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Proceedings of the Chemical Society, Vol. 18, No. 255 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 255,
1902,
Page 179-206
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摘要:
Issued 14111/02 PROCEEDINGS CHEMICAL SOCIETY. EDITED BY THE SECREPARIEX. Vol. 18. No. 255. The following are abstracts of papers received during the vacation, and published or passed for publication, in the Transuctions : 127. cL On the solvent properties of mixed liquids in relation to the chemical characters and solvent properties of their com-ponents.” By H. M.Dawson. The solvent power of mixtures of liquids in its relationship to that of the components has been investigated under conditions such that complicating secondary effects of electrolytic dissociation, high con-centration of the solutions, and interaction of the component liquids are avoided. Measurements of the solubility of iodine were obtained by deter- mining the ratio of distribution between water as standard substance on the one hand, and mixtures of organic solvents on the other.A method of determining this partition ratio is described in which an aqueous solution of potassium iodide is employed instead of pure water. If $he iodine concentration in the aqueous solution remains the same in all experiments, the conditions of experimentation cor-respond almost exactly with the determination of the solubility of a gas in different liquids, the pressure of the gas being kept constant. The organic solvents chosen were such as would not be expected to have any action on each other, or on the dissolved iodine. In 180 these circumstances, it is found that in the majority of cases the solvent power of the mixture is less than the sum of the solvent powers of the components; sometimes, however, it is equal to, or greater than, the sum of the solvent powers of the components.No case of a maximum or minimum solvent power, such as that observed with alcohol-water mixtures in regard to hydrogen, oxygen, carbon monoxide, and carbon dioxide has been found. 128, ‘‘Notes on luteolin and apigenin.” By A. G.Perkin. Kiliani and Mayer (Bar., 1901, 34,357’7) have recently asserted that the author’s tetrabenzoyl-luteolin (Trans.,1896, 69,209) is in reality a tribenzoyl derivative. A re-examination of the original preparation shows that the statement of Kiliani and Mayer is in-correct, and that the substance is without doubt tetrabenzoyl-luteolin. Further experiments with reference to the tinctorial properties of apigenin alsd chrysin confirm the previous results of the author (Trans., 1897, 71, 806).129. “Note on a simple form of Landsberger’s apparatus.” ByE. B. Ludlam. A description is given of an apparatus which has proved most satis- factory to work with. The tube in which the rise of temperature is measured is graduated and placed in the neck of the flask containing the boiling solvent,, the vapour of which enters it from below by means of a simple valve which serves the double purpose of regulating and breaking up the stream of vapour, and also of preventing the solution from running back into an intermediate tube, placed between the in- cretometer and the flask, when the latter is cooled.The graduated tube is also provided with an annular trough which serves as a trap and catches the liquid condensed in the upper part of the tube, conveying it to the condenser, thus making the increase of volume in the tube much slower than it otherwise would be. 130. (( The action of substituting agents on benzeneazo-P-naphthol.” By J. T. Hewitt and S. J. M.Auld. Bromine added to benzeneazo-P-naphthol suspended in glacial acetic acid furnishes p-bromobenzeneazo-/3-naphthol, a result also obtained by Margary (Gazxetta, 1883, 13,438), who assigned to the substance the melting point 160-161°, but which the authors, like Bamberger, find to be 172-173O. In presence of sodium acetate, such a high tempera- ture is necessary before the bromine will attack the azo-compound that 181 the results obtained lead to no definite conclusion as to the structure of benzeneazo-P-naphthol, Nitric acid in presence of concentrated sulphuric acid nitrates the nzonaphthol in the benzene nucleus (para-position), dilute nitric acid attacks benzeneazo-/3-naphthol on warming, giving 1 : 6-dinitro-/I-naphthol as the chief product, and p-nitrobenzeneazo-P-naphtholin smaller amount.With strong acids, benzeneazo-@naphthol behaves as a quinone-hydrazone ;with dilute acids (nitric) or weak acids (acetic) its reactions are more those of an azonaphthol. 131. The condensation of dimethylaminobenzaldehyde with p-naphthol. By J. T. Hewitt, A. J. Turner, B.Sc., and S. W. Bradley. When hydrochloric acid is added to a solution of dimethylamino-benzaldehyde and P-naphthol in cold glacial acetic acid, crystals of the composition HCI,(CH,),N*C,H,*CH(C,,H,OH), are deposited ; these darken at about 150’ and melt at 215’ with decomposition.If, however, a mineral acid be added to a hot glacial acetic acid solution of the aldehyde and P-naphthol, a salt of the corresponding anhydride is produced. Attempts at oxidation were without result ;even bromine does not yield an oxonium salt, but gives the bromide of a bromo-substitution product, C,,H,,BrON,HBr (m. p. 196O, uricorr.). 