|
1. |
Proceedings of the Chemical Society, Vol. 12, No. 160 |
|
Proceedings of the Chemical Society, London,
Volume 12,
Issue 160,
1896,
Page 25-40
Preview
|
PDF (1073KB)
|
|
摘要:
Issued l8j2/ 1896. PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY TDE SECRETARIES. January 23rd, 1896. EXTRA Mr. A. G. Vernon Harcourt,, MEETTKG. President, in the Chair. Professor G. F. FITZGERALD,M.A., F.R.S., of Trinity College, 11ublin, delivered the Helmholtz Memorial Lee ture. The position of the work of Helmholtz was considered with special reference to its chemical aspects, and the later work that had been grafted upon it. Some of the valuable points in the vortex atom hypothesis of matter were noticed, and some of its serious difficulties considered. Analogies on this hypothesis to the asymmetric carbon atom and to the benzene ring were pointed out. The applications of thermodynamics to chemistry were noticed, and a theoretically perfect, semi-permeable diaphragm for non-volatile salts in solution, in which the actions at all points are known, was described.The theory that a substance in solution is like a substance in the gaseous state was criticised, aiid it was contended that from Helmlioltz’s work, and on dynamical grounds, the conditions could not be slike. The theory that’ there was combinatioii between the solvent and body in solution was put forward as a complete explanation of the known phenomena of solution and electrolysis. It was pointed out how Helmholtz had, by his work, made important steps forward in several directions towards a dynamical explanation of Nature. D~scussros. The PRESIDENTsaid that, there were two ways in which we may do honour to a great fellow worker who has passed away.The one is by a rehearsal of the great things he had done; the other-and 26 perhaps this is rather that which the greatest would wish should happen after their own time has passed-is by a continuation of the lines of thought which they have started, and by following the work an which they have been engaged. Of the great variety of work which Helmholtz undertook-and there can scarcely be a greater scientific name than his, if the quality and variety of the work in Tvhich he engaged are taken into account-the lecturer this evening bas naturally insisted on that side which Helmholtz himself selected as most appropriate when he was lecturing to this Society in the year 1881. These inquiries into the nature of molecules and other similar physical speculations which our lecturer this evening has touched upon, are of more recent growth.These are the problems which form our inheritance from that great man. Where work was so abundant there could scarcely be more than the enumeration of the great scientist results which we owe to Helmholtz. There ai=e present this evening, besides many or” our older members, several distinguished men of ficieiice who will say a few words on the sub- ject of the lecture in proposing a vote of thanks to Professor Fitz- gerald for the admirable exposition for which the Society is 80 muc’i indebted to him. Sir JOSEPH P.R.S., said he had much pleasure in proposing L~STER, a vote of thanks to Professor Fitzgerald for his profound and brilliant lectiire.For his own part he felt himself in a world in which he was almost an entire stranger. These magnificent conceptions of physics must necessarily be nearly a terra incogizitu to the surgeon and physician. But physiologists and surgeons are deeply indebted to Helmholtz for what he did in their own domain. They recall with pride that Helmholtz was, in the first instance, a medical practitioner. It is an exceedingly remarkable fact in the case of such a profound and distinguished a physicist, that to the last he retained his love for his old subject, physiology. On this occasion it is not possible to allude to all that physiology owes to Helmholtz, but there are two questions to which reference might be made-his explanation of the accommodating power of the eye for different distances, and what has been for physiologists and ophthalmic surgeons-although Professor Fitzgerald regarded it as a mere triviality in Helmholtz’s achievements-the great invention of the ophthalmoscope, that beautiful instrumeiit by which the interior of the eye can be both illuminated and inspected.How much added to our knowledge of the physiology of the eye, and to the diagnosis of ophthalmic disease, and, consequently, to ophthalmic practice, and also to our knowledge of the various diseases which are found to be dependent upon or connected with affections of the eye-these dis-coreries, even if nothing else had been accomplished by Helmholtz, 27 would be enough to secure the gratitude of physiologists anJ surgeons.Dr. EDWARD said he had great