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Proceedings of the Chemical Society, Vol. 20, No. 283 |
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Proceedings of the Chemical Society, London,
Volume 20,
Issue 283,
1904,
Page 151-172
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摘要:
Issued 30/6/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 20. No.283. D.Sc., F.R.S.,Wednesday, June 15th, 1904. Prof. W. A, TILDEN, President, in the Chair. Messrs. G. Dean, C. D. McCourt, J. C. Smith, R. de J. Fleming-Struthers, and C. H. Thompson were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. William H.R. Allen, c/oStraitsTrading Co., Butterworth, Penang, S.S. Jabez Horace Cooper, 13, Victoria Terrace, Exeter. George Frederick Phillips, B.Sc., Colworth Road, Leytonstone. Edwin Roy Watson, B.A., B.Sc., 1, Fair Street, Cambridge. A ballot for the election of Fellows was held, and the Following were subsequently declared duly elected. Albert Ernest Bellars, B.A. William Edward Onkden.Herbert Frank Brand, M.A. Alfred Pell. W. Eddington Field. David John Pinkerton. Thomas Alfred Gerard. Robert Rodger. James Gray Gilchrist, M.A. Percy Richard Sanders. John Hulme. Charles John Sawer. Herbert Jenkins. Henry Stanley Shelton. John Haalam Johnston, M.Sc. John Weinberg. Rudolf Lessing, Ph.D. James Alfred Wilkinson, M. A Frank Harold Lowe, B.Sc. 152 The PRESIDENTstated that six of the seven Past Presidents to whom the Society desired to do special honour at the Banquet held in 1898 having passed away, the Council felt that there should be no further delay in the publication of a memorial notice of the life and work of each. Arrangements had accordingly been made for the preparation of such notices, which, it was hoped, would be incorporated in the volume of Transactions for the present year.The list includes the name of Frankland, concerning whom a Memorial Lecture had been delivered by Professor Armstrong at a special meeting of the Society in October 1901. Repeated application for the manuscript having been unsuccessful, and nearly five years having elapsed since the death of Sir Edward Frankland, the Council were arranging for the preparation of an independent obituary notice. The PRESIDENTfurther stated, for the information of the Society, that arrangements had been completed for the publication annually of Reports on the Progress of Chemistry under the several heads employed in the Journal for the classification of the Abstracts, with addition of a new section on " Radio-activity." It was expected that these reports, collected into an extra number of the Journal, would be ready for issue to the Fellows early in the spring of each year.The attention of the Fellows was also requested to the notice inside the cover of the Journal relating to the International Tables of Atomic Weights, which are now printed on cards to be obtained from the Society's Agents, Messrs. Gurney and Jackson. Of the following papers, those marked * were read : "111. "The mechanical analysis of soils and the composition of the fractions resulting therefrom." By Alfred Daniel Hall. The object of the investigation was to ascertain the effect of introducing into the mechanical analysis of soils a preliminary treatment of the soil in dilute acid followed by ammonia as first suggested by Schlcesing.For the separation into fractions, the beaker method of sedimentation as worked out by Osborne was adopted, the soil being divided into two fractions by sieves and five by sedimenta- tion from water. Eighteen soils of known history were selected from the Rothamsted experimental plots, to give comparisons of the same soil in an unmanured condition and when rich in humus through the accumulation of organic matter. The proportions in which the groups of particles of given sizes occur in a soil are presumably const'ant for the particular type of soil ; 153 the actual state of aggregation of the particles at any given time or place determines what may be termed the texture of the soil and depends on a number of temporary factors, such as the cultivation to which the soil has been subjected, the amount of humus present, the use of lime or of saline manures, &c.It is held that no method of mechanical analysis can measure the existing texture of the soil, although that texture does ultimately depend on the size of the particles composing the soil. If, however, the method of mechanical analysis can be made to show the ultimate physical constitution of the soil, a measure is obtained of the capacity of the soil to acquire a known texture under given methods of cultivation. On comparing the results obtained by sedimenting the Rothamsted soils with and without the preliminary treatment in dilute acid, it is found that the raw soil rarely yielded as much of the finest or “klay” fraction as did the same soil after washing with acid, and that the difference was greatest when pastures and other soils rich in humus were examined, but practically disappeared with soils which had been deprived of their humus and deflocculated by long treatment with saline manures.As no valid reasons exist for supposing that the acid treatment can break down large particles into smaller ones, it is concluded that in carrying out a mechanical analysis on the raw soil many aggregates of the finest particles are left unresolved, but fall a.part when the humates, which act as a weak binding material, are removed by the treatment with dilute acid followed by ammonia.A further action of the acid treatment is to remove all traces of soluble salts, which would otherwise cause flocculation and interfere with the sedimentation. It is only when dealing with soils containing a fair amount of humus that there will be much difference between the results obtained by the two methods, but, inasmuch as only the acid treatment yields an exact sorting out of the ultimate inorganic particles of the soil, whereas working on the raw soil leaves some of the finest particles still unseparated, the general conclusion is reached that the acid treatment should be adopted in all cases, With the Rothamsted soils, the method involving a preliminary treatment with acid shows the essential identity of soils from the same experimental field whatever the manuring has been, whereas the analyses made on the raw soil give very different results, depending on the treatment the various plots have received.Determinations made of the alumina, silica, and ferric oxide in the various fractions separated by mechanical analysis show that although the proportion of alumina increases as the particles composing the fraction become smaller, these fractions do not possess any chemical individuality, but are determined by the size and not by the chemical composition of the particles. 