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Proceedings of the Chemical Society, Vol. 25, No. 363 |
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Proceedings of the Chemical Society, London,
Volume 25,
Issue 363,
1909,
Page 283-298
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. Thursday, December Znd, 1909, at 8.30 Pam., Professor HAROLDB DIXON,F.R.S.,President, in the Chair. Mr. Stanley Okell was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. : Gilbert Grahame Auchinleck, B.Sc., the Department of Agriculture, Grenada, W.I. Fred Banister, B.Sc., the Grammar School, Doncaster. Howard Canton, 2, Gloucester Road, Regent’s Park, N.W. Herbert Hillier Hughes, B.Sc., 22, Ranelagh Road, Tottenham, N. Douglas Wilshin Mur ch, Selby House, Victoria Road, Wednesbury. John James Beaumont Ree3, B.Sc., Johannesburg College, S. Africa. A ballot for the e1e:tion of Fellows was held, and the following were declared duly elected : A.K. Yegna Narayan Aiyer, 11.A. 0. K. €I. Burger, Ph.D. Jehangir Dhanjishaw Anklesaria. Frank Ward Bury, B.Sc. James Alexander Hadden Arnistrong. William Edward Callister, B.Sc. Donald William Elsoin Barker. William Gordon Carey. Harold Baron, B.Sc. Hardee Chamblis, M.S., Ph.D. Stanley Robert Best, M.Sc. Lakshami Chand, B. A., B. Sc. Hubert Frederick Bottomley. James Perguson Dawson, B. Sc. Henry Shaw Breakspear, B.A. AIfred Charles Dunningham, B.Sc. 284 Edward Chayles Edgar, D.Sc. Francis Hugh Ping. Alfred Edge. Charles Proud. Frederick Watson Edwards. Walter Ritchings, M.Sc. Arthur James Ewins, B.Sc. Frederic William Robinson, B.Sc. Edmund Victor Flack. Pindi Das Sabherwal. George Peters Forrester. Manindra Sinhn. Arthur Forshaw, M.Sc.Spencer Boyd Oortis-Stanford. William Adolf Freymuth. Guy Stephenson. Otto Furstenhagen. George Bertram Stones, M. Sc, George Pomeroy Furneaux, B.A. James Thallon Strachan. Alexander David Gardiner. Edward Walter Taplin. Yenry Dent Gardner, jun., X.Sc. Charles Tnpp. Victor John Harding, M.Sc. Hermann Thorns, Ph. D. Arthur John Harvey. Joseph Grantley Tingle. Robert Douglas Hendry. Hcnry Thomas Tizard, B. A. Eric John Holmyard. Herbert Turner, B.Sc. Benjamin Leech, M. A. Everard Cecil Van Essen. William Ctidmore McCullagh Lewis, Nikolai Waliaschko. M.A. Charles Weizinann, D. Sc., Ph. D. Carl Olof Lundholm. Richard Vernon Wheeler, D. Sc. John Muller, B.A. Herbert Ernest Williams. Roland Victor Norris, bl. Sc. Joseph Pretty Wright. JOBSCornelio Rodrigues Peixoto.Roland Francis Young. Of the following papers, those marked * were read : “270. “A new method for the detection of sodium, caesinm, and rubidium.” By Walter Craven Ball. A solution of potassium bismuth nitrite, to which about 1 per cent. of casium nitrate has been added, produces a yellow, crystalline precipitate of 9CsNO2,GNaNO,,5Bi(NO,),, with traces of a sodium salt, One part of sodium in presence of several thousands of potassium may thus be detected. Conversely, a solutioa of sodium bismuth nitrite is an excellent test for cesium, and also for rubidium, if in not too great dilution. DISCUSSION. Mr. GRANT said that the author had referred to the precipitate HOOPER which was thrown down when the reagent mas exposed to oxidation by contact with the air, and, in connexion with the quantitative determination of sodium, he desired to ask how this precipitate from the reagent was affected by the 50 per cent.acetone which was used to wash the sodium compound, It appeared as if there was some danger of the sodium, as determined under these conditions, coming out too high, and he observed that the last determination quoted by the author was, in fact, B trifle high. 285 ”271. “Note on Dr. Scott’s paper on the molecular weight of tetraethylammonium bromide and the atomic weight of carbon.” By Sir Edward Thorpe, C.B. In determinations of atomic weight when the utmost attainable precision is aimed at, it is customary to reduce the weighings to what is styled a vacuum standard, and the reduction is almost invariably made by a calculation in which the relative densities of air, of the weights, and of the substance weighed are the data.Marignac, as far back as 1843, pointed out that in certain cases, more particularly when the substance weighed was in a fine state of sub-division, this method might be attended with error, due to the tendency of finely-divided substances to occlude and condense air. Inarecent paper(Compt.rend., 1909,149,593), Guye and Zachariades have again drawn attention to this circumstance. They state that with certain substances the error may be so considerable as to affect materially the