pleasure in seconding FRANKLAND the vote of thanks. He expressed the feeling of every Fellow of this Society in saying that Professor Fitzgerald had given an hour’s dis- course of enormous interest and importance to chemists. It would take some time to study and analyse this discourse, and tc! adequately discuss it in detail ; but, whilst chemists had listened to the discussion of numerous points of contact of the work of Helmholtz with their own department of science, they were led anew to admire the intellect of that great man who left, perhaps, no branch of human knowledge untouched during his career. Professor Fitzgerald’B references to the application OF vortex motions to the explanation of the chemical combination and valency were somewhat discouraging, and there were one or two other sections of his discourse which he hoped and believed were slightly too pessimistic.We may hope that when another four or five decades have passed we shall arrive at a point when these physical theories which appear to us at the present moment almost impossible of application to chemical science will then appear perfectly clear ; and when in this room, possibly, another Helmholtz is to be honoured in this way, we shall have the satisfaction of seeing these beautiful physical theories applied with effect to those obscure chemical phenomena on which we are all so anxious to have more light thrown.Lord RAYLRIGHsaid that he might be allowed to add his con-gratulations to the Society on having secured Professor Fitzgerald to give this most int,eresting lecture upon certain aspects of the work of Helrnholtz. He has done it in a may that fern others, indeed if any other, coulll do it. It is to be hoped tbat chemists will take into grave consideration the emphatic warning that Professor Fitzgerald has given, particularly as to the danger of supposing that there is any dynamical similarity between the condition of a gas and that of a dis- solved substance in a liquid. He quite! agreed with much that had fallen from Professor Fitzgerald upon that subject. There is possibly a risk of pushing formal analogies too far, and of supposing that there is a real clynamical similarity, whereas there is, perhaps, only a similarity in mathematical law.Many of the ideas that he has broached required prolonged thought and study to do justice to them. The new idea of the construction of a semi-permeable membrane composed &of minute capillary apertures in a fluid of non-wettable material seems likely to throw great light upon a rather obscure subject. He had long been impressed with the idea that capillarity is very closely con- nected with many ol the problems which we should like to understand better than we do, leading, perhaps, almost into the recesses of 28 nature’s chemical laboratory. His own familiarity with Helmholtz’s work belonged to a different branch of the subject to that which Professor Fitzgerald had considered.Some thirty years ago he had studied with the ardour of youth Helmholtz’s great work on the sensa- tions of sound. Indeed, he had learned such German as he knew mainly from that book. It so happened that within the last year, in connexion with work of his own, he had been revising and con-solidating his knowledge of that work, and he was quite as much impressed as he ever was with the extraordinary force and ability with which all the difficult problems that there arise are treated in turn by the distinguished author. Many of those who have written since upon the subject, and have criticised, perhaps too lightly, some of the positions assumed by Helmholtz-although, of course, no positions are to be considered as beyond criticism-seem to him not to be so familiar as they might be with the great work in which those positions were first of all set out.What Sir Joseph Lister and what Professor Frankland have said will be echoed by all who are acquainted with any side of Helmholtz’s work, that everything that he touched was distinguished by his touch, and that there is scarcely any field of knowledge in which he has not, as it were, left his mark. All will agree that the object which tbe Society has had in view in commemorating the work of Helmholtz is a most excellent one, and that on this occasion it has been admirably attained. Sir HENRYRosco~said that he could not say more than had been already said with regard to this lecture by Professor Fitzgerald, for which the Society was very grateful.He might add, perhaps, one personal reminiscence. He had the great honouia and extreme pleasure, as President of the Society, of introducing Professor Helm. holtz, in 1881, when he delivered the Fnraday lecture here ; and only a few months ago he happened to be at Beidelberg, and was speaking there to Professor