154 “112. “The effect of the long-continued use of sodium nitrate on the constitution of the soil.” By Alfred Daniel Hall. On reviewing the results of the mechanical analysis of Rothamsted soils, it was observed that those which had been manured with sodium nitrate every year gave abnormal results; a further series of fifteen soils was examined drawn from each of the Rothamsted fields where plots with and without sodium nitrate occurred.In general, the use of sodium nitrate has resulted in a lower proportion of ‘‘klay ” being left in the surface soil. This result was most manifest in the mange1 field, where cultivation is frequent, and was not apparent at all in the grass field, where the turf protects the soil from the washing action of the rain. The removal of the finest particles from the surface soil is attributed to deflocculation induced by the use of sodium nitrate and followed by the washing of the finest particles into the subsoil.This hypothesis is confirmed by chemical analysis of the “ klays ” separated in the mechanical analysis, by mechanical analysis of some of the subsoils, which were found to be richer in fine particles beneath the soils receiving nitrate, and by the condition of the same soils in the field, which showed every evidence of deflocculation. DISCUSSION. Dr. VOELCKERsaid that although he could not go so far as Mr. Hall in his estimation of the value of mechanical as against chemical analysis of soil, he nevertheless recognised the importance of the former and the advance which had been made with regard to it. It seemed, however, remarkable in the first paper that such similarity of composition was shown in the different separations formed by washing the soils. In regard to the second paper he could, from his own experiments on the Woburn soil-a light sandy one and very different to that at Rothamsted-quite bear out what bad been noticed with respect to the action of sodium nitrate. On washing the former soil continuously with solutions of this salt, the finer portions of soil were carried down and the subsoil after a time became quite different in texture, form- ing a consolidated mass through which the water would not percolate.This was due, no doubt, as the author had indicated, to the carrying down of the finer particles. In this respect, great differences were noted between the action of sodium nitrate and that of the sulphate and other salts of ammonium.Dr. E. J. RUSSELLpointed out that what was really wanted was a 155 knowledge of the total surface of the soil particles to a depth of say six inches ;mechanical analysis gave very useful results but was not entirely satisfactory. There are some fundamental objections to the method; small particles from near the bottom of the column of liquid are deposited along with the larger particles which take the same time to travel from the top, and the deposit is therefore a mixture. More-over, a disc-shaped particle will tend to place itself broadside on and be deposited simultaneously with a spherical particle of about the same sectional area. Consequently, it cannot be assumed that the particles have even approximately the same surface, although under the microscope the sediment may appear to be fairly homogeneous.Mr. F. J. LLOYDsaid that the study of the physical nature of the soil had been neglected in England, whereas the remarkable researches of Whitney in America had shown that valuable information could be derived from this investigation. He regretted that the author had stated that the physical study yielded more important results than the chemical examination, because in his opinion the nature of the soil could only be discovered by the investigation of both its physical and chemical properties. Mr. T. 8.DYYONDpointed out that the method employed by the author involved the complete disintegration of the soil aggregates pro-duced by years of cultivation.What information of value bearing on the proper treatment of cultivated land could be obtained if the previous history of the soil were obliterated previous to analysis? More practical knowledge could be gained by the rough examination of the soil of a field with a spade than by the old methods of mechanical analysis. Would not this be still more true of the method now proposed ? Dr. LUXMOREsaid that as the aim of mechanical analysis was to determine the structure of the soil it was needful in the first place to know the total quantity of the finest materials, which sometimes formed a layer over the coarser particles. If in addition to this a method could be derived by which the state of tilth could also be deter-mined this would be a further advantage.One great benefit of the preliminary treatment with acid lay in the saving of time which it involved in a long and tedious process, From his own observations on the soils of Dorset he knew that the dissolved material other than calcium carbonate was very small in amount. Mr. HALL,in reply, said that he would not attempt to consider the question raised by Dr. Voelcker and Mr. Lloyd as to the value of the mechanical analysis of a soil ;the method, however, aimed at gauging the behaviour of a soil towards water, and the size of crops even in this humid dimate was determined more by the amount of water available than by the soil constituents usually regarded as plant food. He 156 agreed with Dr.Russell that the working surface of tbe soil particles was probably the factor of most importance, and one which could only be imperfectly deduced from the mechanical analysis. He did not, however, anticipate that it would be possible to estimate directly the behaviour of a soil in the field from any of the measurements they could obtain ;the function of the mechanical analysis was rather to enable one to relegate a given soil to one or other of certain known types, the working qualities of which had been already ascertained by experience. This meant, then, the accumulation of the necessary data for a number of soils, and the first essential was to obtain a method which was so far accurate that it represented the permanent and not the accidental or temporary features of the soil.