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Proceedings of the Chemical Society, Vol. 29, No. 416 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 416,
1913,
Page 167-178
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[Issued 3015113 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 29. No. 416 Thursday, May 15th, 1913, at 8.30 p.m., Professor W. H. PERKIN, LL.D., F.R.S., President, in the Chair. Reference was made to the death, on April 29th, 1913, of Mr. Matthew Algcrnon Aaams, of Maidstone, who was elected a Fellow on February 15th, 1877. The PRESIDENTannounced that the Council have proposed the following gentlemen as Honorary and Foreign Members, and that a ballot for their election will be held at the next Ordinary Scientific Meeting on Thursday, June 5th : Professor Dmitri Petrovitsch Konovaloff (St. Petersburg). Professor Alfred Werner (Zurich). The PRESIDENTalso read the following statement which the Council have received with reference to the Van’t Hoff Memorial Fund : REPORT HOFF COMMITTEE, OF THE VAN’T April lath, 1913.The united Committees of Amsterdam and Rotterdam have received up Go the present a sum of F1.56,000, about F1.6,000 having been contributed by foreign countries. A sum of F1.35,000 has been set aside to defray the cost of the statue to be erected in Van’t Hoff’s native town, Rotterdam, after the design of Mr. Charles van Wijk, of The Hague. It is hoped that the inauguration may take place during the course of 1915. After the expenses have 168 been deducted, the remainder will be allotted to the Van’t Hoff Nemorial Fund for the advancement of original research in pure and applied chemistry. Probably the Royal Academy of Science of Amsterdam will undertake to manage the capital and to assign the annual grants.Certificates were read for the first time in favour of Messrs. : William Rhys-Davies, Swan Arcade, Bradford. Roy Gonqalves Glenday, B.A., Emmanuel College, Cambridge. Victor Lefebure, B.Sc., 25, Belitlia Villas, Barnsbury, N. Duncan James Macnaughten, 31, Clonmel Road, Fulham, S.W. Percy Cyril Lesley Thorne, B.A., Borough Road Training College, Isleworth. Jeremiah Twomey, B.Sc., 21, Onslow Road, Elm Park, Liverpool, Thomas Howard Young, 118, Scotia Street, Winnipeg, Canada. Messrs. A. J. Ewins and H. Finnemore were elected Scrutators, and a ballot for the election of Fellows was held. The following were subsequently declared as duly elected : John Percy Batey, M.Sc.Tech.Harold Charles Lloyd, B. Sc. Horace George Battye. John Francis MCC~~IIII. George Frederick William Blackburn. Harry Bertram Maynard. Edward Cahen. Bhaichand Anupehand Mehta, M. A. Alexander Caruth. Arthur George Abraham Miller, B.Sc. Noel Guilbert Stevenson Coppin, 11.Sc. Ferrand Paget. Arthur Ernest Crutchley. Francis Martin Potter, B.Sc. Vasanji Premji Dalal, 31.A., B. Sc. Julien Pierrre Frederic Pougnet. Harold Davies. Kali Prosonuo Rai. M.A. Blfred Gilbert Dix, B.Sc. Arthur Samuel Robinson, B.Sc. Herbert Garland. John Robert Rufley. Fritz Haber. Reginald Wi 11i am Rusby . Percy Wolmer Hill. Hormusji Kliarschedji Sahiar, M.A. Harold Edward Pollock Hodsoll. Sosale Garalapury Bastry, B.A. Thomas Arthur Holroyd, B.Sc. Xerbert Sutcliffe Shrewbury.Percy Hutchinson, B.Sc. William James Stansfield. Hilton Ira Jones. Thomas Watson. Darab Dinsha Kanga, M.A. Cornelius Williams. B.Sc. Douglas Rayment Keller, B.Sc. Thomas Harrison Winstanley. Emmanuel Francis Kur. Cliftou Wyver. Joseph Stuart Lawson. William John Young, D. Sc., 11.Sc. Of the following papers, those marked * were read: “140. “Studies of dynamic isomerism. Part XV. The influence of light on isomeric change.” By Thomas Martin Lowry and Harold Reuben Courtman. Several substances which readily undergo isomeric change on dissolution were exposed to the action of ultraviolet light by enclos 169 ing the solutions in a silica polarimeter tube surrounded by a silica water-jacket and placed in close proximity to a silica mercury lamp, Of nine substances examined, only two showed any marked accelera- tion of isomeric change.In the case of aminomet#hylenecamphor the increase of velocity was confined to the period of exposure to light, but in the case of benzoylcamphor it persisted after the light was extinguished, as if some chemical catalyst had been produced in the solution. “141. “Derivatives of o-xylene. Part 111. The presence of a mobile nitro-group in each of the two trinitro-o-xylenes.” By Arthur William Crossley and Walter Ryley Pratt. 