determination of the value of an atomic weight.By weighing successively in air and in a vacuum, the same mass of finely-divided material (from 20 to 50 grams, depending on its density), and comparing the weight so obtained with that deduced by the conventional method of calculation, they found that the method of calculation invariably over-corrects the weight, and that the difference between the weight actually observed and that obtained by 3calculation may amount to as much as, or even more than, ___10,000 The extent of the difference appears to depend on several factors. In the first place, it depends on the density of the salt, salts of low specific gravity always tending to show the greatest variation. But it also depends, and in a greater degree, on the physical state of the salt.Thus in the case of fused potassium chloride (sp. gr. 1.97) the differ- ence shown by the salt in powder was 32 milligr ms per 100 grams ; in crystals it was 20 milligrams; in large pieces it was only 5 milli-grams. In the case of fused masses of salts of high density, and in that of fused metals, the discrepancy, if observed, is extremely small, and in such cases is practically negligible. In a recent communication to the Society (Trccns., 1909, 95, 1200), Dr. Scott has given the results of a number of determinations of the molecular weight of tetraethyla mmonium bromide, from which he has deduced an atomic weight for carbon slightly in excess of that obtained by the combustion of carbon, of graphite, of pure charcoal, and that deduced by physico-chemical methods, all of which agree extremely well among themselves and consistently point to the value C = 12-00. The author believes the discrepancy observed by Dr.Scott may be largely, if not altogether, accounted for by the circumstance Erst pointed out by Marignac. Tetraethylammonium bromide is a salt of very low specific gravity (in a private communication Dr. Scott informed the author that he found it to be 1*35),and, as he mentions in his paper, it was employed by him in tha state of a fine powder. Tetra-ethylammonium bromide is not iizcludecl in the long list of substances experimented upon by Guye and Zachariades, and no direct data exist for determining the precise value of the correction to be applied to its so-called vacuum weight.There is, in fact, no substance in the list of so low a specific gravity as 1.35, but considering the nature of the salt it is reasonably certain that it must be as great as, and in all probability greater than, the maximum value hitherto found, The maximum value obtained by Guye and Zachariades was observed in the case of potassium nitrate (sp. gr. 2*09), namely, 33 milligrams per 100 grams. To ascertain what might be the influence of Marignac’s correction in the case of Dr. Scott’s observation, this value of 33 milligrams may be applied. Dr. Scott found that, collec‘tively, 44.17031 grams of tetraethylammonium bromide were equivalent to 22.66675 grams of silver. Applying Guye and Zachariades’ number, the aggregate weight of the tetraethylammonium bromide would probably be at most 44.15573 grams, and ou the assumption that the atomic weight of silver is lO’l08S, this would give the molecular weight of the salt its 210.154. Taking the molecular weight of ammonium bromide as 97-962, on the basis of what is the accumulated testimony of the best determina- tions of the several atomic weights of its elements, me obtain 112.192 as the molecular weight of C8HIG,whence we have C = 12.008.It cannot, therefore, be regarded as established that the weight of the carbon atom in tetraethylammonium bromide, or in the group C8HlG,is different from what it has been lound to be in other carbon compounds. The slight variation which Dr. Scott has observed will, in the author’s opinion, be proved to be mainly, if not entirely, dependent upon the physical peculiarities of the salts he has employed.“272. The correction of weights of substances weighed in air to weights in a vacuum.” By Alexander Scott. Before passing to the consideration of the work of Marignac and of Guye and Zachariades with reference to corrections to vacuum stand- ards, whether by experiment or by calculation in the ordinary way, the author referred to the note on his determination of the atomic weight of carbon by Sir Edward Thorpe (preceding paper). One point 287 especially emphasised was that the value for C,H,, is based on the differ- ence between the molecular weights of tetraethylammonium bromide and ammonium bromide, both values being determined in the same way, with the same balance, pure silver, and the same set of