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Proceedings of the Chemical Society, Vol. 18, No. 253 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 253,
1902,
Page 123-158
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摘要:
Issued 12/6/02 CHEMICAL SOCIETY. EDITED BY THE SECIZETARIES. Vol. 18. No.253. Wednesday, May 3Sth, 1902. Professor MELDOLA,F.R.S., Vice-President, in the Chair. Messrs. J. W. Peck, J. C. Crocker, and J. KewIey were forninlly admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Edmin T. H. Bncknell, Ebley House, Parsonage St., Dursley, Glos. Francis E. Francis, S, Manilla Rd., Clifton, Bristol. George Paton Poliitt, Ph.D., St. Silas Hd., Blackburn, Lanes, Harold James Roast, 3, Manor Park Rd., Harlesden, N.W. Edward J. Wheeler, Albany, State of New York, U.S.A. Of the following papers, those marked * were read : *Ell, “Tarrine, the alkaloid of yew.” By T.E.Thorpe, C,B., P.R.S., and G.Stubbs, The investigation has been carried out on autumn-gathered leaves of male and female trees of the species Tcczus Baccuta.The alkaloid was 124 extracted by digesting the powdered, air-dried leaves with 1per cent. sulphuric acid for 5 or 6 days. The acid liquid was strained and pressed from the leaves, and at once, without concentration, rendered alkaline and extracted with ether. Taxine was obtained in the form of very fine, glistening particles by crushing down the residue from the ether extract. It gives precipitates with most of the alkaloidal reagents, and colour reactions with strong sulphuric acid alone, and when this reagent is mixed with nitric acid, rnolybdic acid, or chromic acid. Taxine is very susceptible to change. At least two substances result from the action of dilute acids upon it., but owing to lack of material the authors have not yet completed their investigation of these products.Several salts have been prepared and analysed. Two compounds with gold chloride have been obtained which have the formula? C37H,2N010,HAuCI,(m, p. 72.5') and C37H,,N0,0,AuCI,(m. p. 132-1 34') respectively. The riiethyl iodide compound, C,7H52N0,0,CH31 (m. p. 121°), has been prepared as a white, amorphous powder by mixing benzene solutions of tho alkaloid and methyl iodide. Although the analytical figures deduced, both for taxine and its salts, are in substantial agreement with the formula, C37H52N010,given by Hilger and Brande (Ber., 1890, 23, 464), the authors are not of opinion that this formula is definitely established.The aIcoholic extract of yew, amounting to about 26 per cent. of the dry leaves, is at present under examination. DISCUSSION. Prof. DUNSTANremarked that the authors had confirmed the accuracy of previous work on the properties of taxine, and he hoped that they would now be able to go further and throw some light on its chemical structure. It had not been yet fully proved that yew- poisoning was due to the presence of taxine, and indeed even the exact conditioiis under which yew becomes poisonous did not appear to have been determined with certainty. Mr. GOLDINGsaid that in the year 1893 he had assisted Mr. Dymond in an invsstigation of the alkaloid of the yew. They found that drying the leaves at 100" destroyed the alkaloid, The extraction of the alkaloid was made from bruised, green, freshly- gathered leaves by Marm8's process, which was repeated several times to purify the alkaloid.Further purification was effected by adding light petroleum to the ether solution, the fractions thus obtained giving the characteristic reactions of taxine. When dry hydrogen chloride was passed into a solution of the alkaloid in anhydrous ether, and a crystalline precipitate was formed, which soon changed to a dark brown paste, phenomena also observed by Hilger and Brande. Cases were on record of animals eating yew with impunity, and a large number of the cases which had proved fatal were due to the eating of witheyed branches.Dr. VOELCKERpointed out that the uncertainty with regard to poisoning by yew extended to the kind of animal eating it as well as the condition of the leaves. A good deal also depended on the conditions under which it was eaten, whether, for example, much grass or other food was eaten along with it. He thought that it was very desirable that the other substances which the authors had obtained should also be studied, but regarded it as essential that the yew examined should be freshly gathered, and not kept for some considerable time as in the case of that employed by the authors. Mr. STUBBS,in reply, said that no work had been done to ascertain if the alkaloid contained methyl groups. He did not think that the substance had been produced by the action of the acid used for extraction upon a glucoside.The material employed had been dried in air, at a temperature not exceeding 60’. They had obtained the same amounts of alkaloid from the leaves both when freshly gathered and after they had been dried. *82. “The sampling of soils.’’ By J. W.Leather. Experiments were made in India to determine the accuracy of the auger method of sampling soils, and the agreement bet ween the samples was tested by determinations of the total nitrogen, the available phos-phoric acid, and the available potash. The results showed that in most cases the agreement was very good between samples, but that in some cases the divergence exceeded 1 in 20, an amount which the author considered too great.The amountsof phosphoric acid in some of the Rothamsted wheat soils, as found by Dyer, were considered with a view to determine the accuracy of the method of sampling which was there employed. The author considered that such a comparison indicated the Rothamsted method to have yielded as good results as the auger method. Both, however, fall short of what is expected in taking samples of commercial products, and it was urged that the newer methods of soil investigation demand more accurate methods of sampling. DISCUSSION. Dr. DYERsaid that it seemed obvious that a sample drawn from many parts of the field was more likely to be accurately representative than a sample drawn from one or few places. Nevertheless, it seemed to him that Dr.Leather’s analytical results, obtained on samples drawn from different parts of the same field, instead of indicating differences in the samples, appeared really to indicate that both the sampling and the analytical work were excellently performed. Some of the analyti- cal figures regarded by Dr. Leather as discrepant, he (the speaker) should himself regard as being in very good agreement. As to the results of his determinations of phosphoric acid in the Rothamsted wheat soils, which Dr. Leather had quoted, it must be remembered that, whilst the samples analysed represented only the first nine inches of soil, the phosphoric acid removed in the crops might, in the case of wheat, on many plots, be drawn to a considerable extent from the subsoil ;and that the influences of vegetation might considerably affect the distribution of soil constituents in the various layers of the soil and subsoil.The ‘‘ original ” phosphoric acid of Broadbalk field, as calculated back from the present contents and known additions and removals, showed, on the whole, as Dr. Leather had pointed out, a fair uniformity, though there were some discrepancies. It was, however, quite probable that the percentage of phosphoric acid in the surface soil was originally by no means uniform on the different plots. Certain of the plots had long behaved somewhat anomalously, indicating some inherent physical or chemical differences in the soil or subsoil. Dr. VOELCKERwas inclined to agree with nr. Dyer, and to regard the results which Dr.Leather had obtained as being very satisfactory, and as agreeing well with one another. It would hardly be a, matter for surprise to those who had followed the work at Rotharnsted, and who knew the infinite pains which the late Sir Henry Gilbert always took to ensure accuracy in every detail, to learn that Dr. Leather’s estimate of gains and loses showed that there could not be much amiss with the Rothamsted method of soil-sampling. Still, it was ob-vious that the more places in which borings of a soil were taken for sampling purposes the more representative would that sample be. There was considerable difference between soil samples taken as at Rothamsted (where at least three holes were selected on each plot), and the block of soil ordinarily sent by a farmer when he wished his soil analysed.In the latter case, no doubt, the method Dr. Leather suggested would give a much more representative sample. The ciifficulty was in the case of soils of stony character, or where lumps of chalk occurred. The auger might veryLreadily, by pushing these stones or lumps aside, or by including them in the boring, ultimately cause a considerable difference in the analysis. Mr. HALLsaid that for some years he had been using an auger for taking samples in the Soil Survey of Kent and Surrey they were carrying out. They used n cylindrical auger one foot long, two inches 127 in diameter, with a slot one inch in breadth, the sides of the slot, and the bottom of the cylinder being each sharpened to a cutting edge.The worm auger was only used for exploring the subsoil to some depth. The auger was undoubtedly most useful for securing a fair sample, especially in field work, where one did not want to be burdened with a great weight of soil ;but there were many soils on which it could not be used, they were either too hard, too stony, or too loose to remain in the tool. The stmeel box employed at Rothamsted could be made to give the most accurate results, but it was not wise to lay down any hard and fast rule as to which was the best tool. The analyst must