3 :4:5-Trinitro-and 3 :4 :6-trinitro-o-xylenes each contains a mobile nitro-grcup occupying position 4 in the former and position 3 in the latter compound. The groups are replaced by the amino- group when treated with alcoholic ammonia (T., 1911, 99, 2345), and it has row been found that many substituted amines behave similarly to ammonia.Derivatives have been prepared from the following primary amines : methylamine, ethylamine, aniline, p-toluidine, 0-and panisidine, benzylamine, and, using the second- ary amines, dimethylamine and piperidine. Ortho-and meta-nitroaniline and methylaniline appear to have no action on the trinitroxylenes, and although interaction takes place between both trinitroxyleiies and diethylamine, aha p-phenylenediamine, only resinous products and no crystalline derivatives could be obtained. It is interesting to note that the mobile group in 3 :4:5-trinitro-o-xylene is situated ortho- to the two other nitro-groups, whereas in 3 :4 :6-trinitro-o-xylene it is ortho- to one and para- to the other, both positions which, as already noticed, seem especially f avourable to replacement.DIscusSION. Dr. FLCRSCHEIM confirmed Prof. Crossley’s conclusion that the mobility of a nitro-group in 3 : 4 : 5-trinitro-o-xylene should even be exceeded in tetranitroaniline. He agreed with the President’s view that this fact could not be entirely accounted for by the influence of the additional nitro-group in the para-position to the mobile group, since the effect of a para-nitro-group would be small in com- parison with that exercised by the two nitro-groups already present in the ortho-positions. The methyl groups in trinitro-o-xylene would, however, largely account for the difference.Methyl was known to lower the reactivity of chlorine in chlorodinitrobenzene and that of a nitro-group in trinitrobenzene; also the tendency of m-dinitrobenzene and s-trinitrobenzene to form additive compounds 170 with amines, the dissociation constant of nitrobenzoic acids, etc. (compare also Blanksma, Eec. trav. chim., 1906, 25, 175). Prof. Crossley’s proof that 3 : 4 : 6-trinitro-o-xylene and Meldola’s trinitroacetylaminophenol exchanged their nitro-groups in diff ereiit positions appeared to be of considerable interest. The cause might possibly be traced to the effect which the residual affinity of the hydroxyl group in Meldola’s compound must have on the amount of affinity at the disposal of the various benzenoid carbon atoms for binding the nitro-groups. Dr.R. SELIGMANasked whether Prof. Crossley had noticed any difference in the mobility of the nitro-groups in 3 :4 : 5-trinitro- and 3 :4:6-trinitro-o-xylenes. In view of the form which the discussion had taken, several speakers having ascribed the mobility to the ortho-position of two nitro-groups rather than to their para-position, it seemed that any such observation by Prof. Crossley should settle the question, as he had two compounds differing ouly in the relative positions of the nitro-groups. In reply, Prof. CROSSLEYstated that at the present time no measurements of value had been made of the relative mobility of the nitro-groups in 3 : 4 : 5-trinitro-and 3 :4: 6-trinitro-o-xylenes.Many experimental difficulties would have to be overcome before this would be possible, and work with this object in view was now being undertaken. *142. I4 Derivatives of o-xylene. Part IV. Synthesis of 4 :5-di-bromo-3-o-xylenol.” By Arthur William Crossley and Sydney Smith. 