care-fully calibrated weights.It mas thus hoped to eliminate any sources of error which might possibly be due either to the method or to personal equation, Therefore, if it is fair to deduct 33 milli-grams per 100 grams of tetraethylammonium bromide, as Sir Edward has done, it would only be fair to take at least 22 milli-grams from 100 grams of ammonium bromide, which would make for the 97,950 grams, which are equivalent to 107.88 of silver, 97.928 to be subtracted from Sic Edward Thorpe’s calculated value OF 210,154, and this gives C= 12.013 (taking H= 1.0075). Further-more, a similar correction ought to be applied to the combustion of carbon, for if any substance is caFable of condensing air in its pores it is carbon. Applying the correction of 33 milligrams per 100 grams to the careful experiments of van der Plaats, with sugar and paper charcoal, we get instead of C = 12.004, C = 11.998, so that the final effect of applying this correction all round is to increase rather than diminish the difference in the atomic weight of carbon as found by combustion methods and by the author’s method, As pointed out by Sir Edward Thorpe, Marignac (BibE.Univ., 1843, 46, 373) stated that there was a slight difference in the value of the correction to vacuum standards as found by the usual method of calculation from a knowledge OF the densities of the substances involved and that found by direct weighing of these substances in a vacuum.This, however, is only very slight, as the following table shows. The a.uthor has added the last three columns to Marignac’s table, taking the best values for the mean densities of the salts, and Marignac’s value of 1.2 milligrams for 1 C.C. of air. Weight Weight in Weight of equal Error in Salt. in air. a vacuum. volume of air. Density. milligrams. AgC10, ...... 100 100*029 0.027 4‘43 -2.0 AgBrO, ...... 100 100-021 0.023 5‘21 +2‘0 KClO, ...... 100 100-054 0.0515 2-33 -2.5 KBrO, ...... 100 100’044 0-0873 3-22 -6.7 KIO, ...... . . . 100 100+030 0.308 3 *89 f0.8 NH,Cl ...... 100 100~080 0.G792 1.515 -0’8 As Marignac’s weighings are only given to milligrams, presumably his balance was only sensible to a milligram, and an examination of the last columns shows, with the one exception of potassium bromate, that the evidence is quite as much against as in favour of his statement that any sensible error exists.The recent paper of Guye and Zachariades (Compt. rend., 1909, 149, 593) gives a list of twenty-six substances, with their densities, ant the errors stated to occur when 100 grams of each are weighed in air in fine powder and the correction for the displaced air applied in the usual way. This error they, like Marignac, ascribe to air con-densed in the pores of the fine powders, although it is difficult to see why "hygroscopicit6," as stated in their paper, should also enter into the question. These errors range from 33 milligrams in the case of potassium nitrate to only 1 for copper oxide.For potassium chloride they give more data, stating that the errors are 5 milligrams for fused Jumps, 22 for crystals, and 32 milligrams for fine powder. This last number means that 32 milligrams, or 27 C.C. of air, are condensed in the pores of 100 grams of finely-powdered potassium chloride, and therefore ought to be evolved with effervescence when the latter is dissolved in ordinary distilled water. This statement seemed so extraordinary that the author weighed in a vacuum and in air potassium chloride in fused lumps, in crystale, and in fine powder, and observed practically no difference between the weights referred to a vacuum, whether found directIy or by the ordinary method of calculation, with this precaution, however, that the calculation was made with the actual density of the air as deter- mined at the time and not an average density as is too often done.The slight differences, which still seem to remain, would be in all probability completely re moved had time permitted the preparation of an exact counterpoise to the vessel used to contain the salt. As, however, all this work has been carried out since Sir Edward Thorpe had most courteously sent the author a copy of the note com-municated by him to the Society, it has not been possible to employ all the refinements which modern science suggests. The apparatus employed mas a large test-tube, with cap carefully ground, arid to which was sealed a good glass stopcock, both capable of keep-ing a vacuum for days, and a small flask similarly fitted.Their volumes were respectively 186.5 and 82.16 C.C. The large tube had to be weighed on a larger and less sensitive balance than the small flask. Salt Salt in Fused salt. ill crystals. fine powder. Weight of tube, vacuous ............... 