examine the soil, and then use his judgment. As to Dr. Leather’s figures, not only did they support his opinion that fair samples could be drawn with the auger, but they showed that he must have been working with an extremely uniform soil, probably of alluvial origin, In England samples taken from adjoining fields on the same formation would vary between far wider limits than those shown by Dr.Leather’s figures. Dr. LEATHER,in reply, said that so far as stones are concerned, the determination of their amount would naturally demand that comparatively large portions of soil should be taken, but this considera- tion would not apply to the examination of the fine earth. Of the Indian soils examined, that at Cawnpore is alluvial, but the geological history of the Poona land is uncertain, *83. LcSomeexcessively saline Indian well waters.” By J. W. Leather. The composition of some well waters from the Muttra District, United Provinces, India, was given in detail. These waters contain from 200 to 2000 parts of salt per 100,000 of water. About one-half of thesaline matter consists of sodium chloride ; the amount of carbonate is about 20 to 30 parts ;the nitrate varies from nothing to 250 parts ;very large amounts of sulphate were present in some of the samples. In three cases, there wasan excess of lime over that required to combine with the nitric, carbonic, and sulphuric acids, thus proving the presence of calcium chloride, Some of these waters are used for irrigating crops.The soil of the district is open, the drainage conditions are good, and no salts accumu- late in the surface soil. These waters provide an indication therefore of the maximum strength of solutions in which plants can grow, a point which is of importance in connection with the alkali lands of America, and the Usar lands of India.It is found practically that, of these well waters, those may be employed for irrigating crops which 128 do not contain much more than about 500 parts of salts per 100,000, or 0.5 per cent. The amount of salts in Usar or alkali land is usually stated in parts in 100 of soil, and it is found in practice that soils containing much more than 0.1 per cent. are infertile. Immediately after irrigation, such a soil would contain a solution of about 0.33 of salts per 100 of water, but after the lapse of a few days, the proportion of water decreases to 10 or 15 per cent., and in this state the above mentioned solution would become concentrated to about 1.0 or 0.66 per cent.respectively. These figures correspond practically with what is known about the well waters. DISCUSSION. Mr. J. SPILLERsaid that in the year 1865 he had occasion to examine some remarkable products obtained from a highly saline spring which discharged itself into Lake Lohhar, India. The water left on evaporation 8.25 per cent. of solid residue, which consisted roughly of two parts of common salt to one of sodium carbonate. A local attempt at a separation of these resulted in a purified product, which had the following composition :- Sodium carbonate .................................... 75.0 ,, chloride ....................................... 0.6 Calcium carbonate ....................................1.9 Sand and ferric oxide .............................. 2.7 Water, nearly ......................................... 20.0 There was no sulphate, bromide, borate, or nitrate. “84. ‘(Nitrobromo-derivatives of fluorescein.” By J. T. Hewitt and A. W. G. Woodforde. The non-fluorescence of alkaline solutions of nitro-derivatives of fluorescein was explained by the assumption that the alkaline salts of orthonitrophenols have the metal attached to the nitroxyl and not to the hydroxyl group (Hewitt and Perkins, TTUNS.,1900, 77,1324). With regard to the position of the nitro-groups in dinitrofluorescein, it was assumed that these occupied positions 2 and 7.(The numbering of the fluoran ring corresponds to Richter’s numbering in the xanthene nucleus.) Additional support was lent to this view by the isolation from the product of alkaline fusion of a small amount of material having a melting point of 114’. Since 4-nitroresorcin melts at 115O, the sub- stances were supposed to be identical, and hence positions 2 and 7 were assigned to the nitro-groups in the Auoran nucleus. It is now shown, 129 however, that this view must be discarded; by adopting suitable pre- cautions, 2-nitroresorcin mtly be isolated in considerable quantity, as had been previously demonstrated by Matras ; the authors' thanks are due to M. Reverdin of Geneva for calling their attention to this work.Dinitrofluorescein is thus 4:5-dinitrofluorescein; acted on by bromine, 4:5-dinitro-2 :7-dibromofluorescein results. This substance closely resembles the original dinitrofluorescein, it dissolves in alkalis with a brown colour, but on warming a blue solution is obtained from NO,)(OH),],.which acids precipitate the hydrate C,H,--C[C,HBr(\coo0/ 4:5-Dinitro-2 :7-dibromofluorescein has been further characterised by its diacetyl derivative, C,oH6Br,N,0,(C,1330),, m. p. 276' ;ddenxoyl derivative, C,,H,Br,N,O,( C,H,O),, m. p. 315O ; sodium salt, C,,H,Br,N2O,Na2,2H,O. Bibromojuorescein, (320H10Br205,obtained by Bayer by the limited action of bromine on fluorescein, is evidently also a 4:5-substitution derivative, since nitric acid produces from it a dinitro-derivative quite distinct from the 4 :5-dinitro-2 :7-dibromo-compound.The benxoyl derivative, C,oH,Br,O,( C7H50),, melts at 240-244'. 2 :7-Dinitro-4:5-dibrornofZuorescein may be obtained either by the action of nitric acid upon 2 :7-dibromofluorescein or of bromine upon 2 :4:5 :7-tetra-nitrofluorescein. This substance dissolves in a1 kalis with a magnificent purple colour not altered by boiling. Nitro-groups only render the pyrone ring unstable if in the ortho-position relatively to its oxygen atom ;this is also shown by the action of ammonia, which reacts with 4:5-dinitro-2 :7-dibromofluorescein, apparently in a similar manner to that observed by Reverdin in the case of dinitrofluorescein, whilst with 2 :7-dinitro-4 :5-dibromofluorescein it merely produces an ammonium salt. The diacetyl derivative, m.p. 215O, dibenaoyl derivative, m. p. 301', and sodium salt of 2 : 'I-dinitro-4 : 5-dibromofluorescein have been prepared. 85. On phosphorus sesquisulphide and its behaviour with Mitscherlich's test." By E. G. Clayton, F.I.C. Many compounds of phosphorus and sulphur have been described, but of these the only one which has received any application on the large scale is the sesquisulphide, P,S3, discovered by Lemoine in 1864. When pure, it is a lemon-yellow, crystalline solid, with a strong odour of hydrogen sulphide, soluble at 15' in 1.6 parts of carbon bisulphide, and igniting in the air at about 100°. Commercially, several qualities of this substance are manufactured.Amongst those which have come under observation have been a coarsely granular, lemon-yellow 130 powder ;a fine-grained, yellow powder o f somewhat duller tint; and a grey product, sometimes very impure. The following are typical analyses : A. B. c. D. Yellow Yellow Yellow Grey(fine-(fine-(coarse-(finelygrained). grained). grained). granular). Water and volatile matter (loss at loo", in an atmosphere of carbon dioxide) ................................. 0.19 8-74 7-31 Phosphorus sesquisulphide, P,S, ... 97 *86 84-95 83'34 Red phosphorus.. ......................... --1-81 Phosphoric acid, H,PO, ............... 1*30 2 '14 1-23 Sulphur, unconibiiied (soluble in Icarbon bisulphide) ..................... 4 -17 -Sulphur, uncombincd (insoluble in carbon dioxide) ........................ 0 -46 -0.17 Calcium phosphate .....................---3.35 Calcium sulphate ........................ -0.27 Iron oxide, &c. .......................... ---1*72 Siliceous matter.. ......................... 0.19 0.80 100'00 100~00 100~00 100'00 Temperntnro at which the specimen became lnniinons in the dark ...... 92" 93" -58" Temperature of ignition .............. 94 96 86" 72 Reaction with Mitscherlich's test ,.. negative negative distinct distinct Morner has recently stated (Suensk ~ar.niaceutisk-Tidskrift,1901, 12, 177) that phosphorus sesquisulphide gives '' more or less positive results " with Mitscherlich's test for phosphorus. The author has examined various specimens of commercial phosphorus sesquisulphide, and applied Mitscherlich's test to each in the following way: 30 grams of the compounds were distilled with 100 C.C.of 10 per cent. sulphuric acid, in an egg-shaped flask connected with a spiral condenser, the operation being conducted in a dark room. The very small amount of light emitted by the lsmpmas screened from the condenser and receiver, which were in complete darkness. In each case, 40 C.C. of liquid were distilled over. The results with comparatively pure specimens, such as A and B, mere absolutely negative, not the faintest luminosity being perceptible in any part of the apparatus. It is evident that pure, or even approximately pure, phosphorus sesquisulphide gives no reaction with Mitscherlich's test, and that Morner's results were obtained with samples containing small quantities of phosphorus, or of phosphorous oxide. Very crude specimens of phosphorus sesquisulphide 131 no doubt occasionally give Mitscherlich’s reaction : thus, with the impure specimen, D (tested after being kept for many months in the laboratory), a distinct luminous cloud played about the exit of the condenser, and in the air of the receiver above the surface of the distillate, which had n faint odour of phosphorous oxide.The sample C, which had been kept for nearly three years, and had undergone considerable oxidation, being quite moist, also gave a decided reaction. The distillate from this also smelt distinctly of phosphorous oxide, The specimens A and B, which gave negative results, had been recently made.Even in these samples some oxid- ation had occurred, but apparently no phosphorous oxide was present. The author is now conducting some experiments with the object of discovering whether exposure and keeping can so induce partial oxid-ation in, or alter the composition of, pure, or nearly pure, phosphorus sesquisulphide as to impart to it after a time the property of giving Mitscherlich’s reaction. Apart from its scientific interest, the point was of considerable practical importance. Meanwhile, the absence both of free phosphorus and of phosphorous oxide from phosphorus sesqui- sulphide of fair quality and purity and comparatively recent manu-facture was clearly indicated by the negative reaction with Mitscherlich’s test, and the following circumstances were corroborative as far as they went.Phosphorus sesquisulphide may be subjected to friction in air at a temperature very considerably exceeding the ignition point of phosphorus without becoming luminous, and with a total absence of ‘‘phosphorus fume” ; it neither ignites nor begins to glow in the dark until a temperature of 92-96’ is reached, and the finely divided residue of a solution in carbon bisulphide, evaporated on filter-paper at the ordinary temperature, neither glows in the dark, fumes, nor ignites spontaneously. 