 competent to deal with this subject could be found, and that all must deeply deplore his loss while engaged in doing such splendid work on the very question under discussion. If we accepted Ditt- mar’s number, which is corroborated by nearly half a dozen separate researches, 15-87, as expressing tbe ratio between the atomic mass of oxygen and the atomic mass of hydrogen, it appeared that the best- determined atomic weights fall into two totally different categories ; some that apparently could not possibly be regarded as multiples of that of hydrogen approaching nearer, while otlhers, seemingly very near to, are now far from being multiples of the atomic weight of hydrogen.Thus, silver, taking the Dittmar ratio, would come out very nearly a whole number, viz., 107.046. The most recent de-terminations of copper would give the value 6309. Tin would be within 0.1 of a unit. In the same way, antimony would be within 0.1. Iodine, however, would be out. Zinc, also, would be de-cidedly out. Berjllium would be iiearly a whole number.Bromine would be 0.26 out. There could be no doubt that in the case of gold, the number would be 195.61 ; while platinum would be 1953.28, cerium 139.06, and boron 10.87, or near thaf. Professor Mallet made reference in his paper, he believed, to chlorine as an element which no one anticipated would come nearer a whole number than half a unit; but, as ti matter of fact, chlorine now came within 0.2, viz., 35-16of this element, and would fall into the class nearly approaching whole numbers. He noticed that Mallet had adopted the latest value of nitrogen. In his 1865 paper, the value 14.045 was given by Etas as the result of a very large number of determinations. Professor Deww said he believed the number 14.055 was deduced entirely from experiments on the synthesis of nitrate of silver.Stas was so coti-scientious that he altered the value from 14*045 in his later paper in 1873, he believed, because the weight of nitrate of silver obtained by synthesis before fusion differed very slightly from the weight after fusion, and he thought that it was not fair to depend on the weight after fusion, because there might be a slight loss of nitric acid Consequently, in his later paper, he adopted 14.055, but that num- ber is the result only of two determinations of the synthesis of nitrate of silver, whereas, in 1865, there were 10 or 12 diEerent reactions from which the atomic weight of nitrogen was shown to be 14.045, not 14,055. This led him to remai-k that if we took the weight of amrxonium as directly determined, which is probably as accurate a weight as any of Stas’s numbers, viz., 18.076, and deducted 14.045 from it, the atomic weight of hydrogen relatively to 107.9 of silver or 16 of oxygen was 1.0077. That would give a ratio of the atomic weights of hydrogen to oxygen, transforming hydrogen to unity, of 1to 15.88, SO that Stas’s determination of the weight of ammonium, 210 deducting his own value for nitrogen, gives the ratio of the atomic weight of hydrogen to oxygen found by Dittmar, Rayleigh, and all the more recent investigatoi.~.He did not say this result is a coin-cidence ; it must be due to the accuracy with which Stas determined the separak atomic weights. It was interesting to observe that the most recent density determinations gave both nitrogen and oxygen a little too high from the gravimetric point of view.Thus the de- terminations of Leduc make nitrogen and oxygen respectively 13.99 and 15.9 instead of 1393 and 15.87; this was what we should expect if the oxygen, as we believe, be a little too dense, being nearer its critical point than hydrogen is, and the same applies to nitrogen. He could not help thinking the proposal made by Professor Mallet that the determination of atomic weights should be given to a Board would not turn out quite satisfactory in practice. But there were many points all would wish to clear up, and it would be a noble piece of work for scjme one to follow out Stas’s own work, namely, to repeat any one of his fundamental syntheses.It would require a man of the type of Dittmar to do such work, however. Dittrnar had, in fact,, attempted the redetermination of one of Stas’s values, and it was very important that we should have an explanation of the difference between the two workers. Dittmar had