4:5-Dibromo-3-~xyZenol,prepared by the method already indi- cated (P., 1912, 28, 333), crystallises from aqueous alcohol in glistening, flattened needles, melting at 97O. The acetyl derivative separates from light petroleum in large, hexagonal prisms, melting at 78O, and the benzoyl derivative crystallises from alcohol in small, transparent rhombs, melting at 153O. *143. The synthetical preparation of the d-glucosides of sitosterol, cholesterol, and some fatty alcohols.” By Arthur Henry Salway.it has already been shown (T., 1913, 103, 399) that ipuranol and some allied compounds occurring in plants, to which specific names had been assigned, are phytosterol glucosides. In many cases these compounds appear to consist of sitosterol-d-glucoside, C27H450.CGII1105, whilst in other instances they seem to be a mixture of the latter with the glucoside of stigmasterol, ~,oH.I90*CGH,1~5* 171 The author gave a description of the synthetic preparation and properties of some glucosides of the above-mentioned type, and also of the glucosides of some fatty alcohols. The compounds which have now been prepared and charact’erised are as follows: (1) Sitosterol-d-glzhcoside, C27H450*C6H1105 (m. p.295-300’) ; (2) cholesterol-d-glucoside, C,,H,,O*C,H,,O, (m. p. 285O) ;(3) ~~yric?/l-d-glucoside, C,,H,,O*CBH,,O, (m. p. 99.) ;(4) ceryl-d-glztcoside, C&EI5,O~C6H~,0,. This compound was obtained in two modifications, melting at 94O and 135O respectively ;and (5) cetyl-d-glucoside, C,6H3,0*C6Hl,0,. Although this glucoside was first synthetically prepared by Fischer and Helferich (Annulen, 1911, 383, 68), it Bas now been somewhat more completely characterised. Several derivatives of the above-mentioned glucosides have likewise been prepared. DISCCSSION. In reply to Dr. Forster, Dr. SALWAYstated that the substances previously designated as ipuranol, trifolianol, cluytianol, etc., were so named in order to indicate their origin and alcoholic nature, and no other method of procedure was possible in the case of new organic compounds of unknown constitution.Since it had now been ascertained that the group of substances referred to were phytosterol glucosides, it was possible to designate them collectively as phytosterolirzs. *144. (‘The rotatory dispersive power of organic compounds. Part I. The measurement of rotatory dispersion.” By Thomas Martin Lowry. A description was given of methods and apparatus suitable for ordinary laboratory use in the measurement of rotatory dispersion. Special importance is attached to measurements of rotatory power for the mercury lines of wave-length 5461 and 4359. *145. (( The rotatory dispersive power of organic compounds. Part 11. The form of the rotatory-dispersion curves.” By Thomas Martin Lowry and Thomas William Dickson. It was shown that the rotatory dispersion in a large number of simple organic compounds can be expressed by the formula: a=& A2 -xo?’ where a,is t,he “ absolute rotatory power ” and A$ is the “dispersion constant ” of the substance.1T2 146. ‘(Synthesis of unsymmetrical derivatives of deoxybenzoia.” By John Cannell Cain, John Lionel Simonsen, and Clarence Smith. The authors have prepared fI-keto-a-4-nz et7~0xyphenyl-P-3 :4-di-.methoxyphenylet ha rae (I) by condensing p-metJboxyph er~ylacetyl chloride with veratrole, and fI-/;eto-P-4-ntethoxyplieti~ll-a-3: 4-di-(1.) (11.) metho~yphenyletiLa.rie (11) by condensing 3 :4-dimethoxyphenyl-acetyl chloride with anisole.Oxinzes of both compounds were also prep a.r ed . 147. ‘:A constant pressure viscometer.’ By William Hamilton Patter Bon. A viscometer was described in which the varying levels of the liquid measured play no part in determining the pressure of flow, and hence no corrections are required for density, etc. Determina-tions can be carried out at different temperatures. A constant pressure of air drives the liquid slowly through a narrow-bore tube, which is made of fused silica. 148. ‘‘The chemical nature of some radioactive disintegration products. Part 11.” By Alexander Fleck. In accordance with the theoretical conclusions advanced inde-pendently by K. Fajans and F. Soddy since the first part of this paper was published (T., 1913, 103,381), it has been found that radium-A is chemically non-separable from radium2 (polonium), and that thorium-D end actinium-l) are, in the same way, similar to thallium.The non-separability of radium-A from polonium was proved by placing two plates of different metals simultaneously in a solution containing radium-A, -23, -C, and -3’ for one minute. There were thus different potential differences forcing the ions of the radio-elements on to the plates, but it was found that the same relative quantities of polonium and radium-A were deposited on each of the various pairs of metals tried. The case of the similarity of the -Dmembers and thallium was shown by a number of reactions and by fractionally precipitating thallium first as chloride and finally as sulphide from an alkaline solution.The concentrakion of the active substance was not altered in any of the fractions. 