Koenigsberger, the eminent mathematician, who was a very intimate scientific friend of Helmholtz. Koenigsberger spoke especially of Helmholtz’s admiration, almost proceeding tc> reverence, for another great man who has passed away, whom we are glad to reckon amongst the greatest of our countrymen, Clerk Mi,xwelI. Helmholtz used to talk of Clerk Maxwell and his work as :Llmost supernatural.Koenigsberger thought that Maxwell was in many respects superior as a scientific physicist to Helmholtz himself. This shows that Helmholtz, in his magnanimity and high character, was the last to belittle the work of others. Professor ARMSTRONGsaid he would like to recall a fact to memory-that probably Helmholtz’s Earaday lecture was the one Faraday lecture which was distinctly an original contribution, which Re can be sure exercised a very important influence on the scien- 29 fific world. A very large share of the attention which has been drawn to this subject of late yesrs which van’t Hoff, Arrhenius, and others have developed to such an extmordinary extent, has arisen out- of that Faradag lecture by Helmholtz.Not only here but in Germany also it attracted very great attention, and was of very much conse- quence. To-night, again, the Society is to be congratulated very highly indeed that Professor Fitzgerald has most distinctly followed the example of the great man who gave the Faraday lecture in delivering a lecture of striking originality. Yrofessor POYNYINGexpressed his own gratitude and that of the other physicists present for the remarkable lecture to which they had had the privilege of listening. The PRESIDENTsaid that there was one fact in respect to Helmholtz which had not been mentioned. Sir. Henry Roscoe alluded to the fact of our own coxntrymau, Clerk Maxwell, having been ranked on $he same plane as Helmholtz as a physicist.Helmholtz himself was half an Englishman. It is always said that in the making of great men the mother’s share is a large one ; and the mother of Helmholta was an English woman. She was a Miss Penn, and was connected with the same family as the founder of Pennsylvania. The vote of thanks on being put to the meetiug was carried by acclamation. Professor FITZGERALD, in replying to the vote of thanks, said that he regarded it as a very great honour to be asked to deliver this lecture, and felt vsry much flattered indeed by the way in which it had been received. He would feel fully compensated for any trouble it had cost him if it helped his fellow workers and honoured Helmholtz. To help others with information was not so high an aim as to help them with moral ideals.The former was his aim; the latter was provided for him by the sympathy and encouragement of fhe Chemical Society. He thanked them for it. February 6th, 1896. Nr.A. G. Vernon Harcourt, President, in the chair. Mr. J. T. Dunn was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of hlessrs. Sidney Barwise, The Lindens, Derby ; Ernest Hunter Fisher, The County Laboratory, St. Albans ; William Henry Merrett, Lambeth Brass and Iron Works, Short Street, Lambetb, S.E.; Joseph W. Patterson, Esq., Avenue Road, West Hartlepool ; H. von Pechmann, Tubingen, Germany ; James Proude, 13, Oak Terrace, Halifax ; Henry Renney, M.D., B.Sc., D.P.H., Durham, Brookfield House, 30 Durham Road, Sunderland ; Henry Fishwick Robinson, B.Sc., Sparth- Geld, Droylsden Road, Newton Heath, Manchester ; John Henry Wolfendeii, 2.26, Ashton Road, Failsworth, Manchester.Of the following papers those marked * were read :-"12, "The molecular weight and formula of phosphoric anhydride and of metaphosphoric acid." By W. A. Tilden and R. E.Barnett. The molecular formuh hs106, Sb,O, P406,P4O6&,and P4s6, have been already established by determinations of the vapour densities of' these compounds. The formula Pz04has been assigned by Thorpe and Tutton to the compound they designate as phosphorus tetroxide, but no determination of the vapour density having been attempted it remains uncertain whether this formula truly expresses the mole- cular weigbt.The authors are of opinion that the low vapour density observed by V. and C. Meyer in the case of phosphoric sulph- ide is due to dissociation of that compound on vaporisation into phosphorus sulphide and sulphur. They have made a series of determinations of the density of the vapour of phosphoric anhydride at a bright red heat with results which point to the formula, Proro,instead of the simpler expression P205,which has always hitherto been accepted, chiefly on the ground of its assumed analogy with the pentasulphide. They have also made determinations of the density of the vapour of metaphosphoric acid, from which they dram the conclusion that this compound is partly dissociated by heat into