“113. “The decomposition of oxalates by heat.” By Alexander Scott. In spite of the simple formulae given to the oxalates, their de- composition by heat is by no means as simple as usually stated. Ordinary precipitated calcium oxalate turns grey on ignition, and this change, which is due to the separation of small quantities of carbon, occurs even with the purest calcium oxalate. This salt gives very little carbon dioxide and carbon, but always a little of each, decom- posing practically in accordance with the equation usually given, CaC20, =UaCO, + CO. Sodium and barium oxalates decompose in accordance with the following equations : 7Na,C20, =7Na2C0, + 3CO + 2C0, + 2C, 8BaC,O, =8BaC0, + 6CO + CO, + C.Magnesium oxalate gives exactly equal volumes of carbon dioxide and monoxide and no carbon, MgC,O, =MgO + CO + CO,, but almost all the other oxalates tested gave notable quantities of carbon dioxide and carbon. *114. Some alkyl derivatives of sulphur, selenium, and tellurium.” ‘I By Alexander Scott. When sulphur is heated at 180’ with methyl iodide, 1 atom unites directly with 3 molecules of the iodide, forming t,he di-iodide of trimethyl- sulphine iodide, which is obtained as an almost black oil, but after this has been freed from excess of methyl iodide the solid, S(CH3),I,12,may be obtained by dissolving the oil in ethyl acetate and precipitating by means of ether, when it separates in dark purple scales melting at 38O.Selenium behaves in an exactly similar way, the Se(CH,),I,I, melting at 39O. To reduce these to trimethyl-sulphine and -selenetine 157 iodides, water is added to their solutions in ethyl acetate and hydrogen sulphide is passed in until the liquid is colourless. As Demarqay has shown, the action of methyl iodide on tellurium at 80' gives rise to tellurium dimethyl di-iodide, Te(CH,),I,, but this is not decomposed by heating to 180°,nor does it give a compound corresponding with those obtained from sulphur and selenium. To obtain tellurium trimethyl iodide, the di-iodide ig dissolved in methyl iodide and equivalent quantities of sodium sulphite and sodium carbonate are added, The reaction takes place thus : Te(CH,),I, + CH,I +Na2S0, +H,O =Te(CH3),2 + Na,SO, +2H1, the hydrogen iodide being then neutralised by the sodium carbonate.The tellurium trimethyl iodide is readily separated from the sodium salts by crystallisation. The di-iodide of tellurium trimethyl iodide, produced by adding iodine to the iodide, is readily obtained in fine purple scales (m. p. 76.5") by precipitation of its solution in ethyl acetate by means of ether. Ally1 iodide readily dissolves tellurium in the cold, giving an orange- coloured oil, from which the element is very readily obtained again. Ethyl iodide reacts in the same way as methyl iodide. The author showed several reactions of tellurium dimethyl di-iodide and its derivatives. *115. The ultraviolet absorption spectra of certain enol-keto- tautomerides.Part I. Acetylacetone and ethyl aoeto-acetate." By Edward Charles Cyril Baly and Cecil Henry Desch. An attempt was made to determine the constitution of the metallic derivatives of acetylacetone and efhyl acetoacetate by means of their ultraviolet absorption spectra. The absorption spectra of alcoholic solutions of the aluminium, beryllium, and thorium derivatives of acetylacetone and the aluminium compound of ethyl acetoacetate were photographed, as well as those of the parent substances. Hartley and Huntington's method of experiment was adopted, but a different method of drawing the curves of absorption was employed. From a consideration of the absorption curves of acetylacetone and its metallic derivatives, it is evident that the constitution of these substances iE very similar, as they all show a strong absorption band, the limits of which are very much the same in every case.Ethyl acetoacetate, on the other band, shows no absorption band, whilst its aluminium derivative shows a strong band almost identical with tho50 of the acetylacetone group. These results appeared at first to indicate that acetylacetone and its 158 derivatives and the aluminium compound of ethyl acetoacetate had the enolic formula, and suggested the keto-formula for ethyl aceto- acetate itself. This view was not upheld by the study of the spectra of ethyl ethylacetoacetate, and its isomeride, ethyl P-ethoxycrotonate ; in both cases, only continuous absorption was obtained without any band at all.The band therefore cannot be characteristic of either the enolic or the keto-modification, but appears to be due entirely to the dynamic isomerism between the two forms. Experiments were made to test this by observing the action of sodium hydroxide or hydro-chloric acid, which should materially alter either the size or the per- sistence of the absorption band ;the former reagent should increase it, and the latter decrease it owing to their accelerating and retarding influence respectively on the dynamic isomerism. It was found that a very small amount (4equivalent) of sodium hydroxide produced a band in the absorption spectrum of ethyl acetoacetate, this band being increased by the addition of more alkali until with excess it was larger and more persistent than that given by the aluminium derivative.Hydrochloric acid was found to have a marked action in decreasing the absorption of ethyl acetoacetate ; its action was better observed in the case of ethyl P-aminocrotonate, when it was found that the absorption band was decreased more and more by repeated addition of small quantities of the acid. The conclusion is therefore drawn that with acetylacetone, ethyl acetoacetate, and their metallic derivatives, a state of dynamic isomer- ism exists in the solution; that the presence of the band in their absorption spectra is due to this isomerism, and that its persistence is a measure of the number of molecules in the state of vibration. It would thus appear that the absorption band is a method of measuring the amount of reaction taking place between two isomeric substances which are in equilibrium."116. '' The action of acetyl chloride on the sodium salt of diacetgl-acetone and the constitution of pyrone compounds." By John Norman Collie. The action of acetyl chloride on tho sodium salt of diacetylacetone was investigated with the object of determining whether the introduc- tion of two acetyl groups into dimethylpyrone would destroy its property of forming salts with acids. As a result of the action of acetyl chloride dissolved in chloroform on the sodium salt, a compound melting at 124' was obtained, which was undoubtedly diacetyldimethylpyrone (compare Thomas and Lefhvre, Bull. Xoc. chim., 1888, 50, 193-194).On repeating this