86. “Atomic and molecular heats of fusion.” By P. W. Robertson. No satisfactory relationship has hitherto been found connecting the latent heat of fusion of substances with their atomic or molecular weights. In the case of the elements, the following is shown to yield satisfactory results.‘‘For the elements with atomic weights above 40 which do not expand on freezing, the atomic heat of fusion divided by the melting point on the absolute scale into the cube-root of the atomic volume is a constant.” That is, Aw/T~F= constant. The numbers have a mean variation of & 10 per cent. The only exception is lead, for which the value of the expression is 25 per cent. below the mean. In the case of the binary inorganic compounds also, the expression Mw/Pa? ,where Pis the specific volume of the solid, yields concordant 132 results. The values of the expression for organic compounds increase with the number of atoms in the molecule, but when compounds of similar constitution are considered, fairly constant results are obtained. To test these relations, the latent heats of the following substances were determined : Thallium = 7.2 Phenanthrene = 25 Lead = 6.45 Phenylacetic acid = 32 Tin = 14.05 Tribromophenol = 13.4 Dinitrobenzene = 29.0 Tribromoaniline = 14.4 Thiosinarnine = 33.4.87. ‘(The preparation of mixed ketones by heating the mixed calcium salts of organic acids.” By E,B. Ludlam. A device for preparing a simple ketone from the calcium salt of the corresponding organic acid was described by Young (7kccns., 1891, 59, 623), which consisted in decomposing the salt at the temperature of boiling sulphur and removing the products by a stream of carbon dioxide.The author has extended the method to mixtures of calcium salts with very satisfactory results. The conclusions arrived at are : (i) That the decomposition is not of one molecule, but of two. (ii) There is a greater tendency towards the production of the mixed than of the simple ketone. (iii) That, for economy, it is advisable to dist’il tbe more expensive salt with excess of the cheaper one. By so doing the yield of mixed ketone from a given weight of the expensive salt is increased. 88. “Isomeric additive products of methyl, ethyl, and propyl benzyl ketone with benzylidene aniline. Part IV.” By F. E. Francis and E,B. Ludlam. The benzy lideneaniline additive products of methyl, ethyl, and propyl benzyl ketones were prepared in the expectation that they would furnish evidence as to the constitution of the tautomeric forms which such compounds are capable of assuming.Methyl benzyl ketone contains the group CH,*CO*CH,-, which in ethyl acetoacetate gives rise to the tazutomeric form CH,. C(0H):CH-, and it was hoped that the work mould have contributed to the solution of the problem of the constitu- tion of the tautomeric forms of that compound. Methyl benzyl ketone gave with benzylideneaniline an additive pro-duct melting constantly at 173” (a). This, under the influence of piperidine, gave the P-modification melting at 182O, and another modi- 133 fication melting at 184O when subjected to the action of a trace of sodium ethoxide. The hydrochloride of the a-modification was un-stable; it gave no fixed melting point, but slowly decomposed between 140’ and 190’.Propyl benzyl ketone gave a similar a-product, crys- tallising in silky needles melting at 136’, rising to 143’ under the influence of piperidine, and to 143’ with sodium ethoxide. Ethyl benzyl ketone gave an a-product melting at 161’, intermediate between 136’ and 173’. Neither the original ketones nor any of the additive products gave any coloration with ferric chloride, and the melting points of the p-and y-varieties fell when they were recrystal-lised from pure benzene. They were thus too unstable to serve the purpose for which they were prepared. -89.“The influence of solvents on the rotation of optically active compounds. Part 111. Influence of benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene on the rotation of ethyl tartrate.” By T. S. Patterson. It was found that in dilute solution the influence of benzene is to lower slightly the specific rotation of the dissolved ethyl tartrate. Toluene has a greater influence of the same kind, and this influence becomes greater and greater in the other solvents in the order in which they are placed above. It was found also that in benzene, toluene, o-xylene, and m-xylene there exists, not only a concentration of minimum rotation, but also one of maximum rotation, which lies at a greater dilution. The con-centration-rotation curves for p-xylene and mesitylene show only a point of inflection.The relationship between molecular-solution-volume and rota tion has been investigated, and it was found that in general, although not with- out exception, the behaviour mas the same as in the monohydric alcohols; when the dissolved ethyl tartrate has a molecular-solution-volume greater than the molecular-volume of the pure ester the rotation is correspondingly low. The relationships between rotation, latent heat of vaporisation of the solvent, and surface tension of the solvent were also discussed. 90. “The influence of solvents on the rotation of optically active compounds. Part IV. Influence of naphthalene on the rotation of ethyl tartrate.” By T. S. Patterson, Naphthalene was found to differ greatly in its behaviour from the benzene hydrocarbons. It has the effect of greatly increasing the 134 rotation of the dissolved ethyl tartrate, and its influence is similar to that of water in this respect as well as in the effect of temperature change.Thursday, June 5th, 1902. Professor THORPE,C.B., F.R.S., Vice-President, in the chair. Messrs. Steel, F. King, s. King, West, and F. M. Perkin were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Edgar Leeder Edlin, B.A., Marsh Parade, Newcastle, Staffs. George Felix Dudbridge Green, 9, Ross Road, South Norwood, S.E. Arthur Francis Hosking, Roskear Villas, Camborne, Cornwall. Douglas K. Jardine, B.Sc., 20, Doune Terrace, Kelvinside, Glasgow.Leonard Smith, 14, West Hill, Highgate, N. The certificate of Ah. Herbert Purtan, London Chambers, Durban, Natal, authorised by the Council under Bye-law I (3) was read. Of the following papers, those marked * were read :-"91. The action of ungerminated barley diastase on starch. Part I.'(( By J. L. Baker. When the diastase from ungerminated barley is allowed to act at 50' on a solution of soluble starch, hydrolysis proceeds until at the end of an hour to an hour and a half the constants of the dissolved matter are = 160-165' and R3.93= 60-65'. After this the reaction is a comparatively slow one, and if continued for 96 hours the reducing power is only increased to R,.,,= 70, the iodine reaction being still blue.An examination of the products, after the reaction had proceeded for 1%to 2 hours, showed that a dextrin and maltose were the sole pro- ducts. After 24 hours, evidence of the presence of glucose was obtained, the amount of this sugar apparently increasing in proportion to the time of conversion. The dextrin, isolated by precipitation with alcohol from the products of the conversion, gave a blue iodine reaction, a specific rotation of [a = 190-195', and a reducing power of R,.,, = 0*55-1". The alcoholic solutions from which the dextrin was precipitated were col- 135 lected and examined and found to contain maltose, glucose if the con-version period was prolonged, but no trace of any dextrin of less com-plexity than described above.Barley diastase acts on the above-mentioned dextrin very slowly, the constants of the solution after 90 hours at 45-50’ being [a]D3.93 =160’ and R3.1)3=32’. The products, which give a blue iodine re- action, consist of maltose, unaltered dextrin, and glucose. The presence of glucose could be detected in 18 hours, but after 90 hours the amount formed had only slightly increased. The action of malt diastase on this dextrin was more vigorous. After 18hours at 55’ the solution, which no longer gave an iodine reaction, had the constants [u]~~.,~= 149.3’ and R,.,, =50-51°. An examination of the products showed that they consisted of maltose, a mixture of achroo-dextrins, and a considerable quantity of glucose. Since barley diastase is without action on maltose, the glucose found in the products from the prolonged action of barley