173 Actinium-B was also proved to be non-separable from lead by a series of fractional precipitations of lead sulphate, in which it was shown that the concentration of actinium-B is constant in all fractions. 149. ‘‘ The estimation of small quantities of lead.” By Alfred Vincent Elsden and John Firth Stansfield. Wilkie’s observations (J.SOC.Chem. Ind., 1909, 28, 636) on the co-precipitation of lead and ferric iron by ammonia have been confirmed, and this property has been applied to the separation and estimation of small quantities of lead. A new method for the estimation of lead in the presence of iro2 was described, and examples were given.150. ‘(The iodocinnamic acids.” By Thomas Campbell James. Three monoiodocinnamic acids are at present, recorded in the literature, all of which are classed as P-iodocinnamic acids. The author has prepared a fourth isomeride by treating a@-dihydroxy- P-phenylpropionic acid (Fittig and Ruer, Annalen, 1892, 268, 27) with a concentrated solution of hydriodic acid at the ordinary temperature. An examination of the properties of the isomerides indicates that Michael’s B-iodocinnamic acids (Ber., 1901, 34, 3658) are correctly described, whilst that prepared by Ortoleva (Gazzetta, 1899, 29, i, 504) is a-iodocinnamic acid, and the new isomeride is a-iodoallocinnamic acid.151. Bate of evolution of gases from supersaturated solutions. LL Part I. Influence of colloids and of snspenaions of charcoal on the evolution of carbon dioxide.” By Alexander Findlay and George King. The velocity of escape of carbon dioxide from supersaturated solution in water, in solutions of potassium chloride, in colloidal solutions of gelatin, starch, dextrin, ferric hydroxide, peptone, agar, and in aqueous suspensions of platinum and charcoal, has been studied. Measurements were made of the velocity of spontaneous evolution of gas from unagitated solutions, but attention was devoted mainly to the study of evolution from well-agitated soln-tions, a suitable apparatus and method of working having been devised, whereby the very rapid evolution of gas can be accurately 174 measured.Whereas, in the case of pure water and soluticns cf potassium chloride, the velocity of evolution is very nearly propor- tional to the degree of supersaturation, this no longer holds good in the case of colloidal solutions, which also show marked differences among themselves. In carrying out the measurements, the solutions were first saturated with carbon dioxide under a pressure of about 760 mm. above atmospheric; the pressure was then reduced to that of the a.tmosphere, and the gas evolved was measured. On reducing the pressure, a period of quiescence, during which practically no gas was evolved, occurred in the case of most of the solutions, but in the case of ferric hydroxide and of peptone no such quiescent period was obtained, and spontaneous evolution of gas took place immediately the pressure was reduced.152. ‘(Viscosity maxima and their interpretation.” By Ferdinand Bernard Thole, Albert George Mussell, and Albert Ernest Dunstan. In view of the investigations recently published by Denison and by Kurnakov and Schemtschushni on the interpretation of maxima in the viscosity-composit4ion curves of liquid mixtures, the authors have investiga.ted more fully the various types of curves obtained for different liquids, particularly with those pairs of compounds the freezing-point composition curves of which have been determined. The results show that in general liquids which give a mixture of maximum melting point give also a mixture with a maximum viscosity, although in certain cases a sagged curve may be obtained if one of the components has a higher molecular comp1exit.y than the compound formed.The position of the point of maximum viscosity is not dependent entirely on the composition of the complex, although in cases where the two components have a strong mutual chemical affinity the maximum viscosity is found with the mix$ure of simple molecular composition, for example, thiocarbimides-amines and sulphuric acid-water. 