101'2616 101'2472 39.0418 YY ,, full of air ............ 101-4876 101.4684 39'1424 ¶> ,, +KCl.................. 215'5230 202.9178 106.8062 Y, ,, +KC1+air ......... 215 -6840 203.0776 106-8648 ,, KC1 in a vacuum ........ 114'2664 101 -6706 67.7544 ¶? ,, in air .................. 114'1964 101'6092 67.7224 ,, air displaced ............... 0.0700 0.0614 0'0420 ,, air along with KCl .........0'1560 0.1598 0.0586 ,, total air .................... 0'2260 0'2212 0.1006 ,, 1C.C. of air in milligrams 1'212 1'186 1'23 Calculated correction for air ......... 0.0703 0.0617 0.0423 Density of snbstanco..................... 1'9698 1.9527 1'9702 Error ....................................... 0'0003 0'0003 0.0003 289 In addition to the three experiments of which the results are given in the preceding table, two other experiments with crystals and fine powder were made with like results. Mr. J. D. Kettle, chief assistant at the Davy-Faraday Laboratory, took finely-powdered benzoic acid (a less dense substance than any of the substances mentioned above), and, on fusing 19.8 grams of it in a vacuum and using a tube of approximately the same weight and volume as a counterpoise, was unable on a still more sensitive balance to detect the slightest change in weight, and no trace of gas was given off on fusion which could be detected by a mercury gauge any more than by the balance; as some of the salts in Guye and Zachariades’ list were apparently hydrated, perhaps some of their results may have been due to loss of water, otherwise no explanation can be given of their most remarkable results.Until a detailed account OF their work, giving the actual weighings, is available, further criticism is hardly called for. “273. ‘(Synthesis of hordenine, the alkaloid from barley.’’ By George Barger. Hordenine, isolated by LQger (Compt. rend., 1906, 142, 108) from barley germs, and recognised by him as p-hydroxyphenylethyldimethyl-amine, OH-C,H,*CH,*CH,*NMe,, has now been synthesised from phenylethyl alcohol, which mas successively converted into P-phenyl- ethyl chloride and phenylethyldimethylamine;the phenolic hydroxyl was then introduced by successive nitration, reduction, and diazotisation.The more obvious synthesis, by methylation of p-hydroxyphenyl-ethylamine (Barger, Z’vans., 1909, 95, 1123), could not be carried out ; by this means only hordenine methiodide was obtainable, but not hordenine itself. *274. (‘Syntheses in the epinephrine series.” By Frank Tutin, Frederic William Caton, and Archie Cecil Osborn Hann. The authors have prepared o-amino-p-hydroxyacetophenone(I) and ~-p-dihydroxy-P-~he~yl~ti~y~mi~(11). HO<I)CO*CH,=NH,.HO/-\CH(OH)*CH,-NH,.\-/ (1.1 (11.) Both of these compounds, when injected intravenously, considerably increase the blood-pressure. The latter compound, however, is the more powerful, and, in its action, more closely resembles epinephrine. The formation and properties of the above-mentioned bases (1 and 11) and of a number of other new compounds were described. 275. “The correction of the specific gravity of liquids for the buoyancy of air.” By John Wade and Richard William Merriman. In determining the specific gravity of liquids to the fifth decimal place, neglect of variations in atmospheric density may lead to serious error, more especially when the water-content of the pyknometer is not determined under the same atmospheric conditions as those obtaining’at the time of weighing the liquid.Analysis of the limits of accuracy of the customary correction formula leads tr, some simple expressions which, with the aid of tabulated constxnts, materially reduce the labour of correction. 276. ‘(Syntheses with the aid of monochloromethyl ether. Part 11. The action of monochloromethyl ether on the sodium deriv- ative of ethyl acetoacetate.” By John Lionel Simonsen and Robert Storey. The authors showed that monochloromethyl ether and ethyl sodio- acetoacetate condense with the formation of ethyl msthoxy-P-rnetlr~omy-crotonate and ethyl ay-diacetylglutarate. 