diastase on soluble starch must be derived from the dextrin. Barley diastase completely liquefies starch paste in 2 to 3 hours at 50°,the products consisting of the above described dextrin and maltose.The dextrin obtained by the action of barley diastase on soluble starch or starch paste diff ers markedly from Nageli’s amylodextrin,” which was reinvestigated by Brown and Morris (Trans,, 1889, 55, 449). In consideration of its general behaviour and close relation to the parent substance starch, the author proposes to term the new dextrin a-amylo-dextrin. DISCUSSION. Mr. A. It. LINGasked if the author had continued the reaction between barley diastase and soluble starch solution for a longer period than 144 hours, in fact until (when working with an excess of the diastase) the final point was reached. It had recently been shown by Mr.B. F. Davis and himself that by the action of the diastase from air-dried malt on starch paste below 60°, the whole of the starch was converted into maltose in 40 hours. He had been struck by Mr. Baker’s observation that maltose was practically the sole cupric-reducing compound formed in the early stages of the reaction between barley diastase and starch solution. With regard to the dextrin which the author had named a-amylodextrin, and which gave a blue iodine re-action, he could not help thinking, in view of what was known of starch- conversion products, that this dextrin (despite its apparent stability towards barley diastase) must have contained soluble starch.An indication of this was afforded by the behaviour of the dextrin towards maJt diastase when the iodine reaction vanished, Mr. BAKER,in reply, said that with regard to the suggestion of Mr. 136 Ling and Dr. Thorne, that a-amylodextrin was a mixture of another dextrin and unaltered soluble starch, he was convinced that a-amylo- dextrin was an entity, from the fact that when this dextrin was acted on by barley diastase for 18 hours at 50°, it split up into maltose and unaltered a-amylodextrin. If this residual a-amylodextrin was then subjected to the action of barley diastase under similar conditions, the same products were formed.This treatment had been repeated many times, and it did not seem possible that under such circumstances, soluble starch could escape the action of barley diastase. ”92. ‘(The decomposition of chlorates. Part V. Potassium chlorate in presence of oxides of manganese, and the theory of perchlorate formation.” By W.H. Sodeau, B.Sc. In continuation of the previous work of the author, it was now shown that the amount of chlorine accompanying the oxygen evolved from potassium chlorate in presence of oxides of manganese was not increased on reducing the pressure under which ths decomposition took place, whilst secondary reactions removing free chlorine from gaseous pro- ducts have previously (T~ans.,1901, ’79,251) baen experimentally shown to be greatly decreased on decomposition under reduced pressure.It was thus seen that no such secondary reaction occurred in the present case. This excludes all theories which assume the cycle of changes to in- clude the formation of a compound containing manganese and chlorine or potassium and manganese, such as McLeod’s well known theory. Oxygen being the only remaining constituent, it followed from this process of exdixsion that the cycle of changes brought about by addition of oxides of manganese was confined to alternate oxidation and deoxida- tion (like the decomposition of hydrogen peroxide in presence of the same substances). It is probable that the formation of potassium perchlorate during the decomposition of the pure chlorate by heat was due to an exo- thermic reaction independent of that which yielded chloride and oxygen.The non-production of perchlorate seemed to be the natural result of the addition of a substance (manganese dioxide) which brings about the transformation into chloride and oxygen at a temperature far below that at which the chlorate begins to give chloride and perchlorate. DISCUSSION. Professor E. J. MILLS said that, in association with Mr. Stevenson, he had, some years ago, investigated the action of manganic oxide on potassic chlorate. They had not been able to find or prepare an oxide free from constitutional water, and any attempt to render the oxide an- 137 hydrous resulted in a loss of oxygen. Eventually, they used the oxide of Beilstein and Javorsky.Their work had reference chiefly to the question of catalysis, and they found that small quantities acted in pro-portion more energetically than large ones. It should be borne in mind that the composition of hot manganic oxide was affected by pressure. Altogether, it was a question whether the numerous difficulties beset- ting the investigation could be satisfactorily surmounted. Mr. SODEAU,in reply, stated that in his examinations of the aqueous extracts of the residues, phenolphthalein was employed with precau- tions against carbon dioxide, and a very small fraction of the amount of alkalinity found by Prof. McLeod would therefore have been de- tected. The extracts were actually slightly acid, and the residual manganese peroxide rapidly absorbed potash from solution."93. Studies in the tetrahydronaphthalene series. I. The diazo-amino-compounds of cc~-tetrahydro-/3-naphthalene."By C. Smith, B.Sc. It has been shown by Bamberger and Bordt (Rer., 1889, 22, 625) that nr-tetrahydro-a-naphthylaminecombines with diazonium salts, yielding azo-compounds. The experiments of the author prove that ar-tetrahydro-p-naphthyl-amine behaves like a benzenoid amine and yields diazoamino-com-pounds. The following compounds have been prepared and examined : p-Toluenediaxoaminotetral~ydro-P-naphthalene, NH. CIOHll,CH,.C6H4*N,* yellow crystals, m. p. 107" ;readily soluble in alcohol and benzene, spar-ingly in petroleum. o-Nitrobenxenediusouminotetrah?/dro-~-n~pJ~thalene, N02.C,H4*N2.NH*C,oH11,orange-yellow crystals, m.p. 134". p-Nit~o-beneenediaxouminotetruhydro-/3-naphtlmZene,N02*C,H4*N,*NH*C,,Hll, well-defined chocolate-brown crystals, melting at 179" with violent decomposition. p-B?.omobenxenedicc~oa~inotetraJ~yd?.o-~-nc~p~thalen~, B *C,H4*N2*NH*CYloH,,, crys tallises in lemon-yellow needles which decompose slightly on exposure to the air and melt at 134". Diazo-a.nzinotetru~~ydro-P-naphthalene,Cl,H,,~N,*KH*C,oH,,, well-defined, amber coloured crystals ; m. p. 104O. P-ilrcc23htJ~aZenecl~a~oc~nain~tetr.a-hydro-@naphthalene, C,oH7~N2~NH*C,oH11,crystallises in light yellow, lustrous plates, m. p. 137-5O. TetraJ~ydro-~-napJ~tJ~alenea~o-~-napJ~thyl-amine, C,,H,,*N2*C,,H,*NH2, dark-red, lustrous crystals moderately soluble in hot alcohol ; m. p.130°. Tetrnhydro-P-naphthaleneaxo-/3-naphthol,C,,H,,*N2*Ul,H6*OH,vermilion-red crystals with a green shimmer, m. p. 153"; it is insoluble in sodium hydroxide, and only sparingly soluble in hot alcohol. 138 DISCUSSION. Dr. MORGANpointed out that the mixed diazoamines of the tetra-hydronaphthalene series are members of an extensive series of diazo-amino-compounds having the general formula XN,HY, which can be produced from one or other of the two pairs of generators, XN,Cl,YNH, and YN,Cl,XNH,, where X and Y are dissimilar aromatic nuclei derived from benzene, naphthalene (Tmns.,1902,81, go), and tetra- hydronapht halene. The genesis of these substances and their decomposition with mineral acids justify the belief that they are solid solutions of the two compounds, XN,*NHY and YN,*NHX.“94. ‘(Experiments on phosphorus tetroxide.” By C. A. West, B.Sc. The author gave an account of the preparation of phosphorus tetroxide and of his attempts to determine its molecular weight. Methods based upon observation of the freezing or boiling points of a solution could not be used, no suitable solvent being found. At a red heat, under atmospheric pressure, the compound does not volatilise rapidly enough to allow of the determination of vapour density, but four concordant experiments at about 1400” led to the unexpected con- clusion that the molecular formula is P8Ol0,that is, twice what would have been expected from comparison with P406and P4010.Some new determinations of the vapour density of phosphoric oxide at this temperature were also made. The mean of six concordant results gave 300.4 for the molecular weight, P,Olo requiring 284. 