water and the anhy- dride, and that the acid must be represented by the molecular formula H2P,0,.DISCUSSION. Mr.DAVIDHOWARDremarked that distilled metaphosphoric acid had been known commercially. Professor THORPE observcd that in the course of his work with Mr. Tutton on phosphorous oxide, he had noticed the volatility of phos-phorus pentoxide, but had not been able to make use of the property, owing to the readiness with which glass was attacked by the heated substance. He agreed with the authors in believing that phos-phorus pentasnlphide dissociates when it volatilises, and that on this account the molecular formula PzS5was open to doubt. He also concurred as to the desirability of redetermining the formuh of many of the metallic metaphosphates."13. " Lead tetracetate and the plumbic salts." By A. Hutchinsolz; M.A., Ph.D., and W. Pollard, B.A., Ph.D. In September, 1893, the authors communicated to the Society a short note on lead tetracetate (Trans., 63, 1136). Since that date the work has been extended, and the detailed results are contnincd in the present paper. Lead tetracetate is obtained when red lead is dissolved in glacial acetic acid, and crystallises from the solution in monosymmetric needles, a :b :c = 0.5874 :1:0.48485. p = 74’ 24‘. The specific gravity of the crystals is 2-28;they are readily soluble In chloroform and hot acetic acid, and the molecular weight deter- mined in the latter solvent is 365 by the boiling point method, and 408 by the freezing point method.Lead tetracetate is decomposed by water with extraordinary ease into lead dioxide and acetic acid ; acted upon by gaseous hydrogen chloride it jields lead tetrachloride, whilst if dissolved in aqueous hydrogen chloride and the solution added to a solution of ammonium chloride, the double salt, (NH&PbCI,, is precipitated. When acted upon by orthophosphoric acid, lead teti-acetate yields a tetraphosphate, to which the formula Pb(HP0d)z is probably to be assigned; a propionate, Pb(C3H5O2)4, analogous to the tetracetate, has been prepared. The authors point out that thrtllic and mangnnic acetates, wit11 properties very similar to those of lead tetracetate: have been described, and give a list of salts of tetravalent lead, owing to the close ana- logies which exist between the stannic salts and the salts of tetra-valent lead.The authors propose that the latter should be termed plumbic salts. “14 “An improved method of determining urea by the hypobromite process.” By Alfred H. Allen. It is well known that in the ordinary way of employing the hypo-bromite process for the determination of urea the evolution of nitrogen in the form of gas is only about 92 per cent. of the total nitrogen present. An increased yield of nitrogen is obtainable by adding glucose, and by certain other devices, but these modifications are open to several objections, and have not met with general ac-ceptance. In a paper recently read before the Society (Trans., 67, 746) Messrs.Walker and Hambly described some suggestive experiments ou t,he transformation of ammonium cyanate into urea. They find that the reaction is never complete, and they iurther point out that the reverse reaction occurs when an aqueous solution of urea is boiled. It follows that a solution containing both ammonium cya- nat e and urea ultimately arrives at a condition of equilibrium, which is upset if ammonium sulphate or potassium cyanate be added to the solution, the urea in each case being rendered more stable. From these results it appeared probable that the incomplete evolu- tion of nitrogen in the hypobromite process of determining urea might be due to a reversion of a portion of the urea to the condition of cyanate, especially as H.J. H. Fenton had shown (Trans., 33, 300) that cyanate mas a product of the reaction of alkaline hjpochlorites on urea, and W. Foster (Trans., 35, 122) made the same observation with alkaline hypobromite. Fenton also found that cyanates evolved no gas when treated with alkaline hypobro- mite, and the author can confirm trhis observation. Hence it. ap-peared possible that by adding a sufficiency of potassium cyanate to the urea solution hefore adding the hypobromite the reversion of the urea to cyanate might be entirely prevented. Experiment has proved this conjecture to be correct. An addition of 0.250 gram of pure potassium cyanate to the solution of 0.100 gram of urea in 5 c.c. of water raised the evolved nitrogen from 91 to nearly 97 per cent.