132. 6L The action of ethyl chlorofumarate on monoalkylmalonic esters.” By S. Ruhemann. The author finds that,, in the presence of sodium ethoxide, ethyl chlorofumarate reacts with the mono-alkyl derivatives of ethyl malon- ate to yield homologues of ethyl carboxyaconitate according to the equation : R*CNa(CO,Et), + CO,Et*CCl:CH*CO,Et = ROC(CO,E t),*C(C0,E t):CH C0,Et + NaCI.The quantity of the unsaturated ester which is produced is small, and decreases as the radicle in the substituted malonic ester increases, Of several homologues prepared, the author has studied especially ethyl phenylcarboxyaconitate, C,H,*C(C02Et),*C(C0,Et):CH*C0,Et, and finds that., on hydrolysis, it loses two molecules of water, and yields a compound, C,,H,03, which is the anhydride of a dicarboxylic acid. This anhydride is not an unsaturated compound, but a deriva-tive of trimethylene having the formula C,H$Y---CO >o.On re-H,C CH CO 182 duction with sodium amalgam, this compound yields s-phenylmethyl- succinic acid, C,H,*CH(C0,H)*CH(CH3)*C02H(m. p. 193"), which is identical with the acid described by Zelinsky and Buchstab (Bev., 1891, 24, 1876). 133,(( Di-sec.-octyl tartrate and di-sec.-octgl dibenzogl tartrate." By J. McCrae. Di-sec.-octyl tartrate was prepared from ethyl octyl tartrate and octyl alcohol by the hydrochloric acid method. It is an oil which boils at 225" (20 mm.) and has [a]y=7.06O. The dibenzoyl deriva- tive was prepared by acting on the ester with excess of benzoyl chloride and was purified by precipitation wjth water from an alcoholic solution. It is an oil with [a]r= -43.94". The rotations of these two compounds are compared with those of other tartaric esters. 134, Qlgcogen from yeast." By A.Harden and W.J.Young.k( The glycogen of yeast was extracted by grinding the yeast with sand, pouring the mass into boiling water, and purifying the glycogen by a combination of the methods of Clautriau and Pfliiger. Expressed yeast juice was employed. The glycogen, free from ash and nitrogen, was compared with glycogen extracted by Pfluger's method from rabbit liver and from oysters. All three samples, dried at 100" in a vacuum over phosphorus pent- oxide, were found to have the composition C,H,,O, and not 6C,H,00,+H,0. Glycogen dried at. 100" in air always retained a certain amount of water. The specific rotations were found to be, rabbit glycogen [a]? = +191.1" ;oyster glycogen [a!:" = +191.2" ; yeast glycogen = +198*3".In view of the low concentrations of the solutions rendered necessary by their opalescence, this difference cannot be considered as characteristic. The glycogen from yeast appears to be identical with animal gly- cogen in composition and optical activity, Slight differences appear to exist in its behaviour towards dilute acids, in the reaction with iodine, and in the opalescence of the aqueous solutions, but these are also exhibited by glycogens derived from various animal sources. 183 135. “The action of acetylene on the acetates of mercury.” By E. Burkard, Ph.D., and M. W. Travers, D.Sc. The authors have investigated the compounds produced by the action of acetylene on mercurous and mercuric acetates respectively, which were briefly described by the late Dr.R. T. Plimpton (Proc., 1892, 8,109). The mercimous compound, which is explosive, has the formula C,€Ig,,H,O, and resembles the already well-known acetylides of silver, copper, and mercury. The mercuric compound appears to be a definite basic acetylide of the formula 3G2Hg,2HgO,2H,O or 3C2Hg,2Hg(0II),; it is non-explosive. Both compounds yield acetylene when treated with acids, and a mixture of di-iodoacetylene and tetraiodoethylene when treated with iodine. Hence it appears that the oxygen and hydrogen in the com- pounds are connected with the mercury rather than with the carbon. 136. d6 The decomposition of water vapour by the electric spark.” By D.L. Chapman and F. A.Lidbury. The experiments described show that when electric sparks are passed through water vapour the decomposition which takes place is consider- able. The products of decomposition are partly separated from one another and take up different positions in the tube. The separation which occurs cannot be entirely accounted for by electrolysis for the following reasons : (1) Hydrogen collects at both electrodes and oxygen in the middle of the spark gap. (2) The hydrogen which collects at the cathode is very largely in excess of that required by Faraday’s law. 137. 6i The chlorination of the dichlorotoluenes in presence of the aluminium-mercury couple. The constitution of the trichloro- toluenes.” By J.B. Cohen and H.D. Dakin. The six dichlorotoluenes were chlorinated, using the aluminium- mercury couple as carrier. In order to identify the products formed: the six trichlorotoluenes were prepared synthetically, together with their nitro- and dinitro-derivatives and the trichlorobenzoic acids which they yield on oxidation. The results shorn that the six dichloro- toluenes, on chlorination, give five out of the six possible trichloro- toluenes. 