95. ‘(The decomposition of compounds of selenium and tellurium by moulds and its influence on the biological test for arsenic.” By0. Rosenheim, Ph.D. A paper has recently been published (Maassen, Ad. Kuis. Ges. A,, 1902, 18, 475) on the biological test for arsenic and the formation of organic compounds of arsenic, selenium, and tellurium by moulds. The author has been occupied for some time on the same subject in its connection with the detection of arsenic in beer and sugar, and had intended to publish his results in a more complete form.In view of Maassen’s publication it has, however, been thought advisable to give a short dsurnt? of the results in this direction confirming those d M aassen. The biological test for arsenic (Gosio, Ber., 1897, 30, 1024) is said to be characteristic of this substance (Abel and Buttenberg, 2.Eyg., 1899, 32, 449). The test consists in the formation of gaseous organic arsenic compounds, possessing a characteristic garlic odour, produced by the vigorous growth of certain moulds (Aspergdbus, MUCOT,and PeniciZZiurn) in media containing arsenic, and permits of its detection where chemical methods fail. When applying this test to certain substances (beer and sugar) which contained selenium and arsenic, the author noticed a pronounced fzecal odour different from that produced by arsenic alone.It was thought that this was due to the presence of selenium, and experiments with soluble selenium compounds con-firmed this view. It was also found that tellurium compounds were decomposed by Penicilliurn brevicaule, giving rise to the production of a very Characteristic odour. Owing to the extreme sensitiveness of the test with regard to arsenic, it was thought necessary to employ absolutely pure compounds of selenium and tellurium. The odour produced by the decomposition of selenium compounds is of a very dis- agreeable character (somewhat like skatol or mercaptan), whilst the gases formed by tellurium compounds possess a pronounced garlic odour.The test is extremely sensitive : 0.01 mg. in I C.C. of liquid is easily demonstrated by a vigorous growth of the mould, Unlike arsenic, pure selenium and tellurium are not attacked by the mould. It was found best to perform the test by using the medium proposed by Abel and Buttenberg (Zoc. cit.), namely, sterilised bread-crumbs, to which the sterilised liquid in question is added after infection with the mould. The author has drawn attention elsewhere (Chem. News, 1901, 83, 277) to the influence of selenium on certain chemical tests for arsenic, and it is evident from the above results that in applying the biological test for arsenic, it is also necessary to take the possible presence of selenium (and tellurium) into consideration.96. “Constituents of Gambier and Acacia catechus.” By A. G. Perkin and E. Yoshitake. The short paper on catechin, just published (Kostanecki and Tambor, Rev., 1902, 35, 1867), renders it necessary to give the results of an investigation which has been in progress for more than two years. The gambier catechu employed has been found to contain two catechins (b) and (c), and a third (a) has been isolated from the acacia catechu. Catechin (b),Cl,Hl,0,,4H,0, air-dried, colourless needles, corresponds in its melting point, 175-177°, with Gautier’s (b) catechin (Bull., 1879, 30, 567), and gives, on fusion with alkali, phloroglucinol, proto- catechuic acid, and an acid resembling acetic acid. The disuzobenzene compound (compare Etti, Monats., 1881, 2, 552), C,5H,20G(~,H,N2)2, salmon-red needles, m.p. 193-195’ ; its triacetyl derivative, C,,H,O,(C,H,N,),(C,H,O),, orange-red needles, m. p. 253-255O ; 140 pentabenxoyl catechin, C,,H70s(C7H50)6,colourless needles, m. p* 1.61-1 53', and tetrabenxoyl catechin, prismatic needles, m. p. 1'71-1 72', have been studied. Molecular weight determinations by the cryoscopic method of the two latter compounds confirm these formula. Catechin (c), C15H1406, air-dried, contains no water of crystallisation, and forms colourless prisms, m. p. 335-237O. It yields an axobenxene compound, C,,H,,O,(C,H,N,),, orange-red needles, m. p. 2 15-21 7', the acetyl derivative of which melts at 250-253', and on fusion with alkali gives phloroglucinol and protocatechuic acid.It has been found at present only in minute quantity. Catechin (a),C,,H,,0,,3H20 (or less probably C,,Hl,0,,3H20) air-dried, forms colourless needles and corresponds in its melting point, 204--205O, with Gautier's (a)catechin. Molecular weight determinations of the pentabenxoyl derivative (prismatic needles, m. p. 181-183') coin-cide with this formula. The axobenxene compound, Cl,H,20,(C,H5~,),, needles, m. p. 198-20Oo, gives a triacetyl derivative, Cl5H,O,( C,H5N,),(C,H30)3,orange-red leaflets, m. p. 22 7-229'. Fusion with alkali gave phloroglucinol, protocatechuic acid, and an acid resembling acetic acid. Cyanomaclurin (Trans., 1895, 67, 939), a constituent of Artocarpus integrifolia, has been found to contain a phloroglucinol group and is probably isomeric with these catechins. 97.LL The decomposition of oxalacetic hydrazone in aqueous and acid solution, and a new method of determining the concentration of hydrogen ions in solution." By H. 0. Jones and 0. W. Richardson. When oxalacetic hydrazone is heated with dilute acids it gives rise simultaneously to pyruvic hydrazone and carboxylic dioxide and to pyrazolone carboxylic acid and water (Fenton and Jones, Trans., 1901, 79, 92), the amounts of the former products being in the inverse order of the concentrations of the hydrogen ions in the solutions used. The hypothesis suggested to explain these observations mas that the negative ion of the oxalacetic hydrazone underment the first of the above decompositions when heated, whereas the undissociated molecule underwent the second.Experiment shows that the results are better explained by supposing that the rate of decomposition into pyruvic hydrazone is proportional to the concentration of oxalacetic hydrazone, whereas the rate of forma-tion of the pyrazolone carboxylic acid is jointly proportional to the concentration of the original substance and of the hydrogen ions. The reaction was investigated in two ways, first the rate of evolu-tion of carbon dioxide at a constant temperature (about SO') was 141 determined, and, secondly, the total amount of carbon dioxide given off at 100' was determined, in both cases water and sulphuric acid of different strengths being used. The results obtained agree with the requirements of the second hypothesis.According to both theories, the amount of carbon dioxide produced 1 satisfies the following equation, log 'Twhere C,=con-1=/3.t,1 --i [Gla,--!centration of pyruvic hydrazone (or amount of carbon dioxide evolved) at any time t, [C2Im its final concentration, and /3 =a constant. The hypothesis of the decomposition of the negative ion requires that /3 should decrease with increasing concentration of hydrogen ions, whereas the view here put forward requires that /3 should in- crease. Now it was found that p did increase with increasing concentration of hydrogen ions. This forms a crucial test between the two views. A quick and easy method for determining the concentration of hydrogen ions in solution has also been worked out and tested.Experiments have been made with the p-bromophenyl hydrazone of oxalacetic acid which decomposes in a similar way, and the results show satisfactory agreement with requirements of the theory stated above. 98. The dissociation constants of oxalacetic acid and its hydrazone." By H. 0. Jones and 0. W. Richardson. The authors have deter mined the dissociation constants of oxalacetic acid and its phenyl hydrazone. The conductivities of solutions of these substances were determined at 25O, and from the results the folIowing values were obtained : For oxalacetic acid, K = 1.33. Oxalacetic hydrazone, K =0.11. 99. Derivatives of butgrylpyruvic acid." By A. Lapworth and A.C. 0. Ham. Certain points of interest arising out of the study of the Claissen reaction as applied to ap-unsaturated ketones (5"ra?zs., 1901, 79, 1283) led the authors to study the action of ethyl oxalate and sodium on benzylideneisopropylmethylketone. The results were not those antici- pated, but the following compounds have been prepared in the course of the work : Berzxylideneisopropylmethylkeetone, CHMe,*CO*CH :CHPh, is an oil (b. p. 274-276'). The oxime melts at 131-132' and the sernicarb-axone at 166-167O. Ethyl isobutyrylpyruvate, CHMe,*CO*CH,*CO*CO,Et, from isopropyl- 142 methylketone, ethyl oxalate, and sodium ethoxide, is a nearly colourless oil which boils and decomposes at 230--232*; it does not solidify at -15’. The copper, michl, calcium, and other derivatives have been prepared.When the ester is hydrolysed with strong potassium hydr- oxide solution under certain conditions and the resulting solution treated with excess of strong hydrochloric acid, a sparingly soluble compound is precipitated in quadratic plates. This is an acid potassium isobutyryZpyruvate having the composition (C7H,,04),*C7Hg0,K ; its solution gives a red coloration with ferric chloride, and becomes yellow on addition of excess of alkalis; it is only decomposed by a large excess of mineral acid ;a similar sodium salt was not obtained. Ethy2 n-butyryZpymvate, Pr*CO*CH,*CO*CO,Et, is similar in proper- ties to the ester described above. When it is hydrolysed with potassium hydroxide, it yields a sparingly soluble acid potassium n-butyrylpyruvate crystallising in asbestos-like needles, which has, however, the com-position (C7H,,04),-C7H,04K.As in the former instance, this substance is very stable towards acids, and no corresponding sodium salt could be obtained. 6‘100. Sulphocampholenecarboxylic acid.” By A. W,Harvey and A. Lapworth. When the residues obtained by evaporating the last aqueous mother liquors in the preparation of ammonium bromocamphorsulphonate were fractionally extracted with alcohol, a small quantity of a new sub- stance dissolved and was obtained in the form of transparent, calcite-like crystals. A small quantity of this product has also been obtained by Dr. Kipping. The compound has the formula O,,H,,SO,NH,, and it is the hydro- gen ammonium salt of an unsaturated, monocyclic, sulphocarboxylic acid, C0,H-C,H14*M0,H,for which the name sulp~oc~nzp~oZenecar60xyZi~ &d is proposed. That it is unsaturated is shown by its aqueous solution instantly decolorising bromine water and an ice-cold solution of potassium permanganate.The normal baviurn aud calcium salts, C,,H1,S05Ba and C,,H1,SO,Ca, crystallise well and are more soluble in cold than in hot water; the normal ammonium salt is very soluble in water. The hydrogen barium and hydrogen calcium salts crystallise in fine needles. The chloride and bromide do not crystallise readily. When solutions of the salts are treated with bromine, a molecular proportion of the latter is at once absorbed, and a very sparingly soluble substance separates.This appears to be a sultonecarboxylic acid, C0,H~~gH,4Br*S0,*0; it crystallises from chloroform in small I 143 prisms, melts and decomposes at 155O, dissolves in alkalis and alkali carbonates, and is reprecipitated unchanged by acids. The investigation of the acid and its derivatives is in progress. 