(cow.) I€the ordinary method of operating be reversed, and instead of adding the urea solution (mixed with potassium cyanate) to a highly alkaline solution of sodium hypobromite, the cyanate be added to the solution of urea, followed by caustic soda when its solution is com-plete, and the bromine solution be then gradually run in, stmill better results are obtained. Under these conditions the yield of nitrogen is from 99% to 100.0 per cent. (corr.). Hence the addition of potas-sium cyanate to the extent of two to three times the weight of the urea present effects a complete evolution of the nitrogen in the form of gas, and prevents the irregularities and uncertainty attaching to the hypobromite process in its ordinary form.The idea of reversing the usual mode of procedure appears to have originated with J. R. Duggan (Arner. Chem. J.,4, 47), who states that fully 99 per cent. of the urea1 nitrogen is evolved as gas if 5 C.C. of urine be first mixed with 20 C.C. of a solution of 20 grams of caustic soda in 100 C.C.of water, and 1C.C. of bromine be gradually added. I hare not been able to obtain so high a yield as 99 per cent. of gas without the addition of potassium cyanate, but the reversed process is in any case a valuable improvement on the ordinary method of working. A convenient arrangement for the reversed form of the process is found in the author’s work on the “ Chemistry of Urine.” In this apparatus it sepmatory funnel is substituted for the sample-tube generally used.Five C.C. of the urine or other solution of urea should be placed in the flask, and 0.250 gram of potassium cyanate added. When solution is complete, 25 C.C.of a 40 per cent. aqueous solution of caustic soda is added, the separator adjusted, and the flask connected to the nitrometer. A solution of 2 C.C.of bromine in 16 C.C. of a 20 per cent. aqueous solution of potassium bromide is t,hen added gradually from the tapped separator. The evolution of nitrogen occurs very promptly, and is usually complete by the time one-half of the prescribed yolume of bromine solution has been .added. The use of silver cyanate, with or without simultaneous addition of sodium chloride, was found less satisfactory than the addition of the potassium salt. It appeared probable that the reaction o€ the alkaline hypobromite with potassium cyanide would result in the format’ion of cyanate, in which case pdassium cyanate could be conveniently extemporised in the liquid.Experiment showed that on adding potassium cyanide to the alkaline hypobromite great evolution of heat occurred, cyanate is formed, but the reaction appears t9 be complex, and the product had not the same effect as previously prepared potassium cyanate. The author intends to investigate this reaction more completely, as it does not appear to have been previously studied. DISCUSSION. hfr. FENTONmade an experiment to show that when sodium hypo- chlorite reacts with urea the quantitr of nitrogen evolved is only one- half of that obtained by the action of hypobromite.He had been unable to find an entirely satisfactory explanation of the fact. Professor THORPEpointed out that Lord Rayleigh had statled that the gas evolved by the reaction of urea, with alkaline hypobromite was not pure nitrogen, and suggested the desirability of examining the gas more fully. Professor TILDENconcurred in regarding this as an important point. Mr. HEHNERthought Mr. Allen’s modified method of using this .alkaline hypobromite would prove of value. He did not consider, however, that the mode of action of the potassium cyanate had been ,completely explained. Mr. GROVESand Mr. PAGEremarked that the simplicity and rapidity of the hypobromite method was a strong recommendation from the clinical point of view, and Mr.PAGEpointed out that the employment OE free bromine, which is required for the “ reversed ” process, would be ,z disadvantage in the wards of a hospital. Mr. CROSSthought it would be of interest in connection with the anomalous behaviour of urea to mention that he had observed that whilst a mixture of sulphuric acid and potassium dichromate failed to cause the evolution of nitrogen from urea, this gas is plentifully evolved if a nitrate is added to the mixture. “15. “ Preliminary note on the absorption of moisture by deliquescentsalts.” By H. Wilson Hake, Ph.D. Some years ago the author, in experimenting with deliquescent I A. B. ' c. D. E. I F. G. H.' Difference Theoretical between Theoretical Theoretical theoretical difference cliff erence ~~~~~~~Original Nearest molecular hydration Substance.hydration Per cent. formula corre- per cent. and found per cent. for per cent. forIper cent. 1 i reached. sponding to C. corresponding hydration 1 mol. H,O 1mol. 1120 to D. per cent. more thin D. less than D. I --.--i-----MgCI,6ET20 . . .. . . . 53.20 1 77.20 I MgC1218H20 77 '33 -0 '13 I----+ 0 *93 -1 *03 ~ 18.18 ' 65 -89 6G -05 -3'36 + 1.35 -1 *46Mg(R'0,)24H20,. n CG* ~ICaC126H20.. . . + . . 49'31 '73 -24 73-35 -0 *14 + 1 *I0 -1 *20 Fe2C1,121T,0 . , . . .. 