operation, the chief substance produced melted at 954O, whilst in another experi- 159 ment, in which the substances were allowed to react at the tempera- ture of a freezing mixture, a compound melting at 75" was obtained. Them three substances were isomeric, having the formula C11H1204, and were produced according to the equations : C7H,02 + 2NaOH = C7H,0,Na2 + H,O. C,H,O,Na, + 2C2H30Cl = C7H,02(C,H,0), + 2NaC1 + H20. (1) Diacetyldimethylpyrone gave no coloration with ferric chloride, and could be sublimed ;when boiled with barium hydroxide solution, a yellow barium salt was produced, which dissolved in dilute hydro- chloric acid and gave a deep red coloration with ferric salts. Bromine was not decolorised by it.The original substance was totally devoid of any basic properties, and gave neither a hydrochloride nor a platini- chloride. (2) The compound melting at 95" gave a purple coloration with ferric chloride solution, and the orcinol reaction with chloroform and caustic soda. When heated with 80 per cent. sulphuric acid, acetic acid and orcinol were obtained; it gave, with bromine, a monobromo- derivakive, (Cl,H1,04Br)(m. p. 79O), and, with acetic anhydride, a mono-acetyl derivative, CI1H1,(C2H3O)O, (m.p. 75"). It dissolves in aqueous soda with a yellow colour, and, after boiling, can be reprecipitated un- changed on the addition of an acid ; it is, therefore, diacetylorcinol. (3) The third substance (m. p. 75") also gave a purple-redcoloration with ferric chloride ;it decolorised a solution of bromine in the cold, and, after heating for some time, gave the orcinol reaction with caustic soda and chloroform, but, on warming with this alkali, it also was transformed into the compound melting at 94", whilst with hydro- chloric acid it changed into diacetyldimethylpyrone (m.p.124"). These curious transformations receive scanty explanation from the accepted molecular constitution of dimethylpyrone, and formulze for pyrone and its derivatives were brought forward with the view of explaining the foregoing transformation. "117. "Our present knowledge of the chemistry of indigo." By William Popplewell Bloxam. As the determination of the maximum amount of indigo obtainable at each successive stage of its preparation (" mahai ") and of the quan- tity present in the leaf of the green plant dependson the purity of the indigotin employed as a standard, the author has estimated the per- centage of nitrogen in the best specimens procurable, and has thus found that they contain only about 90 per cent. of indigotin.Since the pure substances could not be prepared by the action of 160 solvents on cake indigo or the syr,thetical product, the crude indigo was sublimed under diminished pressure, and in this way a well crystallised product was readily obtained which gave the percentage of nitrogen required for indigotin. This pure material when sulphonated and subjected to analysis by the permanganate method was found to give values ranging up to 300 per cent, of the weight of substance taken.As this method is used in ordinary technical analyses of indigo, this result explained the extraordinary variations observed in the published values given for cake indigo and the products obtained during the successive stages of the manufacture (" mahai "). It has also been found that tha red substance occurring in the cake obtained from plant-indigo and known as ''indirubin " or indigo-red, is not, as stated, a derivative OF indigo, as it contains no nitrogen. This material, which may consist of a mixture of compounds, will be further investigated. 118. '(A1:3-Dihydrobenzene." By Arthur William Crossley. Dibromotetrahydrobenzene, prepared by .Baeyer's method (Annalen, 1894, 278, 88), is a colourless, highly refractive liquid, boiling at 116-1 17"/29 mm.When treated with concentrated alcoholic potassium hydroxide, it yields a small quantity ol A' :"dihydro-benzene, but principally the ethyl ether, C,H,*O*C,H,, of hydroxytetra-hydrobenzene as a colourless liquid boiling at 155", and possessing a pungent odour of peppermint. Quinoline removes two molecules of hydrogen bromide from di-bromotetrahydrobenzene, giving A1:3-dihpdrobenzene, which boils at 81*5--82*/767 mm., and, like the dihydrobenzene obtained from dihydroresorcin (Crossley and Haas, Trans., 1903, 83, 494), is characterised by only adding on two atoms of bromine to form 1 :4-dibromo-A2-tetrahydrobenzene melting at 104.5", and decomposing with evolution of hydrogen bromide at 170'.That this substance is in reality a dibromotetrahydrobenzene is proved by the fact that on treatment with quinoline it loses two molecules of hydrogen bromide with formation of benzene. 119. '' The absorption spectrum of p-nitrosodimethylaniline." ByWalter Noel Hartleg. It was pointed out that the usual formula assigned to benzoquinone is less consistent with its chemical properties as an oxidiser than the peroxide formula and that an unreduced benzene ring is in accord with 161 the optical properties of the substance, since its spectrum exhibits powerful absorption bands. The usual formula, on the other hand, contains the partially reduced carbon ring present in hydroaromatic substauces, and the spectra of these are characterised by an absence of absorption bands.The absorption hands in the ultra-violet are always associated with the production of colours, even when the sub- stance examined shows no visible colour, and such substances are in reality chromogens (Trans.,1887, 51, 154-202). Nitroso-corn-pounds of the aromatic series have a powerful and extensive selective absorption in the ultra-violet, and it was thought possible to draw a distinction betweer these and the closely related oximes. The following conclusions mere deduced : 1. The absorption caused by p-nitrosodimethylaniline at the less refrangible end extends into the infra-red, and at the more refrangible far into the ultra-violet. The transmitted rays are thus restricted to a band of yellow and green light bordered on either side by a band of intease absorption.2. There appears to be a decided difference in constitution as judged by their spectra between p-nitrosophenol or quinoneoxime and pnitrosodimethylaniline which cannot be accounted for by a substitution of hydroxyl for the group N(CH,),. 