184 138. The constitution of the nitro- and dinitro-derivatives of the dichlorotoluenes.” By J. B. Cohen and I€,D. Dakin. The authors have determined the constitution of the nitro- and dinitro-derivatives of the six dichlorotoluenes which they had pre- viously prepared (Trans., 1901, 79, 1111).They find that in the case of the mono-substitution derivatives, the chlorine atoms possess a greater influence than the methyl group in determining the position of the entering nitro-group, whilst in the case of the dinitro-compounds the position of the first entering nitro-group appears to be of primary importance in determining the position to be occupied by the second nitro-group, for in all the six dichlorodinitrotoluenes the nitro-groups are in the meta-position to one another. 139. (( Iodonium compounds of the type IRR”R’, and the configura-tion of the iodine atom.” By H. Peters. Further investigation of the phenyl-p-tolyliodonium bromocam-phorsnlphonate described in a previous note (Proc., 1900, 16,62) has confirmed the conclusion that it cannot be resolved into salts of enantiomorphously related bases, from which the inference may be drawn that the three iodine vitlencies are situated in one plane, two of them being symmetrically situated with respect to the third.In the preparation of phenyl-p-tolyliodonium iodide from iodoso-p-toluene and iodoxybenzene, small quantities of di-p-tolyliodonium iodide are formed owing to secondary reactions ;similarly, the crude phenyl-p-tolyliodonium iodide, prepared from iodosobenzene and iodoxy-p-toluene, contains small quantities of diphenyliodonium iodide. The formation of these subsidiary products is not due to extramolecular change of the radicles of the phenyl-p-tolyl salt, and it is shown that the latter is really the salt of a mixed iodonium base.PiLenyl-p-tolyliodonium finitrate, Ph(C,H, Me)I*NO,, cry stallises in prisms melting at 117”. The cldos*ide, Ph(C,H,*Me)I*Cl, crystallises in needles and melts at about 193’. Bi-p-tolyliodonium iodide, (C,IT4Me),I*I, forms well-defined, outa-hedral crystals and decomposes at 143-153’. Di-p-tolyliodoniunt bromoccLsrL~~~o~sul~?~on~te,(CGB,~e),I*CloH,,BrO,S, crystallises in needles melting at 185-186O; it is sometimes obtained in hydrated dodecahedra, very like the crystals of the corresponding salt of the mixed base. Dipheny%odonium 61.omocccmp?iorsul~?ionate,(C6H,),I*CloH1,Br0,S, forms hydrated dodecahedra, the anhydrous salt melting at 165-168’. 185 140. ‘‘Influence of substitution on the formation of diazoamines and aminoazo-compounds.Part 11.” By 43. T. Illlorgan, D.Sc. Mixed diazoamines containing a naphthalene nucleus are readily obtained from the diazotised 0-and m-nitranilines and 1-chloro-P-naphthylamine. The properties and reactions of several are described in detail in the paper. 141. “Observations on the phenomena and products of the decom- position of normal cupric acetate when heated.” By A. Angel and A. V. Harcourt. The authors give a summary of the numerous researches on this subject. One phenomenon which had not been noted previously is bhe formation of a bright coating of copper in the test-tube in which the salt [Cu(C,H302),,H,0] is heated. As this salt does not fuse this must be due to a gaseous compound of copper, proved by the authors to be cuprous acetate, which volatilises at about 200’ and forms, especially when sublimed in hydrogen, feathery, white crystals.The salt was heated generally in a tube in an oil-bath, and kept nearly vacuous by a Sprengel pump and the gases collected. These were found to consist wholly of the oxides of carbon in approximately the ratio 4C0, :CO. The liquid products consisted of water and acetic acid with a trace of acetone. The fixed residue is of a paler or deeper red-brown colour, and consists of metallic copper mixed with a bulky black substance the composition of which may be represented by the formula C,,H,O,. 142. (‘The resolution of P-hydroxybutyric acid into its optically active components.” By A.McKenzie. In a preliminary note (Proc., 1901, 17,213), the author mentioned that he had obtained I-P-hydroxybutyric acid from the inactive acid by aid of the quinine salt. The d-acid has since been isolated by means of the strychnine salt the solvent being ethyl acetate. It was found that for it [.IT=+24.3‘ (C =2.226). Change of concentration has little influence on the value for the specific rotation of the acid (Magnus-Levy) and the salts are active in the same sign as $hat of the acid but to a less degree. In these respects, P-hydroxybutyric acid differs from most other aliphatic oxp-acids. When the Z-acid is heated at looo, it is partly converted into an anhydride. 