277. ‘‘ The relation between the chemical constitution of monazo-dyes and their fastness to light.” By Edwin Roy Watson, A.Chandra Sirkar, and Jatindra M. Dutta. From rules which had been already formulated by one of the authors (this vol., p. 224) it was expected that the dyes sulpho- benzeneazophenolmonosulphonic acid and sulphobenzenoazophenol-disulphonic acid mould be very fast to light. This was found to be the case. Sulphobenzeneazophenol was also found to be very fast to light. Contrary to the usual assumption that a hydroxy- or amino-group must be present in an azo-compound to give it dyeing properties, it was found that azobenzenedisulphonic acid is a dye, and, owing to the presence of sulphonic groups and the absence of any hydroxy- or amino-group, it was found to be very fast to light. It was predicted that phenol would be formed as one of the decomposition products when chrysoidine faded in light, and when this was put to the test phenol was found.It was also predicted hhat the introduction OF bromine atoms or a nitro-group into the phenolic or arylamino-part of a monazo-dye would increase its fastness to light, and that the fastness to light of amino-azobenzone would depend on the position of the amino-group, m-amino- 291 azobenzene being faster than p-aminoazobenzene. The fastness to light of the following dyes was compared : aminoazobenzene, benzene- azodibromoaniline ;benaeneazophenol, benzeneazonitrophenol ;sulpho-benzeneazopldenol, sulphobenzeneazonitrophenol ; p-aminoazobeozene, m-aminoazobenzene, and o-aminoazotoluene.The theory, on which these predictions were based, as to the manner of fading of azo-dyes in light mas not confirmed by this investigation to the extent anticipated . 278. (‘The triazo-group. Part X. Triazoantipyrine.” By Martin Onslow Forster and Robert Muller. The preparation and properties of triazosnLipyrine were described, and attention was drawn to the behaviour which distinguishes it from other triazo-ketones. 279. Volumetric estimation of sulphates.”66 By Alec Duncan Mitchell and Clarence Smith. The method consists essentially of adding a small excess of 2N/5-barium chloride solution, destroying mineral acid by sodium acetate, adding excess of N/lO-ammoniiim dichromate solution, and making up to 100 c.c.; when the precipitate has settled, 25 C.C. of the clear supernatant liquid are titrated with iV/20-ferrous ammonium sulphate solution, using potassium ferricyanide as an external indicator.This has been applied to ammonium sulphate, sodium sulphate, potassium sulphate, zinc sulphate, magnesium sulphate, and copper ammonium sulphate, and gives results accurate to about 0.2 per cent., although in the case of potassium sulphate special precautions have to be adopted to minimise adsorption. Excluding weighings, five determinations may easily be made in a hour. 280. 4L The colouring matter of cotton flowers. Gossypium herbaceum. Part. II.” By Arthur George Perkin. The flowers of the Egyptian cotton plant, a variety of the Gossypiurn herbaceurn, have been found to contain three hitherto unknown glucosides.Quercimeritriiz, C,,H,,O,,, the main constituent, crystal- liees with 3H,O in smftll, yellow plates, m. p. 24’7-249O, dyes mordanted fabrics very similarly to yuercetin, and gives with lead acetate an orange-red precipitate. It forms an octcc-acetyl compound, C21H12012(C2H30)8,colourlesa needles, m. p. 2 14-21 6O, and is hydrolysed with difficulty according to the equacion : C,,H,,O,, +H,O =C,,H +C,H,,O, 292 into quercetin and dextrose (osazone, m. p. 204-205O). isoQuercitrin, C,1H,00,2 (dried at 160°), consists of pale yellow needles, m. p. 217--219O, and is readily hydrolysed by acid : C21J3&(31, +H,O =C,,H,o07 +C6HIZOG with formation of quercetin and dextrose, but differs from quer-cimeritrin in several important respects, With lead acetate it gives a bright yellow precipitate, dyes mordanted fabrics similarly to quercitrin (Trans., 1902, 81, 480), and is present in the flowers in small amount.The third glucoside, gossypitrin, C,,H200,, (dried at 160°), pale orange-yellow needles, m. p. about 200-202’, when hydrolysed gives gossypetin and dextrose : C,,H,,O,, +H2O =C,,H,oOs + C,H,,O,* It yields a bright red precipitate with lead acetate, and dyes mordanted fabrics. The flowers yielded 1.86 per cent. of yellow colouring matter, consisting of quercetin mixed with about 10 per cent. of gossypetin. 281. ‘‘Viscosity and association in binary mixtures of liquids.” By George Senter. In a recent paper (Trans., 1909, 95, 1556) dealing with the viscosity of binary mixtures of liquids, Dunstan and Thole state that the maxima observed in certain viscosity-concentration curves of such systems “invariably occur at or near points of simple molecular oom-position,” and are connected with the formation of definite chemical compounds between the components of the mixture.In this con-nexion they refer to the brief discussion of this subject in the author’s OuJines of Physical Chemistry (p. 305-306), in which it is stated that no general agreement has yet been reached with reference to the