39.92 1 66 *52 6G -59 -0 -07 + 0 $1 -0.63 I NiCl,GH,O . . . . . . . . 43 '38 '70 03 70 -18 -0 -15 + 1-18 -1 '28 1Nn(N0,),3H20... . 23.17 61*54 61 *67 -0'13 + 1 *42 -1 '54 I H2PtCI,*GI€,O . . . , . 20 -85 47 -82 47 -97 -0.15 + 1.16 -1 -22 aH,SO,. . . . * . . . . .. 4-20 1 64 *c3 64 94 -0 *11 +3 15 -2 *43 LiCI.. . . . . . . . . . . . . 0.00 77 *40 77 21 +0-19 t-2-00 -2 '44 salts, found that they exerted a desiccating action on other deliques- cent salts, indicating A difference in the degree of attraction for moisture on the part cjf such salts. More recently experiments were commenced with the intention of measuring, if possible, the relative degree of deliquescence, or specific deliquescence, of certain salts. On exposing known quantities to the air, and weighing them at frequent intervals, in a.11 cases, without exception, a maximum of deliquescence was reached in a few days, and from this point a gradual decline in weight almost invariably followed.This maximum coincides with the formation of a definite hydrate, in a large number of cases, when the salt was pure; the watei* contained in it at its maximum of deliquescence approximately coincides with that required for a definite number of water mole-cnles. As in all such cases, there was a possible margin of 1 per certt. and over for the next one molecule more or less of water, the author concludes that the phenomenon of deliquescence in certain salts, and possibly other substances, is due to a tendency 011 their part to form a definite hydrate. The table on page 34 indicates some of the results obtained at present. The above salts were found to be practically pure on analysis; with less pure salts an approximation to a definite hydrate was ob-tained, but in most cases this was sufficiently close to indicste the probable truth of the hydrate assumption.DrscussroN. The PRES~DEX'T, and Professor DUMSTANProfessor E. W. MORLET. commented on the fact that Dr. Hake had not so far studied the rela- tion of the amount of absorption to the vapour pressure of water in the atmosphere to which t'he salts mere exposed, and pointed out that until Phis had been doiie no positive conclusion could be drawn from the results. 16. Some c'erivativrs of 7-phenoxyethylmalonic acid and of r-yhen-oxyethylacetic acid." By W. H. Bentley, E. Haworth, and W. H. Perkin, junr. y-Phenoxyethy lmaZom'c acid, CsH50*C H2.CH2.C H(C00H)2, is easily prepared by the action of C6H50*CH2-CH2Br,P-bromethylphenyl ether, on ethylic sodiomalonate, and the hjdrolysis of the resulting ethereal salt with potash.It crystallises from xyleue in minute needles melt- ing at 142" with slight evolution of gas. o,-Ph ew oqEu fyric. acid C,H50*CH2*CH,*CH2*C0OH, y-phenoxye thy1 acetic acid, is obtained by heating y-phenoxye thylmalonic acid to 36 160-200" until the evolution of carbon dioxide ceases. It separates from light petroleum in thin plates melting at 64-65'. Heated with fuming hydrobromic acid it loses phenol, forming a bromo-deriva-the, which, on boiling with sodium carbonate and acidifying the product, yields butyrolactone. Di~henozyethyli7zaZolzicacid, (C,H,*O-CH2*CH,),C(COOH),, is ob- tained by acting on ethylic malonate twice with sodium and P-brom-eethylphenyl ether, and subsequent hydrolysis of the product with potash.It crystallises from 50 per cent. acetic acid in prisms melt- ing at, 150' with decomposition. D@henoxyethylacetic acid, (CsHb*OCH2*CH,),*CH-C0OH, is pre-pared by heating diphenoxycthylmalonic acid at 180' until carbon dioxide ceases to be evolved. It separates from light petroleum in needles melting at 88". utyric acid, C6H,0,01-PhenoxyethyZ-~-h?ldro~~~ Ho CH2. H2>H2*c H2 CH. C 00El, results on heating diphenoxyethylacetic acid with hydrogen chloride, dissolved in acetic acid for some hours at 150'. It crystallises from benzene in plates melting at 212", and is very sparingly soluble in ether.Ethylic-~-pl~e~zo~yeth~Z-a-methylnaalonate, PhO*CH2*CH2*CMe(C:00Et)*, is prepared by the action of C6H60*CH2*CH2*Bron the sodium com-pound of ethylic methyl malonate. IL is a thick, colourless oil (b. p. 230": pressure45 mm.), which, on hydrolysis, gives the corre- sponding dibasic acid ~~-phenoxyeihyl-a-methylmalo~icacid. This acid crgstallises from benzene in colourless prisms, which melt at 125O C. ~-.Phenoxyetlcyl-a-i~zetlayZaceticacid is obtained by heating the pre- vious acid at 180' till evolution of GO, ceases, nnd then distilling in a vacuuin (b. p., 207', pressure, 45 mm.). Recrystallised from light petroleum, the acid melts at 80". This acid was also obtained by the action of /3-bromethylphenyl ether on the sodium compound of ethylic methylacetoacetate, and saponifying the resulting ether (a colourless syrup, b.p. 185", pressure 40 mm.) with strong alcoholic potash. a-Methylbutyrolactone