153. Condensation of aromatic aldehydes with pyruvic acid.” By Eva Lubrzynska and Ida Smedley. Piperonal, anisaldehyde, and cinnamaldehyde were condensed with pyruvic acid in very dilute alkaline solution; the Pyunsatur-ated a-ketonic acids formed were oxidised with hydrogen peroxide in neutral solution, and the corresponding &-unsaturated acids isolated. 175 154.‘(The isolation and purification of cerebrone.” By Arthur Lapworth. During the last three years the author has frequently had occasion to prepare pure cerebrone from large quantities of brain. He has found it most satisfactory to extract the material, partly dried in spirit, with boiling methyl alcohol, to precipitate most of the phosphatic materials by neutralising the hot liquid with methyl- alcoholic baryta, subsequently decanting the clear, supernatant liquid, and destroying the remaining phosphatides by adding excess of powdered barium oxide and boiling for several hours. The solvent is then mostly removed, and the residue rendered slightly acid with glacial acetic acid in the presence of chloroform, which is subsequently removed by distillation, and the cerebrone, mixed with choIestero1, extracted by methyl alcohol.domplete separation of phosphatides and cholesterol from the cerebrone may be effected in several ways, of which continuous extraction with boiling acetone is the most efficient (compare Lorrain Smith and Mair, J. Path. Bact., 1910, 15,122; 1911, 16,131; Lapworth, ibid., 1911, 16,255 ; Loening and Thierfelder, Zez‘tsch. physiol. Chem., 1912, 77,202). 155. ‘(Cyaphenine.” By John Edwin Xackenzie. The formula generally assigned to cyaphenine is (C,H,-CN), but its molecular weight does not appear hitherto to have been determined directly.In some experiments performed with the object of obtaining benziminohydrin from benzimino-ethyl ether hydrochloride accord- ing to the equation: C,H5*C<t2Hc1+ AgOH = C,H,*C<:E +AgC1+ EtOH, cyaphenine was found among the products of the reaction. A number of determinations of the elevation of the boiling point of solutions of cyaphenine [prepared by Eitner and Krafft’s method (Ber., 1892, 25, 2266) : it was further purified by distillation under diminished pressure. The product melted at 233O (corr.)] in benzene and in carbon tetrachloride showed that in these solutions it possessed no constant molecular weight. The molecular weights obtained in solutions of the concentration stated are plotted on the diagram (9.176). The cryoscopic method was found unsuitable on account of the very small solubility of cyaphenine in the solvents available. The 176 vapour density was then determined, and gave results agreeing with those required for the formula (CGH,-CN),. 400 300 100 1 2 3 4 5 Brains per 100 grams of solmxt. Molecitlcrr-weight Determinations of Cynphenine by the E'bullioscopic Method.* C21€I,.iN3requires M.W. =309. ~Benzene 5Scrics. Ciwbott. Tetmchloride o Series. Solvent : 9.8561. Solvent : 20.377 pains. w. AQ. M. w. W. AQ. mv. 0.1451 0.195 203 8 0.1156 0'1754 155.3 0.2749 0.305 246.8 0'2221 0.2729 191.7 0'4399 0.390 309-0 0-2963 0.2975 234.6 0.53i7 0-430 342.6 Cat-bon Tclrnchloridc x Scrim 9.9.AQ. M.W. 0.0936 0.1688 119.9 0'1746 0-2239 168% 0.28iZ 0 3120 199.1 These results have been plotted in the diagram above, and as will be Eeen, the molecular weight increases steadily with increase of concentration of the solution, The vapour density was determined by V. Meyer's displacement method, the vaporisation taking place at the boiling point of sulphur : w. V. moist air (c.c.). t. P (mm.). 11.w. 0.1816 34.0 18" 753 319-0 0'1928 14-7 17" 753 320.5 C,,H,,N, requires M. W. =309. * The constants for benzene and carbon tetrachloride employed in the calculations were 27 and 48 respectively. 