186 When the inactive potassium and sodium salts were respectively injected subcutaneously into dogs, the author found from examination of the urine (1) that acetoacetic acid and acetone were present, (2) that a small portion of the P-hydroxybutyrates mas unattacked, and (3) that this product was laevorotatory.Partial resolution of the acid was also obtained by esterification with I-menthol and I-borneol. 143. “The rate of decomposition of diazo-compounds. Part I. Diazo-compounds of the benzene series,” By J. C. Cain and F. Nicoll, The decomposition of an aqueous solution of a diazo-salt is in most cases a simple monomolecular one, conforming to the expression The authors have measured the rate of decomposition of diazo-salts from various bases and find that at temperatures between 20’ and 60” the diazo-salts from aniline and the toluidines conform to the above law, thus confirming some results of Hantzsch at 25” (Rer., 1900, 33, 2517), but being quite opposed to the work of Hausser and Dluller at 40’ and 64O (Bull.Soc. chim., 1892, [iii], 7, 721 ; 1893, 9,353). The authors maintain that the assumption by the latter chemists of a specific I‘retarding action ” of the pheool formed cannot be upheld. A table of constants of the diazo-salts from eight amines shows the very great stability of the diazo-salts from substances containing au acid group (NO, or S03H), The diazo-salt from p-amidoacetanilide follows the law only in acetic acid solution, as in presence of mineral acid the acetyl group is saponified. Of the tetrazo-salts of the diamines, only that from dichlorobenzidine follows the law.The others give in the case of the tetrazo-salts from benzidine and tolidine diminishing, and in the case of that from dianisidine, increasing, values for C, pointing to the probability of the formation of an intermediate substance containing still a diazo-group. 144. “Studies upon the action of sodamide and acetyl substituted sodamides upon organic esters.” By A, W. Titherley, D.Sc.,Ph.D. Sodamide appears to form addition compounds containing the group- ,OR ing -C-NH, when allowed to act on esters in benzene solution if \ONa the temperature is kept low. On warming, further action at once 187 takes place, which varies according to the nature of the ester.With esters of benzoic and other purely aromatic acids, an alcohol splits off and a substituted sodamide results. With esters of fatty and phenyl aliphatic acids, the final result of the reaction is a condensation effected on very similar lines to those brought about by sodium ethoxide, and probably by a similar mechanism. Phenyl benzoate behaves quite differently from the ethyl ester in giving sodium dibenxamide and phenoxide, and the reaction proceeds with great readiness. Ethyl oxalate gives an intermediate product which with water yields sodium oxamate. The action of sodamide with ketones is very different in the ali- phatic series when condensations are brought about from that in the pure aromatic, where there is no action. Acetone with sodamide gives, in presence of benzene after a vigorous reaction, a jelly consisting essentially of the sodium derivatives of the enolic forms of mesityl oxide, phorone, and isophorone.The interaction of acyl-substituted sodamides and esters depends largely on the nature of both these substances, which, if aliphatic, induce various complex changes. In the pure aromatic series, a simple definite change occurs which conforms approximately to the reversible system, R*CO*NHNa + R*CO,R < (R*CO),N*Na + R*OH, but in all probability the mechanism of the reverse reaction is more complex. The reaction is capable of modification in numerous ways, and the acyl-substituted sodamide may be prepared from the amide and alcoholic sodium ethoxide, or (best) from sodarnide.A very good yield of dibenzamide is obtainable from sodium benzamide and ethyl benzoate. Thursday, November 6th, 1902. Professor MCLEOD, F.R.S., Vice-President, in the Chair. The CHAIRMANreferred to the great loss which the Society had BUS-tained since its last meeting by the deaths of Sir Frederick Abel and Dr. J. H. Gladstone, two of its Past Presidents, who had been for more than fifty years Fellows of the Society, Messrs. Garle, Hann, Pollitt, Gill, Moore, and Parkes were formally admitted Fellows of the Society, 188 Certificates were read for the first time in favour of Messrs. : John Frederick Alder, 13, Priestmood Mansions, Highgate, N. Alfred Edward Beanes, Moatlands, Paddock Wood. Herbert Blair, No.3, General Hospital, Kroonstad. John A. H.Brincker, B.A.,M.B.,7, St.Mary’s Terrace, Paddington,W. Vernon Seymour Bryant, B.A., Camborne, Cornwall. Thomas Burnell Carmichael, Parton, Whitehaven. Charles Cockle, Peter Symonds School, Winchester. James Justinian Drought, Johannesberg. Walter Henry Ed wards, The Grammar School, Wellingborough. Wilfrid Russell Grimwade, B.Sc., Melbourne. Edward Gumersall, Atbara, Sidcup. David V. Hollingworth, Aldred House, Crescent, Salford. Alfred Holt, jun., B.A., Crofton, Aigburth, Liverpool. Clements F. V. Jackson, A.Inst.C.E,, Brisbane. John Petty Leather, 17, Carlton Road, Burnley. Frank A. Lidbury, M.Sc., Owens College, Manchester. Ernest Liotard, 2, Rue de France, Nice. Thomas Stratford Logan, 52, Kirkgate, Leeds.Douglas