found in the case of lithium a number something like 6.86, whereas Stas’s value was 7.02. Ditt-mar’s method involved the analysis of lithium carbonate. He also determined the value of sodium by a similar method and obhined absolutely the same Talne as Stas fcr sodium. What was the ex- pla,naticn of such a remarkable difference in the value found by the Stas method ? In the case of cadmium, also, there was apparently difference of half a unit between some of the determinations. What was the reason of these d‘ifferences? He referred to such cases as these two of lithium and cadmium, but there were others, and the problem was to find out how it is that methods nearly equally accurate, but differing essentially, give such discordant results, the work being carried out with the accuracy nowadays attainable.Finally, he was very glad to have had the opportunity of expressing his grateful thanks for the kindness of Stas in the past, and of bearing testimony to the great service he had done to science. Dr. Scott referred to the work on which he was engaged in con- nection with Lord Rayleigh, with the object of determining the den- sities of oxygec and hydrogen, he having undertaken the determina- tion of the volume ratios.Lattedy, he had prepared hydrogen by passing steam into sodium, condensing it in palladium, and had ob-tained oxygen from oxide of silver ; the experiments were made with successive fractions of the two gases driven off from, the solid mate- rials, which were kept in vacuous chambers sealed on to the gas 211 onalysis apparatus. He had now succeeded in obtaining the oxygen and hjdrogen so pure that from the first fraction to the last he could detect no difference between them in the last series of determinations ; whereas on using the hydrogen directly prepared from sodium and steam the ratio was 1to 2.00243, that calculated on the whole of the hydrogen separated from the palladium was 2.00243. The last two figures he could hardly depend on.Dr. Bailey thought that the extraordinary care taken by Stas in preparing and examining his materials, and in studying the changes made use of in his atomic weight determinations, served perhaps more than anything else to impress the student of his works. Refer-ring to his own xork, he mentioned having noticed that materials which are generally regarded as stable and non-volatile may be carried off by steam when their solutions are slowly boiled. Was it not conceivable that potassium chloride might thus be carried off in quantity sufficient to influence an atomic weight determination ? He next spoke of the difEculty of obtaining concordant results in deter- mining chlorine in the compounds of platinum metals.How this arose he was not able to sa8y,but other workers had met with similar difficulties. In closing the discussion, the Cbairman expressed agreement with previous speakers that atomic weight determinations could not well be carried out by an organisation such as Professor Mallet had sug-gested. December 15th, 1892. Dr. W. J. Russell, F.R.S., Vice-president, in bhe Chair. Certificates were read for the first time in favour of Messrs. John Pedrozo d’albuquerque, Barbadoes, W.I. ; William James Cowan, 77, Trinity Road, Wood Green, London; George Davey, Las Trojes Angangues, Michoacan, Mexico ; Daniel 0.Sydney Davies, Khydfallen, Stonebridge Park, Willesden, N.W. ; Samuel Felix Dufton, D.Sc., Spring Wood House, New Cross Street, Bradford ; John Henry Evans, 71, Lambton Road, Cottenham Park, Wimbledon ; Charles Thomas Tyrer, Stirling Chemical Works, Stratford, E.; James Robert Thackrah, M.A., Technical Schools, Plymouth ; John Cundell Wood, 3, Bedford Terrace, Sunderland. The following were duly elected Fellows of the Society :--David Averg, Samuel Robert Adcock, William Smellie Anderson, Horace 212 Vincent Butterfield, Arthur John Bensusan, Arthur James Cooper, Frederick Walter Carlton, Ernest Victor Clark, Andrew Campbell, Andrew William Craig, Lionel Cooper, Joseph R. Denison, Thomas Duxbury. Martin Onslow Forster, William French, Walter Goodall, William Thomas Gronow, Thomas Gray, James G. Hardy, Walter S. Haines, Samuel C. Hooker, Ph.D., Edqar Edward C.Horwill, John Horsfall, Walter Holinshed Ince, Ph.D., John P. V. Tsaac, Samuel Jackson, John Jackson, William George Johnston, G. Krause, Ph.D., Kunwar