interpretation of such curves, and they suggest that the considerations there advanced present no obstacle to the general acceptance of the association explanation of the phenomenon.The experimental work described by Dunstan and Thole was under- taken with the object of throwing light on the displacement of the maxima with temperature, but, unfortunately, observations have only been made over a range of loo (20-30°), which is too small to allow of any very definite conclusions being drawn. However, it is known from the observations of Arrhenius, quoted in the paper, that in mixtures of ethyl alcohol and water, the viscosity maximum at 0’ occurs at a composition of 36 per cent. of alcohol and at 55’ at 50 per cent. of alcohol, so that there is an undoubted shift of the maximum with temperature in this case, and doubtless in other cases. Dunstan and Thole now maintain that such a shift of the maximum does not disprove the association explanation of this phenomenon, and with this the author agrees.It does, however, entirely disprove the suggestion that such maxima invariably occur ‘‘at ” points of simple molecular composition, since the position of the maximum in the case cited alters continuously with rise of temperature through a wide range of concentration, The qualifying word :‘near ” does not seem to have any well-defined meaning in the present case, as a mixture of two Components in any proportions whatever may be looked upon as being ‘‘near ” a point of simple molecular composition. Even if the association explanation of the maxima be accepted, it is improbable that the observations throw any light on the composition of the compounds unless the latter are exceptionally stable, like H,SO,(H,O,SO,) and H2S0,,H20.In this connexion it is suggestive to note that, according to Kremann (Monatsh., 1907, 28, t331), the viscosity curve of the system m-cresol- aniline, at Oo, shows a maximum at 85 mol. per cent. of the former, although the componeuts only form one compound, containing one molecule of each. Similarly, the viscosity curve of the system phenol-aniline shows a maximum at 67 mol. per cent. of phenol, although only one compound is known containing the components in molecular proportions. The numerous investigations on alloys carried out in recent years appear to throw some light on this question. According to Tammann (Zeitsch. ccnoyg. Chern., 1907, 53, 446), it is a general rule that metals belonging to the same natural group form solid solutions (mixed crystals), but no chemical compounds.Now Kurnakoff and Schemtschuschny (Zeitsch. anoyg. Chem., 1908, 60, 1) have shown with reference to the hardness of binary systems (a property allied to viscosity) (1) that the hardness of an unbroken series of solid solutions is often represented by a continuous curve showing a maximum; (2) that a chemical compound may be harder or softer than either of the components. It is not improbable thatl similar rules may apply to the viscosit,y of liquid mixtures. There does not seem to be any reason to assume a priori that the viscosity of a compound must be greater than that of its components, especially if the latter are themselves associated.With reference to the two systems showing maxima specially dealt with in the paper by Dunstan and Thole, cited above, it may be noted that the freezing-point curve of mixtures of acetic acid and water shows no indications of the presence of a compound (Kremann, Monatsh., 1907, 28, 893), although the observations mere made at a lower temperature than the viscosity measurements described in the paper. Moreover, Jones (Zeitsch. physikal. Chem., 1894, 13, 419) has shown that mixtures of ethyl alcohol and water exert their effect on 294 the freezing point of acetic acid quite independently ; he thus obtained no evidence of combination between the first two compounds, although the corresponding experiments with mixtures of sulphuric acid and water showed quite conclusively the formation of compounds. The fact that the maxima on the viscosity curves become less distinct the higher the temperature does not appear very conclusive from the point of view of association, as it is a rule of very wide applicability that the simple laws (in this case, the mixture law) are followed the more closely the higher the temperature.Among the factors which have to be taken into account in dis- cussing the properties of binary systems are to be considered, besides possible chemical combination, alterations in molecular complexity and attractions between the molecules (analogous to the a/v2 term of van der Waals’ equation) connected with alterations of “internal pressure ” (compare Tammann, Innere Krayte und Eigenschaften der Ltjszcngen, Leipzig, 1907). These factors may be more or less connected, but, on the other hand, the existence of unimolecular liquids indicates that there may ,be considerable attraction (measured by the term a/v2)between molecules without leading to chemical combination.The general conclusion is that at present there are no means of reaching tt definite decision on this matter, and we have to depend on rather uncertain criteria which do not all point in the same direction. 