A, RlacCallum, Shawlands, Glasgom. William Mann, B.Sc., Fonnereau Villa, Dartford. John Marsh, 29, High Street, M,aidstone. Joseph William Mellor, D.Sc., Owens College, Manchester. John Price Millington, B.A., Christ’s College, Cambridge. John Phelps, B.A., Trinity College, Oxford. George A. P. Ross, M.B., B.Ch., 20, Westhall Gardens, Edinburgh. John William S’ampson, Helpringham, Heckington. Duncan Simpson, 10, Brynmill Crescent, Swansea. Robert Walter Sindall, 80, Manor Road, Hrockley, S.E. John Seabury Smythe, B.Sc., Ph.D., 143, Smithdown Lane, Liverpool. Walter F. Sutherst, Ph.D., Agricultural College, Holmes Chapel. George Sutnerland Thomson, Government Offices, Adelaide. Henry Letheby Tidy, B.A., New College, Oxford. William Carter White, 113, Gower Street, W.C.Lyndon Wilson, 66, Castle Gate, Newark-on-Trent. Of the following papers, those marked * were read : *145. I‘ The specific heats of gases.” By H.Crompton. It was shown that the molecular heat of any gas at the absolute temperature T may be calculated with the help of a formula of the type A +BT. In this formula A has the same value for all gases and depends on changes in the movements of the molecules of the gas as 189 a whole. B is proportional to Yx logrt, where Vis the volume of the molecule and n is the number of atoms in the molecule. BT depends on interatomic changes taking place within the molecule. If €or V the molecular volume at the normal boiling point of the liquid Mvb is taken, the molecular heat at constant pressure Cp-4.935 + 0~000215Mu~Tlogra(or if common logarithms are used the coefiicient is 0*000564).The molecular heats calculated from this formula are shown to be in fair agreement with those observed. The ratio rE bf the two specific heats can also be calculated with the aid of this formula. DISCUSSION. Dr. TRAVERSremarked that it would be interesting to know how closely the formula would reproduce the values of the specific heats of the commoner gases, which had been determined with great accuracy and over a considerable range of temperature by Regnault, Witkowski, and others. The agreement between the observed and calculated values in the cases cited by the author was, however, remarkable.Dr. PHILIPpointed out that the values of Cp given by the two formuls (Le Chatelier’s and that of the author) would, owing to the difference in the numerical constants chosen, be more divergent the lower the temperature. On this account, a study of the applicability of the proposed formula at low tsmperatures would be specially interesting. Mr. CBOMPTON,in reply, admitted that at low temperatures the results given by the formula did not agree with the observed so well as those obtained at higher temperatures. In explanation of this, he pointed out that the formula was only supposed to hold for an ideal gas, no account being taken of the effect on the specific heat of possible attractions between the molecules.If such attractions existed, they would have a greater influence on the specific heat at low tempera- tures, and this the nearer the gas was to its point of liquefaction, than under ordinary conditions, No doubt a term should be introduced to allow for the effect of molecular attractions, but at present he was unable to make any suggestion with reference to the character of this correction. *14& ‘( The action of nitric acid on bromophenolic compounds.’’ By W. Robertson. The action of nitric acid on bromophenols and their derivatives was studied in order to determine the conditions under which the bromine atom is replaceable by nitroxyl. It has been found that if the hydrogen of the hydroxyl group be replaced by either the methyl or 190 acetyl radicle, no displacement of bromine by the nitro-group occurs when these substances are acted on by nitric acid under similar con- ditions, The bromohydroxybenzoic acids and their methoxy- and acetoxy-derivatives were also prepared, and it was found that with regard to them the same rule applied.The following compounds were described : 2 :6-dibromo-4-acetyl aminophenol, needles, m. p. 185-186' (Holz, J.pr. Chem., 1886, [ii], 32, 68, gives 173-174O; Friedlander and Stange, Ber., 1893, 26, 2262, 185") ; 2-nitro-6-bromo-4-acetylaminopheno2,yellow needles melt- ing at 230' ;2-nitro-6-bromo-4-benxoylaminopheno1,yellow needles, m.p. 247' ; 2 :3 :6-tribromo-4-acetykaminop?