177 It may therefore be concluded that cyaphenine at a temperatare of about 450° has the above formula, but that in chloroform and benzene solutions it undergoes dissociation and association.156. " Note on the identification of proline. By Wilhelm Gluud. Racemic proline is usually identified by its characteristic copper salt, which crystallises from aqueous solution with two molecules of water. In a recent paper Emil Fischer and Gerlach (Ber., 1912, 45, 2453) showed that the copper salt of pyrrolinecarboxylic acid may be confused with the copper salt of proline, and that a complete analysis is necessary to distinguish between the two. In the case of allylglycine, which has the same empirical formula as proline, such a method would be of no value. It was therefore desirable to prepare and examine the copper salt of allylglycine, in case it could be mistaken for that of proline.,Ir-Allylglycine (compare Alpern and Weizmann, T., 191 1, 99, 84) was prepared froin chloroacetamide and allylamine as follows: 8 C.C. of allylamine were mixed with 4 grams of chloro-acetamide, and the mixture cooled in ice until the reaction had moderated. The liquid was left overnight at room temperature, then diluted with 200 C.C. of water, and 30 grams of recrystallised baryta were added. This mixture was heated on a water-bath for three-quarters of an hour, then boiled for fifteen minutes, and evaporated to dryness in a vacuum. The residue was dissolved in 500 C.C. of water, and the baryta precipitated with carbon dioxide. The filtrate was poured into 20 C.C. of 5N-sulphuric acid, and 80 grams of lead oxide (previously purified by boiling with water) were added.The whole mixture was boiled for twenty minutes, then rapidly filtered, and the lead precipitated with hydrogen sulphide. The solution was heated to boiling, then filtered, and the filtrate boiled with precipitated copper oxide for half an hour, rapidly filtered, and the dark blue filtrate concentrated in a vacuum. The copper salt separates in blue crystals shot with violet, in the form of squares or hexagonal plates (2.3 grams), which can be readily recrystallised from water : 0.1165 gave 0.0320 CuO. Clx =21-95. 0.2093 ,, 16.8 C.C. N, at 16O and 768 mm. N=9*48. CloH,,04N2Cu requires Cu =21.79 ;N =9.61 per cent. When dried at 100°/lO-12 mm., over phosphoric acid, there is no change in weight or colour of the salt.The copper salt thus prepared is very similar in appearance to that of proline, but it contains no water of crystallisation, so that estimation of water and 178 copper in a supposed copper salt of proline is sufficient to exclude the presence of allylglycine. On heating the copper salt of a.llylglycine, the same odour is noticed as on heating that of proline, but further experiments are necessary to identify the decomposition products. At the next Ordinary Scientific Meeting to be held on Thursday, June 5th, 1913, at 8.30 pm., when there will be a ballot for the eleciion of Honorary and Foreign Members, the following papers wiil be communicated‘: “The relationship between the absorption spectra and constitution of piperine, nicotine, cocaine, atropine, hyoscyamine, and hyoscine.” By J.J. Dobbie and J. J. FJX. “ Equivalent conductivities of sodium hyponitrite, calcium hypo- nitrite, and hyponitrous acid.” By P. C. RSy, R. De, and N. Dhar. “Double carbonates of the alkaline earth metals and lead with potassium carbonate.” By R. L. Datta and H. Mukherjea. “ The estimation of nitrites by means of thiocarbamide, and the interaction of nitrous acid and thiocarbamide in the presence of acids of different strength.” By M. N. Coade and E. A. Werner. “A case of isomerism in the methylated ferrocyanides.” ByE. G. J. Hartleg. “The constituents of hops.” By F. B. Power, F. Tutin, and H. Rogerson. ‘‘Anomalous rotatory dispersion. A preliminary note on the form of the dispersion-curve.” By T.M. Lowry and T. W. Dickson. “ The nitrogenous constituents of hops.” (Preliminary note.) By A. Chaston Chapman. “Absorption spectra and chemical reactivity. Part 111. Tri-nitrobenzene, trinitroanisole, and picric acid.” By E. C. C. Baly and F. 0. Rice. “Preparation of secondary amines from carboxylic acids. Part 111. Preparation of disecondary amines from dicarbosylic acids.” By H. R. Le Sueur. EREiATUM. PROCEEDINGS,1 9 13. Page 70, line 17 from below, rcad ‘‘0Me‘C H, ‘CH(0Me).CII (0Me)‘C 1-1(OMe) CH(0H ) CH,’OH. ” R. CLAP AND SONS, LTD., BRUNSWICK ST., STAUIE’ORD ST., S.E., AND BUNOAP, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9132900167
出版商:RSC
年代:1913
数据来源: RSC
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