Kishor Kacker, Thomas Torrens Knowles, Charles Thornton Lamb, Francis Colin Moorwood, John Rate Nicholls, James Wyllie Rodger, Hugh Ra,mape, Norman Scott, Rudolf, James Robson, Augustus Schloesser, Ph.D., Ernst Speidel, B.S., George Arthur Shaw, Reginald des Forges Shepherd, William James Sell, Satvaprasad Sarbadhicai*y, Charles Spackmnn, Albert Henry Tnrton, N. T. M. Wilemore, William Williams, Jno. Lowe Whi teside, Jno. Williams, Frederick Henry Wigham, Frederick William Westaway. Of the following papers those marked * were read :-“82. “ The idcnt,ity of caffeine and theine and the interactions of caffeine and auric chloride.” By Wyndham R.Dunstan and W. F. J. Shepheard. Mays (Jowr?%.Physiol., 7, 458; Th~rapeutic Gazette, 1866, 587) and more recently Lauder Brunton and Cash (Ro!y. Soc. Proc., 42, 238 ; Jozwn. PhysioZ., 9, 112) having concluded that “theine” from tea differs in its physiological action in certain respects from “ caffeine ” from coffee, the aiithors have deemed it desirable to compare t,he products from the two sources : they conclude thrit, their identity is beyond question. The observed differences in physiological action must be ascribed either to impurities in the materials used, or to differences in the animals to which they were administered; the circumstance that “ theine ” has been found to be more active and to be capable of producing effects not produced by “caffeine ’’ tends to support the view that the “ theine ” was impure, especially as it is known that tea contains other alkaloids.It is found that when an aqueous solution of caffeine aurichloride is heated, a yellow, flocculent, precipitate of aurochlorocafeine is gradu-ally formed, the C,H,,N,02*HAuC1, being resolved into 2HC1 and CsH,(AuC12)N402; this substance is insoluble in alcohol, chloroform and ether, but dissolves in chlorhydric acid, being reconverted into the aurichloride ; it is contended that the production of this com-pound is better shown by Medicus’s formula of caffeine than by that proposed by Emil Fischer. A compound of caffeine and potassium 213 ~iurichlorideis described, crystallising in dark-red needles ;it readily dissolves in alcohol and water, but apparently dissociates.DISCUSSION. Professor TILDEN, referring to his work on periodides of alkaloids pubiished over 25 years ago (C. 8.Journ., 18,99 ; 19, 14,5), said that he had not been able to notice any difference between the periodides prepared from caffeine and theine. "83. '' Studies cn isomeric change. 11. Orthoxylenesulphonic acids." By Gerald T.Moody, D.Sc. The results described in this and the following note have been obtained in the course of an investigation on isomeric change now being carried on at the Central Institution (cf. these Proceedings, 1888, 77) ; the object in view was to determine whether 1:2: 3-orthoxylenesulphonic acid is converted on heating into 1:2 :4-orthoxylenesulphonic acid.In order to prepare tho Z :2 :%acid, orthoxylene was first treated with two molecular proportions of biomine, whereby it was converted into a mixture of the liquid and solid dibromo-orthoxylenes ; the latter (m. p. 88")-which has been shown by Jacobsen to have the constitution 2CH, : 2Br = 1:2 :4 :5 -was sulphonated by very cantiously heating it in a water-bath with about 10 times its weight of 15 per cent, anhydrosulphuric acid until the mixture became liquid, then keeping it at 75", with con- stant shaking, until complete dissolution of the oil was effected ; the liquid solidified on cooling. The resulting sulphonic acid was con- verted first into barium sal't and eventually into sodium salt.Sodium dibromo1. thoaylenesulphonat e, C6HCr2(CH,), S0,Na + 14H,O, crystal-lises in small' scales, and is easily reduced on boiling it with zinc- dust and sodium hydroxid'e, forming 1:2 :%sodium orthoxylene- sulphonate. The latter crystallises in beautiful, long, flat, mono-hydrated plates ; unlike the sodium salt of the 1:2 :4-acid, it does not effloresce in air. 1: 2 :3-Orthoxylenesulphonic chlorids crystallises from light petroleum in prisms meltiiig at, 47", the sulphonamide crystallising from water in groups of needles melting at 167". The 1 : 2 : 3-wlphonic chloride was converted into the acid by heating 5 grams of it with 20 C.C.of water in a sealed tube immersed in the vapour from