~enol,white needles, m. p. 224' with decomposition ;2 :6-dibromo-4-anisidine, white, glistening leaflets, rn. p.66" (Stadel, Annalen, 1883, 217,70, does not give melting point), and its acetyl and benzoyl derivatives which crystallise in needles melt- ing at 206" and 180' respectively ; acetyl-3 :5-dibromosalicylic acid, m. p. 156' ;acetyl-5-bromosalicylic mid, m. p. 16So;acetyl-3 ;5-dibvomo-p-oxybenxoic acid, m. p. 207' ; ethyl ester of 3 :5-dibronoo-p-oxybenxoic acid, needles, m. p. 99" ;acetyl-3-6~omo-p-oxybenxoicacid, m.p. 155" ; a dibromo-m-oxybenxoic acid, m. p. 202'; 2-bromo-4 :6-dinitro-3-oxybenxoic acid, a yellow substance, m. p. 217-218'. Drscussro~. Mr. W. A. DAVISpointed out that although Mr. Robertson had been unable to isolate intermediate products of nitration in the case of the brorno-phenols he had dealt with, such substances had been obtained by Armstrong and Rossiter in the form of nitrobromo-keto-naphthalenes (Proc., 1891, 7, 89).He himself had for several years been working with this class of compounds and had found that their stability depends largely on the proportion of bromine which they contain. Thus, whilst the nitro-keto-compound of ,@naphthol is so unstable that it cannot be isolated, and the keto-derivatives of bromo-, dibromo-, and tribromo-/%naphthol are stable only at low temperatures, those formed from the tefrabromo- and pentabromo-naphthols can usually be kept for several days in the dry state without under- going change. Moreover, whilst the lower brominated keto-compounds are readily reduced to the corresponding bromonitro-naphthols by sodium sulphite, those derived from the tetrabromo-P-naphthoIs are reducible only by concentrated hydriodic acid."147. 3 :5-Dichloro-0-sylene and 3 :5-dichloro-o-phthalio acid." By A.W.Crossley and H.R.Le Sueur. The high boiling fraction of the liquid obtained by the action of phosphorus pentachloride on dimethyldihydroresorcin, consists of 191 3 :5-dichZoro-o-xyZene, C,(CH,),H,CI,, which may also be produced by the prolonged heating of dichlorodimethyldihydrobenzenewith phos- phorus pentachloride. It is a faintly yellow, highly refractive liquid, which boils at 129' (23 mm.) or at 226' (atmospheric pressure), and ou cooling solidifies to a mass of flaky needles melting at 3-4'. On oxidation withnitric acid, it is convertedinto 3 :5-dichloro-o-phthalic acid, C,H,Cl,( CO,H),, which crystallises in hair-like needles melting at 164' with previous contraction and sublimation.The anhydride (m. p. 89') and several other derivatives have been prepared. "148. ('The combination of carbon monoxide with chlorine under the influence of light." By G. Dyson and A. Harden. Following the method previously described (Proc., 1894, 10, 165), the authors have found : (1) That when a mixture of carbon monoxide and chlorine, dried by being passed through sulphuric acid, is exposed to light, a well- marked period of photochemical induction occurs. (2) The induction lapses slowly when the exposed gns is placed in the dark. (3) The sensitiveness of this mixture to light is greatly diminished by admixture of air, but is not much affected by the presence of carbonyl chloride, hydrogen chloride, excess of carbon monoxide, vapour of carbon tetrachloride, and small amounts of water vapour.DISCUSSION. Professor TILDENsaid one point which Dr. Harden had omitted to mention was the extent to which the gases had been deprived of moisture. He would be glad to hear by what method they had been dried, and whether the authors had observed that the composition of the glass or the condition of the surface in contact with the gases produced any influence on the rate of their combinatioc. Dr. HARDENreplied that the gases were dried by being bubbled through strong sulphuric acid.They had not made any experiments specially with reference to the composition of the glass or the con- dition of its surface, I'"149. The constituents of commerciai chrysarobin." ByH.A. D.Jowett, D.Sc., and C. E. Potter, B.Sc. Araroba, or Goa powder, and commercial chrysarobin, the substance obtained from the former by extraction with solvents as chloroform, have been investigated by Attfield, by Liebermann and Seidler, and by Hesse with varying results. The latter chemist found that crude chrysarobin contained no chrysophanic acid, but was a mixture of two parts of chrysarobin, U,,H,,O,, and one of its methyl ether. He regarded chrysarobin as the anthranole of chrysophanic acid. The authors have examined commercial chrysarobin and find that it con- tains the following substances, but no chrysophanic acid.Chrysarobin, Cj15H1203,is the anthranole of chrysophanic acid and identical with chrysophanohydroanthroneobtained by the reduction of chrysophanic acid. It melts at 204'. When acetylated with acetic anhydride alone, a mixture of diacetylchrysarobin (m. p. 193') and triacetylchrysarobin (m. p. 238O) is obtained, but if sodium acetate and acetic anhydride are used, the triacetyl compound is alone pro- duced. Methyl etheqq of dichrysarobin, C,,H,,07, melts at 160'. It yields a soluble pentacetyl compound, m. p. 135" identical with Hesse's hex- acetyldichrysarobin. Dichrysaro6in, C,,H,,07, does not melt below 250°, but blackens and chars gradually. On acetylation, hexacetyldichrysarobin (m. p.179-181') is obtained. The formula assigned to this constituent is proved by analysis. A substance, Cl7HI4O4,m,p, 18l0,which yields an acetyl compound, m. p. 215-216'. The two latter substances are contained in crude chrysarobin in only small amount, the greater portion consisting of the two first-named substances. Methylchrysarobin was not found to be a con-stituent of crude chrysarobin. Both chrysarobin and dichrysarobin yield chrysophanic acid on oxidation, and P-methylanthracene by dis- tillation