was obtained from the previous acid by first treating with aqueous hFdrobromic acid, and then boiling the result- ing bromo-acid with sodium carbonate solution. The lactone was then reconverted into y-bromethyl-a-methylacetic acid by treatment with HBr. This acid, which is very unstable, is a brownish, oily substance ; its ethyl ether is also unstable, and could not be distilled. PpChlorethyl-cc-methyl acetyl chloride was obtained 37 as a colourless liquid (b. p. 189') by the action of phosphorus pent&-- chloride on a-me thylbutyrolactone.This chloride, when acted on by aniline, gave an anilide, ClCH,*CH2.4H*CONH'C6H5, which crystal- CH3 lises from light petroleum in colourless prisms (m. p. 106'). 17. "Note on the preparation of glycol." By E. Haworth and W. H. Perkin, jun, This paper describes a modification of the usual method of prepara-tion of glycol, which consists in decomposing in a given volume of aqueous potassium carbonate, successive quantities of ethylene di- bromide, by which means a concentrated solution of glycol is obtained, and subsequent loss by evaporation is reduced to a minimum. 18. "Luteolin." By A. G. Perkin. Luteolin, the yellow colouring matter of Weld (Reseda Zuteola), was first isolated by Chevreul (J.Chim.Mkd., 6,157), and has been sub- sequently investigated by others. The formula C,,H,,O, was assigned to it by Moldenhauer, C12H805 by Schutzenberger and Paraf, and C15HloO6 by Hlasiwetz and Pfaundler. The results here obtained agree with C,,H,,08 and C15H1006,and that the latter is correct is proved by the production of Farious derivatives. In it similar manner to quercetin, fisetin, and morin (Trans., 1895, 644), luteolin combines with mineral acids, yielding the crystalline compounds and C15H~oO~HCl.H,0,Cl,Hl,06~E~Od,~,5~~o~6HBr*~~~ which, in contact with water, are decomposed into luteolin and the free acid Luteolin yields a tetracetyl compound, C,5H60s(C2H30),, colourless needles, m. p. 213-215', a tetrabenzoyl compound Cl5H6o6(C,H,0)4, m. p.2O0-2Olc, and a dibromo-compound, Cl5H8Br2O6,yellow needles, ni. p. 303'. The acetjl compound of this latter, C,,H,BrZO6(C2H,O),, melts at 218-220". Rochleder has previously found tbat luteolin, by frision with alkali, yields phlorogiucin and protocatechuic acid, but pre- liminary experiments have shown that though the former is so pro-duced, the presence of thc latter could not be detected. There was, how-erer,isolated a second substance in the form of nearly colourless needles, melting at 210°, but giving no coloration with ferric chloride. On methylation, luteoh yields a compound of the formula C15K606(CH,),, m. p. 191-192. It is considered probable tbat luteolin is very similarly constituted to fisetin, C,,Hl0O6,or tetrahydroxy-/3-p11enyl-,,-0 OH OH/\/\/-\OH1 1 I\--/ppon, Herzig (Be,.., 1895, 28, 293), a/>g ,which it.very closely resembles. 19. “An examination of the products obtained by the dry distillation of bran with lime.” By W. F. Laycock, Ph.D. Considerable quantities oE bran and unslaked lime, in the propor- tions of ‘I :2 by weight, were subjected to dry distillation. The resulting distillate consisted of a black oil floating on an aqueous solution. The solution contained considerable quantities of ammocia, chiefly aA bicarbonate also amines and pyrrols, together with small amounts of ketones, and ethyl alcohol. The oil after redistilling was treated with dilute hydrochloric acid and the pyridine bases thus separated were afterwards purified.The unchanged oil mas freed from small amounts of ketones by shaking with sodium bisulphite solution. The residual oil consisted of a mixture of hydrocarbons and pyrrol homolopes with small quantities +of fnrfuranes and an indole. 20. “ Constitution of glycocine.” By Jbj i Sakurai. Since the publication of my paper on the “ Constitution of glycocine and its derivatives,” (Proc. 137), important facts have been contributed to the history of the subject by eminent authori- ties, and it is interesting to observe that these new facts are either .confirmatory of the ring constitution or, at least, in conformity .with it. Walker (Proc., 137)has made the very important observation that -glycocine is virtually a non-condudor of electricity, whilst phenyl-glycocine, hippuric acid, and aceturic acid are far better conductors than acetic acid, and has concluded that these glycocine derivatives must.be open-chain compounds and that, by analogy, glycocine itself ’has not the ring constitution. But if electric conductivity of glycocines proves anything as to their constitution it must be con- eluded, by the very same reasoning that glycocine itself, being a non-conductor, cannot be an open-chain compound. A probable explanaticn of the difference in the electric