boiling xylene, the tube being, from time to time, removed from the bath and shaken ; the resulting solution was cautiously evaporated on a steam-bath.The crystalline acid thus formed remained dry on being exposed to the air for several days ; a small portion was converted into sulphonamide, which melted sharply at 167", showing it to be the unchanged 1:2 : 3-acid; the rest was 2 14 placed in a tube standing in an oil-bath heated at 115-120", and a current of dry air drawn over it during two hours, at the end of which time the acid had become dark grey in colour. The sulphonamide prepared from the thus-heated acid melted sharply at 144", showing that the 1: 2 :3-acid had been completely converted into the isomeric 1: 2 : 4-acid.On repeating the experiment, the same result was obtained ; and it is worthy of remark that in both cases only a very slight indication of the formation of sulphuric acid was obtained. "84. " Studies on isomeric change. 111. Phenetoilsulphonic acids, C,H,(OEtjSO,H." By Gerald T. Moody, D.Sc. In a note published early in the year (these Proceedings, 1892, 90) the author stated that oiily one sulphonicacid is formed by the inter- action of sulphuric acid and pheJetoi1 under ordinary conditions ; Lagai not long afterwards controverted this statement (Be?-., 1892, 1839) and asserted that he had isolated it second acid frorn the pro-duct of sulphonation : describing its chloride as a syrupy liquid, and its amide as crystallising €ram water in feathery iieedles melting at 146". Lagai however, quoted no analyses, or other evidence to show that his compound melting at 142" was really a derivative of phenetoil.In order to obtain orthophenetoilsulphonic acid, parabromophenol was ethylated. The bromophenetoil thus formed boiled constantly at 228-230", and readily sulphonated when shaken with an equal bulk of ordinary oil of vitriol. The resulting bromophenetoilsulph-onic acid crystallised from the acid solution in characteristic prisms. It was readily reduced by digestion with zinc-dust arid sodium hydroxide solution. The sodium salt of the resulting ortho-acid, C6H,(OEt)S0,Na + H,O, crystallised in slender needles ; it afforded a sulphonic chloride which crystullised from light petroleum in thin plates melting at CB", from which a sulphonamide was obtained, crys- tallising in very long, flexible needles, melting at 156".These melting points place beyond doubt the fact that Lagai's compound molting at 142" is not phonetoilorthosulphonamide. On the other hand, the sulphonic acid giving a chloride aiid amide melting at 62" aud 156", respectively, is shown to be a plienetoil derivatike by its behaviour on heating. The pure acid was formed by digesting the sulphonic chloride melting at 62" with dilute alcohol for 12 IIOUTS, and then evaporating the solution ; it mas obtained as a crystalline mass, per- mauent in air. A small quantity of this product was converted into sulphonamide, which was found to melt at 156"; the remainder was placed in a tube contained in an oil bath and heated for three hours at looo, a current of dry air being passed through the tube ; during 215 the process, the acid darkened somewhat in colour, and was eventually found to contain a minute qaantity of sulphuric acid.The acid thus heated gave a sulphonamide which meltTedsharply at 1.50", showing that a complete change to the para-acid had taken place. %5. "Formation and nitration of phenyldiazoimide." By William A. Tilden and J. H. Millar. Phenyldiazoimide, N3*C6H5,is readily prepared by the interaction of nitrosyl chloride and phenylhydrazine dissolved in excess of g!acial acetic acid, together with ouly a small quantity of resinous bye-products. When gently heated with ordinary strong nitric acid, the imide yields about two-thirds of its weight of the paranitro-derivative (m.p. 74")' together with smaller quantities of two crystalline bye-products not yet fully examined. Nitrophenyldiazo-iniide forms a convenient source from which to obtain Curtius' diazoimide, about 40 per cent. of the calculated quantity of the compound being obtained, as shown by Noelting, Grandmougin and Michel (BEY.,25, 3328), on boiling it with alcoholic potash. *86. "The production of naphthalene derivatives from dehydracetic acid." By J. N. Collie. The author has further examined the yellow substance referred to in his previous notice (these Proceedings, 1892, p. lSS), and arrives at the conclusion that the condensation of diacetylacetone probably occurs in the followiiig manner :-CH,-v=CH-C=CH-C-CH3 pJQ - cH3(YJ:cH;CHI,-CO-C.h.