with zinc dust. Crude chrysophanic acid as obtained from rhubarb contains pure chrysophanic acid, m. p. 190' (acetyl compound, m. p. 206'), and the methyl ether of dichrysarobin, and not the methyl ether of chryso- phanic acid as previously stated by Hesse."150. '' The constituents of an essential oil of rue." By F. B. Power and F. H,Lees. In order to prepare some methyl nonylketone, the authors obtained a quantity of oil of rue labelled 01. Rutae., Ang., from an English distiller and found subsequently, on inquiry, that it was not distilled from the native-grown herb. From their results, taken in con-junction with those of Thorns (Bw. deut. pharm. Ges., 1901, 10, 3) and von Soden and Hexle (Pharm. Zeit.,1901, 46,277 and 1026), the authors regard it as most probably of Algerian origin. The oil was lighb brown in colour. d 15*5°/160=0*8405,uD= -3'48' for a 100 mm. tube. It was completely soluble in two parts 193 of 70 per cent.alcohol. The following constituents were identified : (1) methyl n-heptylketone, b. p. 194.5-195*5' at 763 mm., d 14'/16'= 0.8296 (semicarbazone, m. p. 119-120') ; (2) methyl n-nonylketone, b. p. 231*5-232*5', d 20*5'/16' =0.8263 (semicarbazone, m. p. 122') ; (3) methyl n-heptylcarbinol, b. p. 198-200°, d 19'/16' =0.8273, uD= -3'44' in a 50 mm. tube; acetate, b. p. 213-215', aD= -3'3' in a 50 mm. tube (oxidation ofd 20~5°/160=0~8605, alcohol to the corresponding ketone, b. p. 195-199', semicarbazone, m. p 118-119'); (4) methyl n-nonylcarbinol, b. p. 231-2333 uD= -1'18' in a 25 mm. tube (oxidation to corresponding ketone, oxime, m. p. 46-47'>; (5) a blue oil of high but not constant boiling point ; (6) acetic acid ; (7) a basic substance having the odour of quinoline ; (8) a mixture of free fatty acids; (9) methyl salicylate ; (10) an ester of valerianic acid, apparently ethyl valerianate; (11) pinene (nitrosochloride, nitrolpiperidide, m.p. 119-120') ; (12) I-limonene (tetrabromide, m. p. 103') ; (13) cineol (compound with tetraiodopyrrol, m. p. 114-1 15', and hydrobromide, m. p. 55-56'), The relative proportions in which the above-mentioned substances were found to exist in the oil are approximately as follows : the two ketones constitute 80 per cent., and were present in about equal amounts. The two alcohols represent about 10 per cent., the methyl n-heptylcarbinol preponderating ; they were present partly in the free state and partly as acetic esters. The terpenes, together with cineol, amount to about 1 per cent., and the blue oil to about 0.5 per cent.From the non-ketonic portion of the oil, a small amount of an undistillable, viscous substance, probably a decomposition product, was separated. Since the substances associated with the ketones and alcohols are present in such small amount, and the limonene is the more rarely occurring I-form, the authors conclude that all these substances are natural constituents of the oil. "151. ('Methyl P-methylhexyl ketone." By F. E.Lees. Ethyl sec.-hexylacetoocetate, CH,*CO*CH(C,H,,)*CO,Et, was prepared by the condensation in alcohol at 100' of ethyl sodioacetoacetate with sec.-hexyl iodide; it is a colourless oil which boils at 130-132" (17 mm.), and at 243-245' under atmospheric pressure, Methyl P-methylhexyl ketone, CH,*CO*CH,-CH(CH,)*(CH2)3*CH,, was prepared by the hydrolysis of ethyl sec.-hexylacetoacetate with 30 per cent.aqueous potassium hydroxide. It is a colourless oil with a pleasant, fruity odour, boiling at 184' (769 mm.), and having the density d 15'/16'= 0-8319. Its semicarboaone forms needles and melts at 75' ;its oxime is a colourless oil. 194 152. u Di-indigotin.” By J. Moir, M.A., D.Sc. The author’s object in the following experiments was to prepare the diphenyl analogue of indigotin, in order to ascertain what influence the doubling of the molecule would have on the colour, since this exercises a marked influence in the case of the benzidine dyes as com- pared with ordinary azo-dyes derived from aniline.Although success- ful in preparing the new substance, the yield was so poor and its properties so troublesome to investigate that only a meagre description of it is possible. The method consisted in applying the synthesis of indigo employed by F. Baeyer & Co. to benzidinedicarboxylic acid instead of to anthr- anilic acid. 4 :4’-Benzidine-3 :3’-dicarboxylic acid was prepared from o-nitro-benzoic acid by reduction with sodium hydroxide and aluminium powder until the solution, which was at first dark red, became paler by the conversion of azo- to hydrazo-acid ;it was then precipitated with excess of acetic acid, and the hydrazo-acid thus obtained boiled with strong hydrochIoric acid to convert it into the benzidine derivative, which was obtained on dilution as an almost insoluble powder, coloured pale green by some oxidation product which could not be removed.It was dissolved in the smallest possible quantity of potassium carbonate solution and mixed with excess of neutral potassium monochloracetate solution. On boiling the mixture for some hours, a small quantity of a crystalline precipitate was