101. ‘‘ Some properties of camphorquinonephenylhydrazone.” By A. Lapworth and A. (3, 0. Hann. It has been found by Betti (Bey., 1899, 32, 1995) that camphor-quinonepheny lhydrazone (“ camphormethylenehydrazone ”) usually exists as a mixture of two desmotropic forms, One of these melts at l8O0, gives a reddish coloration with ferric chloride in benzene solu- C*N:NPh tion, and is therefore probably the enolic form, C,H,,<8.0H .The other, melting at 155O, may be isolated by adding a trace of piperidine to a solution of the hydrazone in benzene ;as it gave no distinct colour with ferric chloride, it was supposed to be the ketonic form, With Betti’s permission, the authors have carefully studied the pro-perties of the compound, and, although they are able to confirm all his statements with regard to the enolic form, they have not been able to isolate a second modification in the pure state, although there can be no doubt that one is present; they think that the substance melt- ing at 155’ must be a mixture of both forms. The speed with which equilibrium between the two forms, in various media, is attained was investigated by observations of the mutarota- tion. Equilibrium appears to be reached most rapidly in alcoholic solution, a constant rotation being observed at once.In chloroform or benzene, however, the change occurs very slowly, as in 1 per cent. solution at the ordinary temperature it occupies several days. In benzene, with solutions varying in concentration from 0.1 to 1 per cent., the initial rotation, when the pure enol is used, is about = + 325O, and falls to between + 205’ and 290’ according to the concentration. With all specimens of mixed material, even when pre- pared by Betti’s method, a fall was invariably observed in dilute solu- tion, indicating that the enol was still present in considerable amount. The effect of catalytic agents on the rate of change in benzene was carefully studied. Traces of bases, if not too weak, whether primary, secondary, or tertiary, accelerate the change, and, amongst others, ammonia, aniline, pipedine, pyridine, brucine, and strychnine were tried and found to be effective.Acids, on the other hand,retard the change, and it is possible to arrest the fall in rotation at any point desired by the addition of a minute quantity of trichloroacetic acid, when it will again proceed on addition of a trace of a base, 144 In all cases, as was to be expected, the state of equilibrium was found to be independent of the catalytic agent. 102. '(Optically active esters of /3-ketonic and /3-aldehydic acids. Part I. Menthyl hgdroxymethylenephenylacetate." By A.Lapworth and A. C. 0. Ham. The authors propose to investigate certain aspects of the question of tautomerism involving the migration of hydrogen atoms by the employ- ment of esters of P-ketonic and /3-aldehydic acids with optically active alcohols of high molecular weight. It is hoped that the compounds may thus be obtained in a crystalline and, therefore, more easily purified form, and that by observation of the change of rotation, further evidence with regard to certain obscure points may be obtained. Nenthyl Izydroxyrnethylertep~~enylacetccte,HO*C:CPh*C02CloH1g,may be prepared by the action of sodium on a mixture of menthyl phenyl- acetate and formate dissolved in anhydrous ether. It is precipitated from the aqueous solution of its sodium derivative on addition of acids as an oil which rapidly soldifies, and crystallises from light petroleum in transparent prisms or pyramids, which belong to the tetragons1 system.These melt at 82-43' and exhibit tribol uminescence, which is sufficiently brilliant to be observed in broad daylight. Its freshly prepared 2 per cent. solution in chloroform has [a],= -74.6'; this falls in 2 few days to about -71". In absolute alcohol, the rotation is [a]D= -64 go, and falls only slightly, if at all, in course of time. Although its alcoholic solution is rapidly coloured violet by ferric chloride, its solution in ether or benzene is not affected unless it is boiled with the salt for some time, or a trace of a base is added, when a similar coloration develops.The solid probably repre- sents the aldehydic form of the ester (Wislicenus, Ann., 1900, 312, 34). The copper derivative crystallises in green prisms which melt and de-compose at 92-95"; the sodium derivative forms thin, transparent plates. The phenylcarbamate, N HPh-CO,*CH: CPh*C0,-CI0Hl9, crystallises in long, slender needles melting and decomposing at 235-237". The acetate, AcO*CH:CPh*CO,-CloH,g, separates from ethyl acetate in needles melting at 51-52". The oxime is immediately precipitated as an oil on mixing solutions of the ester with one of free hydroxylamine or hydroxylamine acetate. With phenylhydrazine, the ester is converted into the diphenylpyr- azolone which is obtained from the corresponding ethyl ester.The enolic modification of the ester appears to be very unstable, and under conditions in which the liquid enolic ethyl ester may be obtained, the above compound was always produced. No evidence of the existence of isomeric copper or acetyl derivatives could be obtained. 145 103. Optically active esters of P-ketonic and P-aldehydic acids Part 11. Menthyl acetoacetate." By A.Lapworth and A. C.0. Hann. Menthyl acetoacetate may be obtained in small quantity by the action of sodium on menthyl acetate, but is far more easily prepared by heating menthol with ethyl acetoacetate until alcohol ceases to come off. These observations were made before the authors were aware that Cohn had prepared the ester by the latter process (Mosiatsh., 1900, 21,200-204).As Cohn has since notified (Ber., 1900, 33,734) that he had abandoned the work, with his concurrence the authors have resumed the study of this substance and its derivatives. The compound may be obtained in large, lustrous, probably mono- clinic prisms which the authors believe to represent the ketonic form. Its rotation in 2 per cent. solution in benzene is initially about [a],= -61-62' but slowly increases to about -68O, owing doubtless to partial conversion into the enolic form; similar changes are observed when it is dissolved in chloroform, light petroleum, and dry ethyl acetate. The duration of the change varies greatly with the purity of the solvent, as the compound is exceedingly sensitive to catalytic agents.As usual, all bases accelerate the change, and the mutarotation, unlike that of camphorquinonehydrazone, and of nitrocamphor is accelerated by traces of acids also. Equilibrium between the two forms appears to be attained almost at once in alcohol, prkctically no alteration of rotation with time being noticeable. The copper derivative of the ester crystallises from alcohol in green prisms which contain alcohol ;these rapidly become opaque and finally have the melting point 117-118'. The ester readily affords a well-defined semicccrbaxide, NH2*CO*N2H2*CMe:CH*C0,C1OH19,flat needles, m. p. 143-144' ; in benzene [aID= -56.1'. The p-nitrop~enyl~~ydra~~~, C6H,N02*N,H2-CMe:CH.C0,.C,oH19,brilliant prisms, m. p. 105-1 06" ; in benzene [aID= -42.5".Menthyl P-arninocrotonate, NH2*CMe:CH*C0,CloHlg, prepared by the action of gaseous ammonia; forms large, transparent plates, m. p. 88-89" ;in benzene [a]*= -105.2'. Menthyl ~-phenylaminocrotonate NHPh*CMe:CH*C02CloH,g, crystallises in flat, rectangular plates m.p. 85-86' ; it has [a],,= -98.2'. Menthyl benx~kccminocrotonccte, CH,Ph*NH:CMe:CH*C02CloHlg,crystallises in flat needles, m. p. 85-86' ;in benzene [a],= -59.8'. Menthyl C-benxoylacetoacetate, CHBzAc*C0,C,oH19, is an oil ;in benzene [ = -44.3' ;its copper derivative forms slender needles, is sparingly soluble in most media, and melts at about 230'. Neither the oxime, the isonitroso-, nor bromo-derivatives of the ester have yet been obtained in a pure condition.The ester condenses readily with aldehydes, forming, in some cases, well crystallised compounds. Unlike ethyl acetoacetate, when con-densed with benzaldehyde at the ordinary temperature by the aid of piperidine, it affords, for the most part, a monobenzylidene compound. 104. “The mechanism of simple desmotropic change.” ByA. Lapworth and A. C. 0. Hann. Briihl has advanced the hypothesis (Bey., 1899, 32,2329) that enols (which are weak acids and electrolytes) are transformed into the iso- dynamic ketones, by a process which involves initial ionisation into hydrogen ions and organic ions or ‘‘residues,” which may reunite in two ways, so that finally the ketone is produced in this manner : -+ :C=C*OH f-f :C=C-O+H -+ :CH-d=O.He found, as he anticipated, that the velocity of transformation of enolic ethyl mesityloxideoxalate in solution into the ketonic form increases roughly with the dielectric constant of the medium. Although the principle here introduced appears quite reasonable, and more capable of experimental and theoretical development than any other yet suggested, it is clearly incomplete, since ketones, although apparently non-conductors, are known to exist in equilibrium with their conducting enolic forms, and the velocity of transformation must be far slower than the ionisation velocity. Since change of internal structure is necessary, and isomerisation appears to increase with ionisation, the authors think that Briihl’s suggestion would lead to the following view of the processes involved in a keto-enol transformation (compare Tram., 1901, 79, 1266).X=Y-Z-H ++ X=Y-Z-+H1 xzy-2-f-f ,-x-Y=Z (-X-Y=Z+H +-+ XH-Y=Z Here it appears necessary to assume that ketones themselves are very slightly ionised, which is consistent with the views of Thiele, Vorlander, and others. According