3. The alkyl substituted phenols and anilines absorb varying quan- tities of the ultra-violet, the absorption not extending into the visible spectrum, but the introduction of the NO, as distinguished from the NOH group, extends the absorption far into the coloured rays. This appears to be a characteristic effect of the nitrosyl group in conjunc- tion with the benzene ring. 4. Although the absorption of rays in the blue and violet by pnitrosodimethylaniline is strong, there is at a certain dilution a transmission of the greater part of the ultra-violet.This explains the action of Wood’s screen, which cuts off the visible rays while it transmits some of the ultra-violet. On testing the solu- tions of p-nitrosodimethylaniline, it was found that some red rays were still transmitted, but it is quite possible to adjust the thickness of the solutions so that with a quartz lens and electric light what appears to be perfect darkness causes the fluorescence of uranium nitrate and barium platinocyanide. The appearance of the crystals was brightest when some obscure or feeble blue rays were transmitted. From a consideration of the facts referred to in connection with conclusion 3, and the previous observations on benzoquinone and its oxime, dioxime, chloroimide, and dichloroimide, it appears to be not improbable that a solution of p-nitrosophenol is a mixture of two tautomeric forms, the one a phenol and the other nn oxime. 162 120.The influence of solvents on the rotation of optically active compounds. Part VI. The relationship between solution-volume and rotation of the dialkyl and potassium alkyl tartrates in aqueous solution.” By Thomas Stewart Patterson. Values for the molecular solution-volumes of dimethyl-, diethyl-, di- n-propyl, potassium methyl-, potassium etbyl-, and potassium n-propyl- tartrates are given, and the changes of volume due to solution in water compared with the corresponding changes in rotation.It;is shown that in both series a contraction of 1 C.C. per gram-molecule produces the greatest change of rotation in the methyl and the least change of rota-tion in the n-propyl ester, and that the perplexing rotation changes of these compounds, due to solution in water, can at least be brought into harmony when a causal connection between solution-volume and rotation is assumed. 121. ‘(The constitution of hydrastinine.” James Johnston Dobbie and Charles Kenneth Tinkler. The study of the absorption spectra of hydrastinine, C,,H,,O,N, has yielded results precisely similar to those obtained with cotarnine (Twns., 1903, 83,598). Solutions of hydrastinine in ether or chloroform are, like the solid substance, colourless, and their absorption spectra are practically identical with the spectra of hydrohydrastinine, a compound which is generally considered to have the constitution represented by formula I.Prom this, it is argued that the carbinol formula 11,which represents hydrastinine as differing from hydrohydrastinine onlF in the replace- ment of an atom of hydrogen by a hydroxyl group, should be preferred to the open-chain or aldehydic formula of Roser, which would leave the agreement between the absorption spectra of the two substances elltirely unexplained. CH,*Y*CH, CH(OH)*T*CH,C7H402<(7H2.CH2 C,H,02<CH2-C H, 1. 11. Hydrohydrastinine. Hydrastinine (carbinol form). On the other hand, the aqueous or alcoholic solutions of hydrastinine, which are yellow and fluorescent, give spectra which agree with those of the hydrastinine salts.It would therefore appear that, under the influence of these solvents, hgdrastinine changes from the carbinol to the ammonium base, the hydroxyl group shifting from the carbon atom to the nitrogen and forming the complex >N(CH,)*OH. 163 The spectra of the colourless solutions agree closely with those of the corresponding solutions of cotarnine. The spectra of the coloured solutions possess three absorption bands corresponding in position with two bands in the cotarnine spectra. All the hydrustinine derivatives examined give spectra which are identical or nearly so with those of hydrohydrastinine or of the hydrastinine salts.Alcohol imparts a yellow colour to an ethereal solution of hydrastin- ine, the depth of colour increasing as the proportion of alcohol to ether is increased. An examination of the spectra of such solutions shows that as alcohol is gradually added the carbinol form changes into the ammonium base form. The opposite change is brought about by the addition of alkalis to the yellow solution of hydrastinine compounds, the disappearance of the fluorescence marking the complete conversion of the ammonium base form into the carbinol form. 122. “The influence of moist alcohol and ethyl chloride on the boiling point of chloroform.” By John Wade and Horace Finnemore. Chloroform, when made from alcohol, contains a small quantity of ethyl chloride, the absence of which from chloroform made from acetone detracts from its efficiency as an anaesthetic.The ethyl chloride de- presses the boiling point of the chloroform ; it was partially isolated by fractionation through a Young’s evaporator column, and was identified by conversion into silver propionate. Incidentally, the authors have isolated binary mixtures of chloro-form and alcohol, and chloroform and water, and a ternary mixture of chloroform, alcohol, and water, all of minimum boiling point. The first binary mixture boils at 59*4’/760 mm., has a sp. gr. 1.4125 at 15’/15O, and contains 7 per cent. of alcohol, The second binary mixture boils at 56.1’/760 mm., and contains about 1 per cent. of water.The ternary mixture boils at 55*5’/760 mm., and contains 4 per cent. of alcohol and about 3.5 per cent. of water. The water in both these mixtures separates at once from the distillate. 123. ‘‘Limonene nitrosocyanides.” By William Augustus Tilden and Frederick Peacock Leach. The nitrosocyanide referred to (Proc., 1902, 18,163) by Tilden and Burrows a$ a liquid is found to be a crystalline, optically active solid, m. p. 90-9lo, and [.ID + 165O; it yields a bonzoyl derivative, which crystallises in shining plates melting at 107’. The nitrosocyanide has R monomoiecular structure, C,,H,,NO*CN, and, the formula for limonene having been recently established by Perkin, the nitrosocyanide must be represented as follows : This compound is obtained by digesting limonene P-nitrosochloride with potassium cyanide, It is also the chieE product of the same treatment of the mixed a-and P-nitrosochlorides.It has not yet been obtained from pure a-nitrosochloride, which yields a viscid product, but from the latter a benzoyl compound is obtained, which is identical with the benzoyl derivative of the P-nitrosocyanide, The investigation will be continued. 124. '' Photochemically active chlorine. 