conductivities of glyco-cine and its derivatives, which gives every support to the view .of the cyclic constitution of the glycocines seems obvious to me. It is that while glycocine itself appears not to form an addition corn- ,pound when dissolved and, consequently, could undergo no ionisabion, its derivatives do form such addition compounds, these being, as .pointed out in my paper, open-chain compouuds and, therefore, .capable of more or less ionisation.Betake is an example in point which, in the anhydrous and hydrated states, is, by universal admis- .sion, N(CH,) 3*CH2*C0.0 and H0*N(CH3),.C H2-CO-OH, respecti vely. I irilden and Forster (Trans., 67, 489; Proc., 151) find th-tt the 39 primary action OE nitrosyl chloride upon glycocine and several OE the acid-amides is to replace the NH2-group by C1, glycocine, in this manner, producing chloracetic acid. This fact they consider to be at variance with the ring formula of glycocine.The difficulty, how-ever, does not exist. There being, as they say, complete removal of the NHB-group by NOCl with formation of N2,H20,and HC1, thc remaining group will be CH,*CO*O,and this, like ethylene oxide, will L.1 almost inevitably combine with hydrogen chloride, and produce chlor- acetic acid. This explanation is in conformity with that which Tilden and Forster give of the production of acetic acid from acetamide, where they assume that acetyl chloride is first formed, and then acted upon by water. The ring formula of glycocine gives yet another explanation o€the formation of chloractic acid, and again from Tilden and Forster’s standpoint. Admitting, as they say, that by the action of nitrosyl chloride there is an interchange between NH, and GI, of the divalent group, NH,, there will H left along with the C1, but hydrogen and chlorine being both monovalent, the H will go to the half-freed 0, so as to give rise to chloracetic acid.H(NH,)*CH,*CO*O-Hi( Cl)*CH,*CO*O, i.e., Cl*CH,*CO*OH. L---J These two explanations of the production of chloracetic acid from glycocine differ only in assuming or not that hydrochloric acid has a, temporary existence apart from the rest of the elements prior to the formation of chloracetic acid. A full account of the facts supporting the theory that the glyco-cines are closed chain compounds is contained in the Jozirizal of the College of h‘cience, linp. Univ.,Japan. ADDITIONS TO THE LIBRARY. I. By Purchase.Boltzrnann, L. Vorlesungeu iiber Gastheorie. Theil I. Thearie der Gase mit Einatomigen molekiilen, deren Dimensioneu gegen die mittlere Weglange verschwinden. viii +204 pp. Leipzig 1895. 8vo. Maxwell, T. C. Ueloer Faraday’s Kraftlinien. 130 pp. Leipzig 1895. 8vo. (Ostwald’s Klassiker der Exakten Wissenschaften. 69.) Meyer, L., und Mendelejeff. Das Natiirliche System der Chemi- schen Elementes. 134 pp., with a Table. Leipzig 1895. 8vo. (Ostwald’s Klassiker der Exakteu Wissenschaften. 68 ) 40 Seebeck, T. J. Magnetische Polarisation der Metalle und Erze durch Temperatnr-Differenz. 120 pp. Leipzig 1895. 8~0. (Ostwald’s Klassiker der Exakten Wissenschaf ten. 70.) Rideal, S. An Introduction to the Study of Disinfection and Disinfectants, together with an account of the chemical substances used as antiseptics and preservatives. With 19 figures and a folding plate.xii+328 pp. London 1895. 8ro. Carpenter, W. L., and Leask, H. A Treatise on the Manufacture of Soap and Candles, lubricants and glycerin. Second edition, revised and enlarged. With 104 figures. xii+446 pp. London 1895. 8vo. 11. Donatiom. Pelouze, J.,and Fremy, E. Abrkg6 de Chemie. Deuxieme Qdition. Partie I. Pr’otions prkliminaires et RilQtallo’ides, avec 5 planches. Partie 11. M6taux et M6tallurgie, avec 1 plsnche. Partie III. Chemie Organique, avec 1 planche. 638 + 332 pp. Paris 1853. 8\70. From B. H. Brough, Esq. Nicholson, William. The Firstl Principles of Chemistq-. Second edition, with improvements. 560 pp.London 1792. 8vo. From B. H. Brough, Esq. Meyer, Dr. Lothar. Die Atome u. ihre Eigenschsften. Sechste Auflage. xviii+171 pp. With a diagram. (Die Modernen Theorien cier Chemie u. ihre Bedeutung fur die Chemische Mechanik i. Erstes Buch). 8vo. From the Publishers. Catalogue of Scientific Papers (1874-188s). Compiled by the Hioyal Scciety of London. Vol. XI. (Pet-Zyb). 902 pp. London 1896. 4to. From the Royal Society. At the next meeting on Thursday, Febrnary 2M1, there will be a ballot for the election of Fellows, and the following papers will be. read :-c “ The oriyin of colour ; the yellow 2 : 3-h-jdroxgnaphthoic acid.” “ Note on etherification.” “ The relation of pinene to citrene.” By Prof. Arrustrong, F.R.S, HAUILISON ANC som,PRINTERS IN OXUINARP TO HER MAJESTY, ST.J~AXTLN’SLANE-
ISSN:0369-8718
DOI:10.1039/PL8961200025
出版商:RSC
年代:1896
数据来源: RSC
|
|