to this view, bases should accelerate and acids retard the change, and the state of equilibrium should be independent of the catalytic agent, but dependent, not only on the two dissociation constants, but also on the velocities indicated in the second line. It is, in fact, perfectly consistent with the properties of Certain isvdynamic pairs, for example, nitro- and isonitro-camphor (Lowry, Trans.,1899, 75, 22 l), and camphorquinocehydrazone.However, the complete difference in behaviour of camphorquinone- hydrazone and menthyl acetoacetate toward acids indicates that there 147 are at least two classes of substances, and that more than one type of process may go on. To account for the action of acids in accelerating the speed of migra-tion of a hydrogen atom, in certain cases, on a principle similar to that proposed by Briihl, it seems necessary to assume that the compounds may react as bases. Since, as before, a change of structure is involved, the change may be conventionally analysed as follows : X=Y-Z-H+H f-f XHyY-Z-H XHTY-Z-H f-, XH-YyZ-H XH -Y TZ -H f-f XH-Y=Z+H where the dot indicates the direction in which the “free affinity” of Y is temporarily disposed, a convention easily understood by reference to models.The process thus represented requires an acceleration of the change by acids, and a final state of equilibrium independent of their presence. Clearly, a compound might react in either or possibly in both ways, according to the conditions. In nearly all cases observed, however, the first process would appear to go on, the latter being somewhat exceptional, at least as an important factor. Obviously, the state of equilibrium must be the same when attained by either process. 105. Trimethylbrazilone.” By W.H.Perkin, jun. During the course of a long series of experiments on the constitution of brazilin, it was shown (W. H. Perkin and A. W. Gilbody, Proc., 1899, 15,27) that trimethylbrazilin, HO*C,6H,oO(OMe)3, on oxidation with chromic acid, yields trimethylbrazilone, HO*C,,H,O,(OMe),.It was also stated that nitric acid converts trimethylbrazilone into a sub-stance crystallising in yellow needles, which dissolve in alkalis, forming an intense purpls solution ; this, on standing, yields besides p-methoxy- salicylic acid, MeO-C6H,(OH)*C0,H, two neutral substances melting at 118” and 206’ respectively. Since the yellow substance did not give the usual qualitative tests for nitrogen, it was at first thought that it did not contain this element ; subsequent quantitative experi- ments, however, demonstrated the presence of nitrogen, and showed that the substance has the formula C,,H,,OgN. It is proposed to name it nitrohydroxydihydrolrinzethylbrazilone.The two neutral substances having the melting points 118Oand 206O are probably isomeric, and have the formula C9H1,04N,and as they each contain two methoxy-groups, they are apparently nilrodimethoxy- methylbenzenes, the former (m. p. 1lS’j being probably identical with the compound N0,AOMe Me!,)OMe 148 which has already been prepared by H. Cousin (Ann,. Chim. Phys., 1898, [vii], 13,480), and which melts at 117’. There is, however, a possibility that the very sparingly soluble substance of melting point 206O has a higher molecular weight such as that represented by the formula (C,H,,,NO,), . When nitrohydroxydihydrotrimethylbraziloneis oxidised with per-manganate, it yields 2-carboxy-5-methoxyphenoxyaceticacid, and since it also yields an acetyl compound, it is probably a lactone, having the formula 0 or some formula closely allied to it.The author has not yet concluded his experiments on this interesting nitro-compound, but finds it necessary to publish this short note because of a recent publication of Bollina, Kostanecki, and Tambor (Ber., 1902, 35,1675), which contains a description of some experi- ments on this compound. The author hopes that these chemists will allow him, for a short time longer, the uninterrupted investigation of this substance. At the next meeting, on Wednesday, June 18th, at 5.30 p.m., there will be a ballot for the election of Fellows, and the following papers will be communicated : ‘‘Elimination of a nitro-group on diazotisation.Dinitro-p-anisidine.” By R. Meldola and J. V. Eyre. ‘‘A new type of substituted nitrogen chlorides.” By F. D. Chattaway.‘‘The colour-changes exhibited by the chlorides of cobalt and some other metals, from the standpoint of the theory of electro-affinity,” By F. G. Donnan and H. Bassett, jun. ‘‘The stereochemical formula of benzene.” By J. E. Marsh. “An accurate method of determining the compressibility of vapours.’ ’ By B. D. Steele. ‘‘The molecular condition of borax in solution.” By H. S. Shelton. ‘6 Preliminary notice of some new derivatives of pinene and other terpenes.” By W. A. Tilden and H. Burrows. “The preparation of pure chlorine and its behaviour towards hydrogen.” By J.W. Mellor and E. J. Russell. “The union of hydrogen and chlorine. Part V.” By J. W. Mellor. CER,TIFICATES OF CANDIDATES FOR ELECTION AT THE NEXT BALLOT. N.B.-The Eames of those who sign from ‘(General Knowledge ” are printed in italics. The following Candidates have been proposed for election. A ballot will be held on Wednesday, June lSth, 1902. Ball, James Handby, St. Stephen’s Villa, Limerick. Analytical Chemist,. B.Sc. Honours Chemistry, Victoria Univer-sity. Analyst to The Condensed Milk Company of Ireland, Ltd. Past Experience. (1)Assistant to Dr. Campbell Brown. (2) Chemist to The North of England Chemical Works, Berwick-upon-Tweed. (3) Science Master of The Carpenters’ Company’s Technical Institute, Stratford, E., and at The Blue School, Wells, Somerset.J. Campbell Brown. Herbert B. Stocks. W. Collingwood Williams. Charles A. Kohn. J. G. Taylor. Bucknell, Edwin Thomas Holman, Ebley House, Parsonage Street, Dursley, Glos. Chemical Laboratory Assistant. Student in the Merchant Ven-turers’ Technical College Laboratory (Bristol) three years. Five and a half years as Assistant in the Rugby School Chemical Laboratory. G. Stallard. James Leicester. J, Wertheimer. F. N. A. Fleischmann. B. P.Dawd-Smitli. 150 Burt, Bryce Chudleigh, University Settlement, Bermondsey, S.E.. ; Univ. Coll., Gower Street. Research Student at University College. B.Sc. (Lond.), first class hon. Chemistry. Late Student and Associate of Merchant Venturers’ Coll.Bristol (four years). At present Research Student at Univ. College, London. William Ramsay. F. G. Donnan. Edward C. Cyril Baly. Morris W. Travers. Alex. Findlay. Claudet, Arthur Crozier, 27, Daleham Gardens, Hampstead, N.W. Assayer and Metallurgist, and Analytical Chemist. Associate of the Royal School of Mines. Fellow of the Institute of Chemistry. W. C. Roberts-Austen. John S. Sellon. Thos. Kirke Rose. George Matthey. A. K, Huntington. >4Xough, William Thomas, 3, Watford Villas, Bnttersea Park, S.W. Science Master, Owens School, Islington. Science Lecturer, City of London College. A.R.C.S. (London) ; 1st Honours in Chemistry, South Kensington Exams, ; Fellow of the Physical Xociety of London ; Late National Scholar. William A.Tilden. W. H. C. Jemmett. W. Palmer Wynne. A. E. Dunstan. Chapman Jones. James C. Ph,iEip. A?. 0.Porster. Davis, Henry Wilson, 18, Crescent Road, Kingston Hill, Surrey. Analyst, Government Laboratory. First Class Certificate School of Mines, Theoretical and Practical Chemistry. Thirty years’ expe- rience in analytical work in Government Laboratory, London. T. E. Thorpe. C. H. Burge. H. J. Helm. J. Woodward. Edwd. Jones. C. Proctor. 151 Ferris, Percy J., Heathfield, Seymour Grove, Old Traff ord, Manchester. Chemist in firm of Chemical Brokers, Liverpool. For 3 years student in Chemical Laboratories of the Owens College. For 1 year research student under Prof. W. H. Perkin. H. B. Dixon. J. Campbell Brown. W. H Perkin, jun.Arthur Smithells. J. No~manCollie. Poll, Edgar William, 40, Sutton Street, Lambeth, S.E. Brewer. Engaged at Lion Brewery, Belvedere Road, S.E. Have studied chemistry for a considerable perioci. During the past four years have been under the tuition of Matthew J. Cannon studying chemistry in relation to brewing. Obtained prize medal in brewing, 1899 ; silver medal honours, 1900, City and Guilds Examination. Have assisted Mr. Cannon in investigation work. Desire to join the Society to keep in touch with scientific progress. Matthew J. Cannon. C. A. Mitchell. M. Cannon. As.thur R.Ling. J. Jackson. ArtiLur Hart Zey. Francis, Francis E., 8, Manilla Road, Clifton, Bristol. Lecturer and Demonstrator in Chemistry, University College, Bristol.B.Sc. (Victoria) ; Ph.D. (Erlangen) ; A.I.C., 1892 ; Assist-ant Lecturer in Chemistry at Univ. Coll., Liverpool, 1895. Senior Lecturer and Demonstrator, Univ. Coll., Bristol, since 1896. Author of “ Zur Kenntniss der o-Amidobenzylamine ” ;“The Dinitrosamines of Ethylenaniline and its Derivatives ” ;‘‘ The Separation of N-and iso-Heptane from American Petroleum ”;‘‘Action of Fuming Nitric Acid on Paraffins and other Hydrocarbons ”; ‘‘ Derivatives of Dibenzyl Ketone.” Sydney Young. . Philip J. Worsley. W. A. Shenstone. J. Campbell Brown. W. Collingwood Williams. Garle, John Longsdon, 136, Holland Road, Kensington, W. Consulting Chemist. Student at ‘University College, Loodon, 152 Demonstrator at Pharmaceutical Society.Assistant to Charles J. Wilson, Esq. I am desirous of attending the meetings of the Society and obtaining its publications. J.Norman Collie. Edward C. Cyril Baly. William Ramsay. F. G. Donnan. Charles J. Wilson. Gow, Alexander, 38, Clarendon Sheet, Cambridge. Student. Lecturer in Chemistry. Borough Road Training College, 1893-97. Chief Science Master, County High School, Isleworth. Isleworth, 1897-1900. B.Sc., London, 1893,in Chemistry. Studying Chemistry at Cambridge under Dr. Ruhemann. 