11. A preliminary notice." By Charles Hutchins Burgess and David Leonard Chapman. A considerable number of experiments have now been performed with the purpose o€ discovering the conditions under which the activity of chlorine gas or its solution is induced and destroyed (this vol., p. 52), the following being a brief summary of some of tho results obtained : (1) Active chlorine is formed by the action of light or heat on in-active chlorine.(2) Moist chlorine, when heated to the boiling point of water and then cooled to the ordinary temperature, is rendered almost as active as by the action of light. (3) By the passage of the electric discharge through inactive chlorine (compare J. W. Nellor, this vol., p. 140). It has also been shown that freshly prepared electrolytic gas and chlorine are almost at their maximum activity, and in measuring the activity of either of these gases it is very necessary to make sure that the chlorine contained in the control actinometer is inactive. It has now been observed that aqueous solutions of certain acids and salts are more effective in removing the activity than pure water.An active solution of chlorine in water can be prepared either by leaving the liquid in contact with active chlorine or by heating aqueous solutions of chlorine. Only a very small fraction of the activity is removed by pumping the chlorine out of an active solution under diminished pressure, and when an active solution is distilled in a vacuum both the distillate and the residual liquid are active. Aqueous solutions of chlorides through which ozone has been passed are more active than solutions of the same strength which have not been thus treated. The residual liquid remaining after removing the chlorine under 165 diminished pressure, when treated successively with potassium iodide and N/10thiosulphate, still retains a large proportion of its activity.The condition of the moist chlorine having been found to be the cause of the induction pexiod, experiments were made for the purpose of deciding whether this phenomenon ir; due to the format,ion of a compound of the type Cl,,H,O, which is subsequently destroyed by hydrogen with the formation of hydrochloric acid. Comparative measurements of the induction period and of the rate o€ formation of hydrochloric acid after the induction period were made, and on applying the law of mass action to the results it was seen that if the foregoing assumption is correct then at least one-half of the chlorine in the actinometer must have been converted into the com- pound CI,,H,O before hydrochloric acid began to be formed in appre- ciable quantity, a result which is obviously absurd.The conditions of formation of active chlorine precisely correspond with those which are known to be necessary for the substitution of hydrogen in the side chain of a benzene compound. 125. ‘(Additive compounds of anhydrous magnesium bromide with organic oxygen and nitrogen compounds.” By John Joseph Sudborough, Harold Hibbert, and Stanley H.Beard. yH,*C(OEt)( OMgBr)*$23, In attempting to prepare CE€,*C(OEt)(OMgBr)’CH, by the action Of a dry ethereal solution of ethylene dibromide on ethylsuccinate in the presence of dry magnesium, an additive cornpound of magnesium bromide and ethyl succinate was obtained. This is an extremely hygroscopic, crystalline solid which may readily be prepared by the direct union of its components; it has the composition (CH,*CO,Et),,MgBr,. Additive products of other organic oxygen compounds, such as ether, amyl ether, benzaldehyde, cinnamaldehyde, benzophenone, pyruvic acid, and ethyl benzoate, have been obtained.Amines and nitrites appear to be capable of forming similar additive compounds, wbereas hydrocarbons are not. The compounds are all extremely hygroscopic and difficult to obtain quite pure. 126. DiEerentiation of primary, secondary, and tertiary amines. A preliminary note.” By John Joseph Sudborough and Harold Hibbert. L. Meunier (Cornpt. rend., 1903, 136,758)has shown that primary and secondary amines react with magnesium methyl iodide in ethereal 166 solution according to the equations RNH, + CH,*MgI =RNH-MgI+ CH, and RR'NH + C€I,*MgI = RR'N'MgI + CH,.It is now shown that with primary amines and a solution of magnesium methyl iodide, in amyl ether the reaction proceeds quan- titatively in the cold, as stated by Meunier, but that when the solu- tion is heated a second molecule of methane is set free, presumably according to the equation RNH*MgT+ CH;MgI = RN(MgI), + CH,. When a secondary amine is used, only one molecule or methane is evolved for each gram-molecule of the compound, even on heating. Tertiary amines do not evolve any gas when mixed with Grignard'a reagent. The compounds examined so far have been p-toluidine, P-naphthyl- amine, diphenylamine, carbazole, and dimethylaniline.It is the intention of the authors to extend the work, and on these reactions to base methods for the characterisation of amino- and imino-groups and for the estimation of the amounts of primary, secondary, and ter- tiary amine in a mixture, 127. ('Influence of radium radiations on labile stereoisomerides." By John Joseph Sudborough. The relative effects of exposing labile stereoisomerides to sunlight and to radium radiations have been examined. The substances used were allo-cinnamic, a-bromo-do-cinnamic, and P-bromo-allo-cinnamic acid9. It has been already shown (Trans., 1903, 83,685, 1166) that these acids are transformed to a large extent into the more stable isomerides by the action of light or heat.Prolonged exposure in the dark to the rays from pure radium brom- ide (1 mg.) does not affect the melting points of the acids. The three acids, melting respectively at 68', 120-121°, and 159-160°, were exposed to the radiations during a period of four months: at the end of this time no change in appearance and practically no alteration in melting point could be detected ; the melting points found were 68', 118-121°, and 158-160'. Specimens of the same acids were exposed to sunlight on March 17th, and by April 7th the melting points were considerably affected. The do-cinnamic acid then began to melt at 60', the a-bromo-do-acid at loo', and the P-bromo-aZZo-acid at 145'. On June 13th, the allo-cinnamic acid began to melt at 60' and was nearly completely fused by 120', although a small amount of solid still remained at 145'.The a-bromo- do-acid began to melt at 90' and was completely fused at 105'; the /3-allo-acid began to melt at 120' and was completely fused at 135O, 167 thus indicating that the three allo-acids are transformed into the stable isomerides more readily under the influence of light than by prolonged exposure to radium radiations. 