282. ‘‘ Preparation of anhydrides by the action of thionyl chloride on salts of organic acids.” (Preliminary note.) By William Smith Denham. The author has shown (T1*ans.,1909,95, 1235) that sulphur mono- chloride acts readily ou the sodium or silver salts of organic acids in presence of indifferent solvents, forming unstable sulphur compounds of the type (R*CO,),S,, which, on spontaneous decomposition, give anhydrides of the acids, together with sulphur dioxide and sulphur.Since, according to one view, thionyl chloride has a constitution similar to that of sulphur monochloride, attempts have now been made to obtain compounds of the type (R*CO,),SO by the substitution of thionyl chloride in the above reaction. Intermediate compounds of this type were not obtained, but it was found that reaction takes place smoothly and readily between typical silver salts and thionyl chloride, with evolution of sulphur dioxide and formation of the acid anhydride, probably according to the equation : 2R*C02Ag+ SOC1, = (R*CO),O + W,+ AgCI.As in this case sulphur dioxide is the only product in addition to the anhydride, this modification of the reaction possesses obvious advantages as a method of preparing anhydrides over that in which sulphur chloride is used. The reaction is carried out as described in the case of sulphur chloride, that ia, by adding thionyl chloride dissolved in dry ether to a slight excess of the silver salt suspended in the same solvent, the containing vessel being cooled if necefsary. After filtration from silver chloride and distillation of the ether, the anhydride is left in good yield, and generally nearly pure. In this vay, acetic, benzoic, and succinic anhydrides have already been obtained.Whilst sulphur chloride does not, under these conditions, react with silver oxalate or with silver malonate, thionyl chloride does react, but only decomposition products have been obtained. The author proposes to apply this method to the preparation of anhydrides of hydroxy-acids and of optically active acids, and to the preparation of mixed anhydrides. Preliminary experiments indicate that this may be successfully done, and the author made this preliminary announcement in view of the fact that H. Meyer (Chem. Zeit., 1909, 33, 1036) outlines a method of preparing anhydrides of sulphonic acids from the corresponding alkali salts by the action of thionyl chloride. 283. A new synthesis of oxazole derivatives." By Robert Robinson.The author has found that certain acyl derivatives of w-aminoaceto-phenone are condensed, under the influence of sulphuric acid, to oxazoles. w-Benzoyluminoacetophenone, prepared by benzoylating w-aminoaceto- phenone, crystallises in needles, melting at 123', and when warmed with sulphuric acid furnishes 2 :5-diphenyloxazole (E. Fischer, Ber., 1896, 29, 207). w-Phenyl~etylccminouceto~henoizeis obtained by the action of phenylacetyl chloride on o-aminoace tophenone stannichloride in the presence of potassium hydroxide; it forms colourless needles or prisms melting at 104". The oxims melts at 154O, and the phenyl-hydrazone at 184-185'. When w-phenylacetylaminoacetophenoneis dissolved in sulphuric acid, it gives rise to 5-phenyZ-2-benzyloxazob,crystallising in long, flat needles melting at 89'; the picrate melts at 103".a-Kydroxy-P-phenylacetylamino-a-phenylethane, OH CHPh CH2*NH C0 CH,Ph ,pre-pared by reducing o-phenylacetylaminoacetophenonewith sodium and dilute methyl alcohol, forms colourless prisms melting at 99' ; it does not condense to an oxazole. On warming w-benzoylaminoace to- veratrone with sulphuric acid, 2-phenyl-5-veratryZoxaxole is obtained in slender needles melting at 97", and, in a similar manner, 2-be?zzyl-5-veratryloxaxole, colourless needles, melting at 86", is obtained from 296 o-phenykacetylaminoacetoveratrone,which melts at 135O, and is prepared from w-aminoacetoveratrone stannichloride and phenylacetyl chloride, Reduction of 2-0ximino-5 : 6-dimethoxy-1-hydrindone and benzoylntion of the hydrochloride of the resulting 2-amino-compound furnishes 2-benaoykamino-5:6-dimethoxy-l -hydrindone, which crystallises in needles melting at 224’; the compound does not condense to an oxazole under the influence of sulphuric acid.284. 