5.Ruhemann. R. S. Morrall. M. M. Pattison Muir. Hugh Ramage. H. 0. Jones. Hallowell, Thomas Butterworth, Ladyshawe House, New Mills, Derbyshire. Analytical Chemist to Calico Printing Works, Birch Vale, Derby- shire. Having studied Chemistry at the Owens College, and been Assistant for five and a half years to A.W. Duncan, Esq., F.C.S., in the Analytical Laboratory of Messrs. J. Woolley, Ltd., Manufacturing Chemists, Manchester. Have held my present position for nearly two years. Arthur W. Duncan. W. T. Lawrence. Wm. A. Bone. J. F. Thorpe. H. B. Dixon. Hann, Archie Cecil Osborn, 54, Wood Vale, Forest Hill, S.E. Teacher of Chemistry. For four years Student in the Chemical Dept., Goldsmiths’ Technical Institute, New Cross. Now Assistant Lecturer in the same. Engaged on Research Work with Dr. Arthur Lapworth. Arthur Lapworth. Stanley J. Peachey. Alfred W. Harvey. Gerald T. Moody. William J. Pope. Arthur H. Coote. Harrison, Walter Ernest, 43,Mostyn Road, Handsworth, Staffs.Science Master, Technical School, Handsworth. Associate of the Royal College of Science, London. Eight years Senior Science Master, Addey and Stanhope School, S.E. Now Science Master, Handsworth Technical School, Staffs. Wm. Ping. J. W. Shepherd. J. H. Wolfenden. Chas. Wood. T. A. Cheetham. Chapman Jones. S. Whalley. Jumes C. Phitip. S. Parrish. Alex. IT.Bain. Leader, George Herbert, Sexe9’s School, Blac kf ord, Wedmore, Somerset. Senior Science Master at Sexey’s Secondary and Technical School. A Student, during 1898, in the Chemical Laboratory of the Merchant Venturers’ Technical College, Uristol. Chemical Laboratory of Uni-versity College, Bristol, 1899-1 900, and the Chemical Laboratory of University College, London, 1901.B.Sc. Lond. (with Honours in Chemistry and Zoology), 190 1. Associate of University College, Bris tol. Sydney Young. F. G. Donnan. J. Werthoimer. Edward C. Cyril Baly. William Ramsay. Morris W. Travers. Lessner, Charles B., Fonda de Porto, Carril, Spain. Metallurgical Chemist and Assayer. Studied Chemistry and Metal- lurgy at Battersea, Chelsea, and Woolwich Polytechnics, Northampton Institut,e, Birkbeck Institution, King’s College, &c. Student Institu- tion Mining and Metallurgy. Two years Assistant to Messrs. Hollo-way, Lake, and Currie. Assayer to the Kai Syndicate, Gold Coast Colony. George T. Holloway. Herbert S. Wallace. Philip Schidromitz. Alec. A. Beadle. C. J. Head. John Wilson. Moody,James Butler, 111, Manchester Road, Burnley, Lancs.Head Brewer at Massey’s Burnley Brewery Ltd., Burnley, Lancs. 154 Formerly student under Dr. Graham and Mr. Alfred C. Chapman, of London, and Dr. Miller? of Manchester. Alex. K. Miller, Alfred Chapman. John F. Rolfe. Tom Crossman. Pred R.Xtone. Moore, Thomas Henry, 19, Sandmere Road, Clapham, S.W. Chemist. Major Exitm. of the Pharmaceutical Society. W. Watson Will. .Frederick B. Power. Harold C. Sayer. F. Filmer De Molyan. J. Bernard Coleman. E. F. Harrison. O’Connor,Sinnott Valentine, 14, Selskar Street, Wexford. Pharmaceutical and Analytical Chemist, A Licentiate of the Pharmaceutical Society by Examination. Charles R. C. Tichborne. J. Armstedt Ray, jun. Henry Boyers.John Barclay. Thomas Tyrer. Phillips, Percy Philip, Ph.D. Haslemere, Morris Avenue, Manor Park, E. Chemist. Certificate of the City and Guilds of London Institute in Applied Chemistry. P1i.D. Gottingen. Researches published : (1) ‘‘Amidoamidines of the Naphthalene Series,” with Prof. Meldola (2) ‘‘Beitriige mr Kenntnis der D-d-Fenchenderivate und der Fencho- carbonsaure,” with Professor Wallach. Raphael Meldola. 33. 0. Forster. G. T. Morgan. James C. Phizip. WiZZiam Robertson. Pollitt, George Paton, Ph.D., St. Silas’s Road, Blackburn, Lancashire. I have studied Chemistry at Owens College, Manchester, and at the Polytechnicum of Zurich under Professor Lunge. I have obtained the degree of Bachelor of Science, Hons. Chemistry of the Victoria University and that of Doctor of Philosophy of the University of BBle, my Dissertation for which latter degree, “On the use oE Oxide of Iron as Contact Substance in the manufacture of Sulphuric Anhydride from Sulphur Dioxide and Air,” will shortly be published.Harold B. Dixon. D. L. Chapman. W. H. Perkin, jun. Wyndham R. Dunstan. J.F. Thorpe. G. Lunge. 155 Powney, William E. F., 67, Barretts Grove, Stoke Newington, London, N. Analytical Chemist and Assayer; Chief Assistant to Geo. T. Holloway, Esq., Consulting Chemist and Metallurgist, of 57, Chancery Lane, London, W.C. Studied Chemistry for three years under Prof. Meldola, F.R.S., at Finsbury Technical College, Leonard Street, City Road, E.C. Have held present position for nearly six years. Qualified to teach Chemistry and Metallurgy under the Board of Education, Member of the Society of Public Analysts, and of the Society of Chemical Industry. Student-member of the Institution of Mining and Metallurgy.George T. Holloway. Alec. A. Beadle. Philip Schidrowitz. D. A. Louis. Raphael Meldola. Ralph, Stephen Jamieson, 22, Stanley Place, Eccleston Square, S.W. Assistant Research Chemist. Certificated Student, Technical College, Finsbury. Research Assistant, Imperial Institute, Scientific Depart- ment. Raphael Meldola. Ernest Goulding. F. Southerden. Henry H. Robinson, J. Vargas Eyre. E.H. Millel.. Thomas A. Henry. Ralphs, Edwin, Hongkong. Senior Grade Master, Queen's College, Hongkong (Hongkong Civil Service).Student in Chemistry since 1885. First Class Advanced Certificates in Inorganic Chemistry (Theor. and Pract.), also First Advanced Certificates in Organic Chemistry (Theor. and Pract.), Science and Art Dept. Desire to keep in touch with Chemical Progress. Charles A. Fogg. T. M. Nightingale. A. L. Thornton. Walter Ratcliffe. Harold Rostroo. Jno.L.Whiteside. Rby, Prafulla Chandra, Calcutta, D.Sc. (Edin.). Chemical Laboratory, Presidency College. Has 156 been for a long time Assistant to the Professor of Chemistry in the Presidency College, Calcutta. Is the author of several pipers, princi- pally upon the Nitrites of Mercury, which have appeared in the T~ansactions, Zed., ccnorg. Chem., Annalen, and Calcutta journals.Alex. Crum Brown. James Walker. J. Gibson. William Ramsay. Edwcwd Bivem. Roast,Harold James, 3, Manor Park Road, Harlesden, N.W. Student of Chemistry three years. Engaged in Analytical work, and Assaying. Desire Membership of the Society as I wish to attend the meetings and to have the Society’s Journal. Isaac Sydney Scarf. John Grove Johnson. Harold W. Harrie. Charles A. West. H. Y. Loram. Skertchly, William Pearson, The Laboratory, 11, Billiter Square, E.C. Analytical Chemist. Fellow of the Institute of Chemistry of Great Britain and Ireland, Member of the Society of Chemical Industry and of the Society of Public Analysts. Contributor of original papers to me Analyst. Eleven years Chief Assistant to Mr.Otto Hehner, F.I.C., F.C.S. Otto Hehner. Bernard Dyer. Alfred C. Chapman. Arthur R. Ling. B. E. R. Newlands. Stanger, William C.S., 72, Belle Vue Road, Ipswich. Schoolmaster, Higher Grade School, Ipswich. Student in Chemistry 1892-1895 ; Durham College of Science under Dr. Bedson, Prof. of Chemistry, A.Sc. (Durham) in Chemistry and Physics (1894). In sole charge of Chemical Dept., Ipswich Higher Grade School. Have now under instruction approx. 500 pupils in Chemist,ry per week. P. Phillips Bedson. S. Hoare Collins. F. C. Garrett. E. J: cox. Duncan T. Richards. I?. 1;. Taylor. W. J. Stainer. 157 Stewart, Hector, 479, Collins Street, Melbourne. Mining Engineer and Metallurgical Chemist (1X.C.E.). Master of Civil Engineering, Melb.Univ. Twelve months in charge of works for the treatment of gold ores, including chlorination, concentration, and assaying, Victoria. Four years assayer in charge of laboratory of the Lye11 Tharsis M. Co., Tasmania, engaged on ore, rock, slag, and other analyses and assays. Memb. Austrn. Inst. of Mining Engineers. H. W. Potts. R. Dubois. Henry C. Jenkins. A. W. Craig. J. Dennant. Wells, John William, Springburn, Blackburn. Medical Practitioner. M.B., C.M. Edinburgh, 1887. D.P.H. (Victoria) 1901. Am enga.ged on experiments on the relation between chemical constitution of fats and their digestibility, and desire Chemical Society’s publications. Robert H. Pickard. Jas. F. Burnett. Harold B. Dixon. William Lewins. William Carter.Arthur CEegg Bowd Zer. W. H. Duckworth. Praneis V. Dadishire. West, Joseph, 50, Poplar Grove, Fenton, Stoke-on-Trent. Analytical Chemist. Analytical and Consulting Chemist to the Stafford Coal, Iron, and Chemical Works. Formerly of the Darwen and Mostyn Iron Works, Darwen. Lancashire and Cheshire 1st prize in Honours Chem. S.K. Formerly Student at Blackburn T. Schl. and Darwen T. Schl. C. Gerland. George George. G. W. Burman. Hurqj F. Dixon. Geo. P. Rees. Wheeler, Edward J. Albany, State of New York. Analytical and Consulting Chemist. Has taught chemistry since 1888 at different times at Williams College, at Union University, in departments of Medicine and Pharmacy. As Analyst in employ since 1591 of State of N.Y. Board of Health and Department of Agricul-ture, N.Y.John A. Miller. Joseph E. Geisler. Willis G. Tucker. E. G. Love. J. H. Wainwright. 158 The following certificate was authorised by Council under Bye-law I.(3) : Purtan, Herbert, London Chambers, Durban. Public Analyst for Borough of Durban. Studied at Aberdeen University. Teacher of Chemistry at Seamen's Hospital, Greenwich. Assist'aat to R. H. Davies. F.I.C., &c., Apothecaries' Hall. Manag-ing Director, Natal Chemical Co. W. H. Pay. T. G. Mrtcdonald. J. S. Jnrnieson. A. Pady. RICHARD CLAY AND SONS, LIMITED, LONDON AND BUKC:.&Y.
ISSN:0369-8718
DOI:10.1039/PL9021800123
出版商:RSC
年代:1902
数据来源: RSC
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