128. ‘‘ Notes on analytical chemistry.” ByeGilbert Thomas Blorgan. I. The Separation of Arsenic by Distillation in Hydrogen Chloride. -A modification of Piloty and Stock’s apparatus (Beis., 1897, 30, 1649) was described in which the mixed sulphides of arsenic and antimony were distilled in a current of hydrogen chloride, so that the vapours did not come into contact with organic matter until after passing through a cooled aqueous solution of hydrogen sulphide.In dealing with a mixture containing arsenic in the two states of oxidation, the distillation was first carried out in hydrogen chloride, when the arsenious sulphide precipitated in the receiver represented the tervalsnt arsenic. On repeating the distillation of the residual liquid in a current of hydrogen chloride mixed with hydrogen sulphide a second precipitation of arsenious sulphide was obtained, this being derived from the arsenic originally present in the quinquevalent condition. 11. The Estimation of Ccoabon by Oxidation with Chromic Acid.-Phosphoric acid was substituted for sulphuric or hydrochloric acid in the gravimetric estimation OF carbon dioxide in native carbonates, and when these substances contained organic matter, chromic acid was subsequently added to the contents of the distilling flask and the operation repeated, the second increase in weight of the tared absorp- tion tube being due to the oxidation of the organic carbon.The mixture of chromic and phosphoric acids was also used in estimating the total carbon in cast iron and ferromanganese, the employment of a non-volatile acid instead of sulphuric acid obviating the risk of carrying over acid fumes into the weighed absorption tube. 129. GL Nitrogen chlorides containing two halogen atoms attached to the nitrogen.” By Frederick Daniel Chattaway.Very few substituted nitrogen chlorides containing two halogen atoms attached to a single nitrogen atom have been prepared, the best known being those derived from the primary alkylamines. Stable, well-crystallised compounds having the general formula RSO,*NCI, are yielded by all the sulphonamides, and a few have already been described by Kastle, Keiser, and Bradley (Amer. Chem. J.,1896, 18, 491). 168 They are most easily prepared by dissolving the sulphonamides in a solution of bleaching powder and adding acetic acid, when they sepa- rate as crystalline solids. The dichloroaminosulphonamidesare not easily hydrolysed even by boiling with water ;they dissolve in caustic alkalis, apparently yielding salts of the monochlorosulphonamides, which can be recrystallised from water.With hydrochloric acid, hydriodic acid, or alcohol, they react vigorously, the sulpbonamides are regenerated, and chlorine, iodine, or ethyl hypochlorite is liberated. On heating rapidly, the dichlorosulphonamides decompose with slight explosion, whilst the tetrachlorodisulphonamides explode with great violence. This beha- viour is noteworthy, as the latter compounds are the only substituted nitrogen chlorides yet prepared which detonate in a way resembling the explosion of nitrogen chloride itself, These compounds, as well as the chlorosulphonalkylamidesand the corresponding bromine derivatives, are being further studied, as they are very reactive and promise to be of considerable value in organic synthesis.Moreover, the dichlorosulphonamides are so easily pre- pared, crystallised, and aoalysed that they may prove of considerable use in the investigation of sulphonic acids. The following compounds were described : Benzenesulphondichloroamide, C1,H5*S0,*NCI,, colourless plates, m.p. 76" ;p-boluenesulphondichloroamide, CH,-C,H,~SO,*NC'l,, long, four-sided prisms, m. p. 83' (Kastle, Keiser, and Bradley, Zoc. cit.) ; o-toluenesulphondichloroamide, CH;C,H,*XO,*NCI,, colourless plates, m. p. 33' ;m-nitrobenzenesulphondichlorodiamide,NO,*C,H,*SO,*NCI,, faintly yellow, six-sided plates, m. p. 121' ; o-nitrotoluene-p-sulphon-dichloroamide, CH,*C,H,(NO,)*SO,*NCl, (1 : 2 : 4), pale yellow, four-sided prisms, m.p. 101' ; benzene-m-disulphontetrachloroamide, C,H,(SO,*NCl,),, colourless rhombs, m. p. 128" ; naphthalene-1-sulphondichloroamide, C,,H7*S0,*NC1,, pale yellow plates, m. p. 91' ; naphthalene-2-sulphondichloroamide,colourless plates, m. p. 68" ;naph-thalene-2 : 7-disulphontetrachloroamide, C,oH,(SO,=NCI,),, clusters of colourless pyramids, m. p. 165' ; anthraquinone-2-sulphondichloro-amide, C,,H70,*S0,*NCI,, yellow plates, m. p. 177". 130. Sulphonphenylchloroamides and sulphontolylchloroamides." By Frederick Daniel Chattaway. In a paper on the action of sodium hypochlorite on the aromatic sulphonamides, Raper, Thomson, and Cohen (l'rans., 1904, 85, 371) state that they were unable to obtain benzenesulphonphenplchloro-smide, which was too unstable to be isolated in a pure state.This 169 and other similar compounds can, however, easily be obtained if pre-cautions are taken to avoid the presence of catalytic agents mhicb bring about transformation. They are well-crystallised, comparatively stable substances, and show the characteristic behaviour of chloro-amino-derivatives, The method of preparation and the properties of benzenesulphonpheny lchloroamide and of a number of similar com- pounds were described. 131. “ Stereoisomeric glucoses and the hydrolysis of glucosidic acetates.” By Edward Frankland Armstrong and Paul Seidelin Arup. The results obtained on hydrolysing several of the glucosidic ace- tates by alkali were described and discussed in the light of the evidence recently brought forward regarding the stereoisomeric glucoses.It was shown that the acetyl groups are removed with unequal readiness from the penta-acetates of glucose and galactose and from sucrose octo- acetate, and with equal readiness from the tetra-acetates of the methyl- glucosides and galactosides. Kreman’s observation (Monatsli, 1902, 23, 479) that the two isomeric pents-acetates of glucose are hydrolysed at equal rates is confirmed. 