-C0-~-CO-CK, UH UH At first he was inclined to the belief that the substance was a quinone, but, as all attempts to reduce it failed, and as itl did not, iii other respects, behave as a quinone, he has abandoned the idea; moreover, it is impossible to explain the formation ot' a quinone from diacetylacetone by any simple interaction such as the mere elimina-tion of the elernelits of water involves.The substance yields a diacetyl derivative when heated with acetic anhydi-ide, and affords bromine substitution derivatives when treated with bromine. A trimethylnaphthalene is produced on distilling the diacetate with zinc-dust. Finally, it is pointed out that the 2-aceto-1-naphthol described by Wilt (Ber., 21, 321) and the 3-aceto-1-naphthol prepared by Erd- 216 mann (ibid.,p.635) closely resemble the compound from diacetyl-acetone. 87. "A new synthesis of hydrindone," By F. Stanley Kipping, Ph.D., L).Sc. In a previous note (these Proceedings, 112, 107) it has been stated that a hydrocarbon of the composition C,H2 and other compounds are produced by the action of phosphoric anhydride on phenylpropionic acid ; as the whole behaviour of the hydrocarbon pointed to its having a high molecular weight, it seemed probable that its formatioil was brought about by the condensation of tno or more molecules of some intermediate product, possibly hydrindone. As this assumption could only be satisfactorily settled by preparing the hydrocarbon from hxdrindone, attempts were made to synthesise the latter by treating phenylpropionic chloride with aluminium chloride ; a few trials had already been made, with but sliglit success, when the writer's atten-tion was called to a note by Hughes (these Proceedings, 96, 70), in which similar experiments with phenylpropionic chloride, carried out at Marsh's suggestioii, were described ;on continuing the experiments, it was soon found that, although HEghes failed to obtain hydrindone, it can be easily prepared in large quantities by the method suggested, and that, under suitable conditions, the yield of pure compound is 50-60 per cent.of the theoretical, its formation being expressed by H2-CHz*COC1= C6H,<~~>cHzthe equation C6H5*C + HCl.The ketone prepared in this way crystallisea in colourless, waxy plates meltiiig at 41--42"' and is identical with the hydrindone ob- tained by Gabriel and Hausmann (Bey., 22, 2019) from ethylic orthocyanobenzjlacetate, and by Konig (Inaug. Diss., Leiyxig, 1889) from orthocarboxyhydrocinnamic acid. Several derivatives of hydrindone have been prepared and charac- terised :-The hydrazone, C,,H,,N,, crptallises from dilute alcohol in almost coloiirless needles melting at 127-1'28". The hydwxime, C7,Hs:NOH, cr.ystallises from benzene in colourless needles melting at 140-141". The wifro-derivative, C,H,O*NO,, is a colourless, crystal- line substance melting at 75-76". When he 1ted with moderately concentrated sulphuric acid, hydr- indone yields a compound of t,he composition C18H,,0; this condensa- tion product crystsllises from dilute alcohol in yellowish plates melting at 141*5-142-5".When warmed with phosphoric anhydride, Iiydrindone is converted into a yellowish, crystalline substance, which, judging from its general behaviour, is identical with the hydrocarbon obtained by treating phenylpropionic acid with phosphoric anhydride. 217 The investigation is being continued in other directions, as it appears probable that similar intramolecular condensations may be brought about in the case of other benzenoid compounds containing a side chain with the aid of aluminium chloride. 