44 Ethyl benzoylacetate ’’ By Edward Hope and William Henry Perkin, jun. The authors have made a careful investigation of the conditions under which ethyl benzoylacetate is converted into mono-and di-sub- stitution derivatives, and of the behaviour of these on hydrolysis. ADDITIONS TO THE LIBRARY. I. Donations. Cook, John. Clavis Naturae: or, the mystery of philosophy unvail’d. pp. xiv + 405. London 1733. From Mr. C. H. Cribb.Iron and Steel Institute. Caraegie Scholarship hlemoira. Vol. I. pp. xii + 368. ill. London 1909. From the Institute. 11. By Purchase. Laubenheimer, Kurt. Pbenol und seine Derivate als Desinfektions- mittel. pp. vi + 156. Berlin 1909. (Recd. 24/11/09.) Loeb, Jucques. Die chemische Entwicklungserregung des tierischen Eies. (Kiinstliche Parthenogenese.) pp. xxiv +269, ill. Berlin 1909. (Recd. 24/11/09.) Moser, L. Die Bestimmungsmethoden des Wismuts und seine Trennung von den anderen Elementen. (Die chemische Analyse, Vol. X.) Stuttgart 1909. Newlands, John A. R.,and Newlands, Benjamin E. R. Sugar. A handbook for planters and refiners. pp. xxxvi+876. ill. London 1909. (Recd. 10/11/09.) Oppenheimer, Carl. Die Ferment0 und ihre Wirkungen.Spezieller Teil. 3rd edition. pp. xi + 491. Leipzig 1909. (Recd. 24/11/09.) Ostwzbld, 1Volfgan.g. Grundriss der Kolloidchemie. pp. xiv + 525. Dresden 1909. (Recd. 24/11/09.) 297 Starling, Ernest H. The Mercers’ Company Lectures on the fluids of the body. pp. viii+ lS6. London 1909. (Kecd. 27/11/09.) Zerr, George, and Riibencamp, R. A treatise of colour manufacture. A guide to the preparation, examination, and application of all the pigment colours in practical use. Authorised English edition by Charles Mayer. pp. xiii+605. ill. London 1908. (&ecd. 271 11/09.} 111. Panzphlets. Aschan, Ossian. Ueber die Konstitution des Isopiuens. (From the Ofversigt Finska Vetensk. SOC.Forha?idZ.,1908-1909, 5 1, A.) Barger, Geoqe, and Dale, Hermy Hallett.The wnter-soluble active principles of ergot. (From the J. Pliysiol., 1909, 38.) Barger, George, and Walpole, George Stanley. Isolation of the pressor principles of putrid meat. (From the S. Physiol,, 1909, 38.) Dale, Henry Hallett. Note on nutmeg-poisoning. (From the Proc, Roy. SOC.Me&., 1909.) Dale, Henry Hallett, and Dixon, Walter Ernest. The action of pressor amines produced by putrefaction. (From the J. Physiol., 1909, 39.) Goerner, Pc~ul. Aromatische Nitroderivate insbesondere Kitro-phenole als Alkaloidfaellungsmittel. pp. 45. Strassburg 1908. Nebraska, University of. Agriculturat? Experiment Station. Twenty-second annual report. pp. 158. ill. Lincoln, Nebraska, 1909. Neubauer, Otto. Ueber den Abbau der Aminosauren in gesunden und kranken Organismus.(From the Deut. Archiw. klin. Med., 1909, 95.) Palladino, Pietro. Du poids absolu des corps BlBmentaires et dhpendance de leurs proprich& chimiques et physiques du poids absolu et de la forme. pp. 44. ill. Genova 1909. Pfyl, B., and Rasenack, P. Ueber die Verpuffungs und Ver-brennungsprodukte von Zelluloid. (From the ATbeiten K. Gesund-heitsamte, 1909, 32.) Rusconi, Arncalclo. Ricerca dell’ alcool etilico nel cloroformio. (From the Arch. Farrnacol. sper. Sci.afini, 1909, 8.) Zimmerman, Joseph. Ueber die Spaltung des Ggpsophila-8aponins. pp. 58. Strassburg 1909. 298 JULIUS THOMSEN MEMORIAL LECTURE. The Julius Thomsen Memorial Lecture will be delivered by Professor Sir EDWARD C.B., F.R.S., at the Ordinary Scientific Meeting THORPE, on Thursday, February 17th, 1910, at 8.30 p.m.At the next Ordinary Scientific Meeting on Thursday, December 16th, 1909, at 8.30 p.m., the following papers will be communicated : ‘‘ The production of para-diazoimides from alkyl-and aryl-sulphonyl- para-diamines. A general reaction.” By G. T. Morgan and J. A. Pickard. “ Organic derivatives of antimony. Part I. Tricamphorylstibine chloride and triphenylstibine hydroxynitrate and hydroxysulphate,” By G. T. Morgan, Miss F. M. G. Micklethwait, and G. S. Whitby.‘(The constituents of Rumex ecklonianus.” Ey F. Tutin and H. W. B. Clewer. ‘‘The influence of non-electrolytes on the solubility of carbon dioxide in water.” By F. L. Usher. Lr Ethyl hydroxyisobutyrate.” By W. Parry.‘‘ The condensation of benzaldehyde with resorcinol.” By F. G. Pope and H. Howard. R. CLAY Ah’D SONS, LTD., BRE.41) ST. HILL, E.C., AND BUNOAY, SUFFOLH.
ISSN:0369-8718
DOI:10.1039/PL9092500283
出版商:RSC
年代:1909
数据来源: RSC
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