132. “The colouring matter of the flowers of Butea frondosa.” By Arthur George Perkin. In a former communication (J. J. Hummel and A. G. Perkin, PYOC., 1903, IS,134), it was considered probable that butein from Buteu frondosa exists in ‘a colourless, as well as in a yellow form. These modifications are, however, distinct substances.The colourless com- pound now termed butin, Cl,H1,O,, crystallisiag from alcohol in colourless needles and from dilute alcohol in pale yellow needles with &H,O, melts at 224-226’. The tiaiacetyl compound, Cl,HgO,(C,H,O),, forms colourless leaflets (m. p. 123-125’), and the benxoyl compound, C,,HgO,(C,H,O),, colourless needles (m. p. 155-157’). On fusion with caustic alkali, butin gives resorcinol and protocatechuic acid, and at a lower temperature resacetophenone is also formed. By methylation, two isomeric methyl ethem, C15H902(0CH3)3,are produced: (a) yellow leaflets (m. p. 156-158’) containing a free hydroxyl group, and (b) almost colourless, flat needles (m. p. 119-1310). Butein, C15H1205,orange-yellow needles (m.p. 21 3-215”), crystal-lises from dilute alcohol with lH,O; it is obtained in small quantity together with butin from the plant, and can be prepared from butin by the action of hot dilute caustic alkali or alcoholic potassium ace- tate ;acetylbutein, Cl5H8O5(C,H,O),, forms ‘pale yellow needles (m. p 170 129-131'). On fusion with alkali, butein gives the same decom-position products as butin, and on methylation the same two trimethyl ethers, (a) m. p. 156--15So, and (b) m. p. 119-121'. When digested with boiling dilute alcoholic sulphuric acid, butein is partially reconverted into butin, and by digesting the trimethyl com-pound (m. p. 119-121°), which is really butin methyl ether, with alcoholic potash and water it passes into the butein methyl ether (a) (m.p. 156-158'). Again, on digesting butein methyl ether with alcoholic sulphuric acid butin methyl ether is obtained. Bu tein has the constitution of a tetrahydroxybenzylideneacetophenone (c halkone) : OH OH/\OH /)OH ,I\/bO*CH :CHI\/ as proved by the synthesis of its trimethyl ether (m. p. 156-155s') by the condensation of veratric aldehyde with resacetophenone mono- methyl ether. Kostanecki and his colleagues (Ber., 1904, 37, 784) have shown that with dilute sulphuric acid chalkone methyl ethers give the corresponding flavanone compounds, and as both butein and its methyl ether in this way yield butin and its methyl ether respectively, there can be little doubt that butin has the following constitution : 0 OH 133.''Cyanomaclurin." By Arthur George Perkin. Cyanomaclurin (Trans., 1895, 67, 937) which exists in jackwood (Artocurpus integrifoolia) in conjunction with morin, crystallises from water in the anhydrous form, and is now shown to be isomeric with the catechins, C1,H,,06 ;it forms a pentu-acetyl compound, C15H906(C2H30)5, separating in colourless needles (m. p. 136-138'), a pentabenxoy2 compound forming colourless prisms (m. p. 171-173'), and the axobenxene derivative, Cl,H,,0,(C,H,N2)2 (m. p. 245-247"), gives an acetyl compound melting at 209-210'. On fusion with caustic alkali, cyanomaclurin gives P-resorcylic acid (not cresorcylic acid as previously suggested) and phloroglucinol, and with pine wood and hydrochloric acid it resembles the catechins in giving the phloroglucinol reaction.171 With boiling dilute hydrochloric acid, a brown amorphous compound is produced ; this is identical in appearance with the so-called fourth anhydride from Gambier catechin, and has the same percentage com-position. Cyanomaclurin thus appears to represent a catechin in which the catechol nucleus is replaced by resorcinol. 134. '(The determination of acetyl groups." By Arthur George Perkin. The substance (approximately 0.5 gram) in 30 C.C. alcohol is distilled with 2 C.C. of sulphuric acid, a little fresh alcohol being added from time to time. The distillate is collected in standard alcoholic potash, and this is boiled in order to saponify the ethyl acetate present, the mixture being subsequently titrated with sulphuric acid.The opera- tion is complete in about an hour and sufliciently accurate for general use. The following results have been obtained : Acety lalizarin gave acetic acid = 37.59. Theory 37.04. 99Acetylquercetin = 58.44. ,, 58-59. Acety1purpurogallin = 62.40. ,, 61.86.99 Acetylcatechin (m. p. 129-130") ,, = 60.18. ,, 60.00. Acetylcatechin (m. p. 158-160°j ), = 60.24. 60.00. 7,Acetylbutin = 45*60,45.34.,, 45-23, With acetanilide and its homologues reliable results are also obtained, employing, however, 4 C.C. of sulphuric acid, and longer dis- tillation. Thus acetanilide itself gave acetic acid = 44.74 and 44.55 per cent,, whereas theory requires 44.44.It has been previously shown that, with alcoholic potassium acetate, acetyl derivatives of the phenols evolve ethyl acetate. This process can be employed for acetyl determinations in some instances, and is still under investigation, but as yet has not been successful in all cases. By this means acetyl- butin gave 45.60 (p. 169) and acetylbutein 54 per cent.; in the latter case the theory requires 54-54 per cent. 6'135. Note on the catechins." By Arthur George Perkin. In a previous communication (Trans., 1902,81,1160) it was pointed out that whereas Qambier catechu contains a catechin, ClaH1,O, (m. p. 175-1'77*), the pentabenzoyl derivative of which melts at 151-15307 yet a catechin, CI,HI,O,, which was isolated from Acacia catechu melted at 204-205", and gave a benzoyl compound, melting at 172 181-183".It is now found that the acacia catechingives an acetyl de-rivative, Cl,H,06(C,H,0),, forming colourless needles (m. p. 158-1 60°), and a tetramethyl ether, C15H1002(OCH3)4,separating in colourless prisms (m. p. 152-153O). The corresponding substances from the Gam- bier catechin (Kostanecki and Tambor, Ber., 1902, 35,1867), melt at 129-130' and at 142---143", respectively. For acacia catechin the name I' acacatechin ') is proposed. 136. ('A constituent of Java indigo." By Arthur George Perkin. Rswson (J. Soc. Dyers and Colourists, 1899,15,129) has shown that Java indigo contains a yellow colouring matter. This substance, Cl5HIOUtj,forms yellow needles, melts at 276-277O, and gives an acety 1 compound, Cl,H,O,(C,H,O),, which separates in colourless needles and melts, when crystallised from methyl alcohol, first at 116-120" and subsequently at 181-182".The colourin matter is identical with kampherol (Z'rarns., 1902, 81,587). LIST OF FELLOWS. As the List of Fellows for 1904 is now in active preparation, no change of address received after July 30th can be included in it. THE LIBRARY. The Library will be closed for Stock-taking from Monday, August 8th, until Saturday, August 20th, 1904, inclusive. Fellows are particularly requested to return all books belonging to the Library not later than Wednesday, August 3rd. H CLAY AND SONS, LTD., BREAD S'P. HILL, E.C.. AND BUNOAY, SUPFOLK.
ISSN:0369-8718
DOI:10.1039/PL9042000151
出版商:RSC
年代:1904
数据来源: RSC
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