88. " The resolution of methoxysiiccinic acid into its opticalIy active components." By T.Purdie, Ph.D., B.Sc., and W. Marshall, B.Sc. The authors find that inactive methoxysuccinic acid-prepared from fumqric acid by the addition of the elements of methylic alcohol-can be resolved into optically active components by means of the acid cinchonine salt, the salt of the dextrogyrnte acid being less soluble in water and crystallising moye readily than the corre- sponding salt of the laevogyrate acid. The separation of the active acids effected in this manner, however, was ozily partial, th;! mctallis salts obtained after removal of the cinchonine being mixtures of active with more or less inactive salt, from which the latter had to be separated by fractional precipitation or crystallisation. In a first series of experiments the elimination of the inactive salt was effected by means of the different solubilities of the calcium and hydrogen potassium salts, the salts of the active acids being more soluble than those of the insct'ive acid.When solutions containing equal quantities of the oppositely active hydrogen potassium salts were mixed, the inactive salt was instantaneously precipitated. The specific rotatory power of the active acids in a 5 to 10 per cent. aqueous solution is about 33"; they melt at 88-90", the iuac- tive acid melting at 108". The qecific rotatory power of the normal ammonium and potassium salts is of the same sign as that of the acids, but not so great, and it does not vary much with change of concentration ; that of the calch and barium salts is of opposite sign to tbat of the acid, and diminishes rapidly with decreasing con-centration, the sign of the rotation of the latter salt being reversed in very dilute solutions.$39."Optically active ethoxysuccinic acid." By T. Pnrdie, Ph.D. B.Sc., and I. Wallace Walker, &LA. When spores of Penicillium glauczim are sovn in a solution of the inactive acid ammonium salt of the inactive ethoxysuccinic acid formed by the addition of the eltments of ethylic alcohol to fumaric acid, to mhich nutritive mineral salts 1,are been added, an abundant growth of mjcelium ensues, the result being that the Iaevogyrate component of the inactive acid is consumed, the dextrogyrate 218 'bein? left unaltered. The specific rotatory power of the acid in a 5 to 10 per cent.solution is about +33" ; it melts at 76--,?0", while the inactive acid melts at 86". The active acid nmrrionium salt crystallisps with one molecular pro- portion, the corresponding inactive salt with half a molecular pro- portion, of water. The inactive acid can also be resolved into its active components by means of the cinchouidine salt, the salt of the dextrethoxysuccinic acid being less soluble in water than its oppositely active isomeride. The active components were not obtained in the pure state by this process, hiit oppositely active acid ammonium salts were obtained which crystallise exactly like trhe salt prodnced by means of PeiziciZ-Zi~cm,and whose specific rotations approximated in amount to that of the latter.The authors find a close parallelism in respect of optical activity between the dextromethoxysucci~iates, and dextrethoxysuccinates, tlie remmks about the former in the preceding abstract applying in general to the latter. The ethoxysucoinates are, however, more dextrorotatory or less laevorotatory than the corresponding mehhoxy- succi nates. The bearing of some of thctse observations on the theories advanced by P. A. Guye (Annulen, [6], 25, 145) and by Crum Brown (Proc. 3.8. E., 17, 181) regarding the relations of opkicnl activity to the nature of the radicles which are united to the asymmetric carbon atom is discussed. 90. '' The formation of benzyldihydroxypyridine from benzyl-glutaconic acid." By S. Ruhemann, Ph.D., M.A.Ethylic benzylglutaconate (cf. AnnuZen, 222, 262) slowly dissolves in a concentrated aqueous solution of ammonia at loo", forming a coloured liquid, from which acids precipitate benzyldihydroxypyridine -a substance which exhibits both acid and basic properties. It crys-tullisps in glittering plates which melt at 184"; its dibenzoate melts at 164". On oxidation, it readily Fields coloured products possessed of tinctorial powers. 91. "The action of nitrous acid on 1-a-amido-2-p-naphthol: a correction." By R. Meldolrt, F.R.S. In a paper published conjointly wit'h G. T. Morgan (Trans., 55, 114): wherein we had occasion to identify a-amido-/3-naphthol in the presence of other bases, we stated that the yellow crystalline snb-stance obtained by the action of nitrous acid was nitroso-@naphthol.219 At the beginning of the present year a, paper by Grandmougin and Michel appeared (Ber., 25, 972), in which these authors stated that the compound in question was 6-naphthaquinone. I repeated the experiment, at the time, and confirmed their statement. Tbey have called attention to the discrepancy in another paper just to hand RAT.,25, 3429), and ask for furkher details. In reply, I have only to state that I was not particularly concerned at the time with the nature OE the crvstalline compound, and it was not very closely investigated, as will be seen on reference to our paper (Zoc. cit., p. 120). The snperficial examination of the substance which we made led us to tbc helief that it was nitroso-/%naphthol, as it had a similar melting point, and was soluble in alkali, and the subject was not further pursued, as it was beyond the scope of our investigation.The subsequent investizations by Grandmoa Tin and Michel have convinced me that the snbstance which we had in hand was impnre /J-naphthnquinone, possibly mixed with some P-naphth aquinoneanilide, owiny tn the retention of ;Itrace of aniline salt. The formation of /3-naphthaquinone by the action of nitrons acid on a-amido-p-naphthol is a most unexpected discovery, which conld not possibly have been foreseen, and the credit of which is entirely due to these authors. have frequently had occasion to repeat this test in the coiirse of some recent investigations of which the results mill be communicated to the Sqciety snbsequently : the method described by Grandmoupin and Michel is certainly the simplest and by far the most eflective pet made known for preparing pure P-naphthaquinone in large quanti- ties.92. "Note on the action of phenylhydrazine on mono- and di- carboxylic acids at elevated temperatures." By W. R.Hodgkinson and A. H. Coote. Phenylacetic acid and phenylhydrazine readily interact when heated together at 120", forming CsH5*N?H~.CO*CH2*CsH5(BUTOW,Annden, 236, 196). In preparing this and similar hydrazides for another investigation, it was observed that a certain amount of decomposition took place, ammonia being one of the products.The course of tohe decomposition in the case of several monobasic benzenoid acids was, therefore, studied. When heated with an equivalent quantity of phenylhyd~azine phenylacetic acid at first gives off water at temperatures up to 150", the act'ion then becomes more energetic, nitrogen and ammonia baing evolved, light oils distilling over ; and as the temperature is raised, between 260"and 350",a, thicker oil distils over, a slight tarry residue being left in the retort. The lighter oils were found to con- 220 sist of benzene and aniline. The greater portion of the heavy oil boiled between 320"and 370"C. On fractionating, a heavy substance was ob- tained, boiling at about 340",free from nitrogen, which on analysis gave figures corresponding to the formula G14Hl2O2=CsH,*CH2*C0*C6H5, viz., 85.8 per cent.carbon and 6.22 per cent. hydrogen, the theoretical values being 86.0 and 6.12. The decomposition cannot be very directly formulated. The first stage is the formation of the hydrazide, CGHg*CH2*CO*NH.NH*C6Hg; but on heating this, NH-NH is split off, which immediately breaks up and reduces neiqhbouring molecules of phenylhydrazine partly to aniline and partly to benzene, with liberation of nitrogen and am- monia. In the case of orthotolnic acid, C,H,*CH,*COOH, a similar action takes place, but the amount of high boiling oil (ketone) is somewhat less, and the amounts of benzene and aniline somewhat greater. In the case of phenylpropionic acid action also takes place in a manner analogous to that observed in the case of phenylacetic acid.Some dibasic acids, for example, succinic acid, exhibit a behavionr similar to that described when heated with phenylhydrazine, am- monia and nitrogen escaping, while a high boiling oil, free from nitrogen, distils over. The authors desire to reserve the further study of these inter- actions for a short time. RESEARCH FUND. A meeting of the Committee will be hold in Jannnry. Fcllows desiring grants are requested to make application to the Secretaries before January I4th . KOPP MEMORIAL LECTURE. An extra meeting of the Society will be held on February 20th, 1893, at 8 P.M., the anniversary of the death of Hermann Kopp, when a lecture will be delivered by Professor Thorpe, F.R.S. HABBISON AND SONS, PRINTEBS IN OBDINARY TO HER MAJESTY, ST. MARTIN'S LANE.

ISSN:0369-8718    

DOI:10.1039/PL8920800203

出版商:RSC    

年代:1892

数据来源: RSC