obtained, which was filtered off and dried. It melted above 300° and is probably bisphenylglycine-o-carboxylic acid. HO,C C0,H I I This was boiled during 4 hours with excess of acetic anhydride and dry potassium acetate, and finally taken to dryness on the water-bath. This process closes the indoxyl ring. The product freed from in- organic substances by washing, on digestion with dilute sodium hydroxide, dissolved, the solution becoming green, whilst a pellicle of the di-indigotin formed on the surface.Air was passed into the diluted solution and the olive-green substance was filtered off, washed, and dried, The filtrate was also dark green and gave on acidify-ing a dark green carboxylic acid, which probably results from the formation of the indoxyl ring at one end only of the first substance, The properties of the di-indigotin precluded any exact investigation. It is only very slightly soluble in boiling p-toluidine, giving a solution distinctly bluer than the original substance as first prepared in fine 195 suspension. It gives an olive-green solution in concentrated sulphuric acid, but is apparently not sulphonated at looo.It was not analysed, because it was impossible to guarantee its uniformity, but its stability precludes the possibility that it is merely a substituted indigotin. The following scheme probably represents its formation : <->-NO2 -3-/-\-N*.NH /-\ + -L[/ -\-/ 602H C02H H0,d NH2-/-\ /--\-NH2 71-+ \,J-\-/ + FH2 -+ H02C C02H C02K CH,*COI I Y Di-acetyl-di-indoxyl. + I i "Di-indigotin.'; 11 c-co co-c An attempt to confirm this by obtaining the same substance by another synthesis was made. All the methods involving potash fusion failed, but the method of Blank (Ber., 1898, 31,1816) was partially successful and is here given as involving the preparation of a new sub- stance.Benzidine was heated with a solution of half its weight of di-ethyl bromomalonate in ahloroform until the odour of the former had gone ;the product was boiled out with chloroform and benzene and the filtered extracts concentrated and cautiously treated with ligroin, when the new ester crystallised out in plates. After two recrystallisations from ethyl acetate, it was white and melted sharply at 138". An analysis showed it to be the expected ethyl benxidino-dimalmate, ./-\-N 12 196 0.1564 gave 0.3542 CO, and 0.0918 H,O. C=61.73; H=6.52. 0.2562 ,, 12.80 C.C. moist nitrogen at 21Oand 759 mm. N =5.69. C,,H,,O,N, requires C =62.40 ;H =6-40;N =5.60 per cent. It forms minute, lustrous plates, sparingly soluble in alcohol and in cold benzene, easily so in hot benzene, ethyl acetate, and chloroform.It is slowly hydrolysed by alkalis, the solution giving, with acids, a flocculent precipitate of the corresponding acid. On the analogy of Blank’s indigo synthesis from ethyl anilinomalon- ate, the new ester was heated to 200’ in an oil-bath until the evolu- tion of vapour ceased. The product was dissolved in a little acetone, filtered, and precipitated by alcohol, giving a dark gum (whilst the alcoholic solution gave a little of the unchanged substance in needles, identified by mixed melting point). On boiling the gum with alcohol, a red resin was left, and the alcoholic solution was concentrated and hydrolysed by sodium hydroxide, giving a deep green solution, but no other evidence of the presence of di-indigotin in solid form.Evi-dently the action of heat on ethyl benzidinodimalonate is not analogous to its action on ethyl anilinomalonate, for many other tem- peratures than 200’ were tried, but witqh even less success, The author has prepared another new substance by boiling benzidine dicarboxylic acid with dry chlorac?tic acid and dry potassium chlor- acetate: carbon dioxide was split off, but the product was acetylated as in the former synthesis. A crystalline carboxylic acid (lance-shaped, white crystals, m. p. 292’) was isolated and recrystallised from boiling ethyl acetate. Analysis showed C =64.94 ; H =4.85 ;N =7.91 hence the formula C,,H,,O,N,, and probably the constitution /-LA CO*CH, CH,.C()*NH-/’T )CH*CO,H CO 153. “Note on the localisation of phosphates in the sugar cane.” By C.H. G. Sprankling. As very little work has been done with regard to the position of mineral constituents in plants, the author selected the sugar cane as a convenient plant to ascertain the position of the phosphates therein. Equal portions of three sound canes were thoroughly dried, and after being ground to a fine powder, weighed quantities were ignited, using a slight modification of Fluckiger’s method (Zeit. and. Chem., 1889, 27, 637). The ash in each case was extracted with dilute nitric acid, and the final ignited residue taken to be silica; the phosphates in the nitric acid solution were estimated. 197 From the results of his experiments, the author draws the following conclusions : (a)Phosphates are immediately absorbed by the roots of the plant.(a) These phosphates are rapidly transferred to the upper parts of the plant. (c) A quantity of phosphates is stored in the upper portions and leaves of the cane. (d) The silica is transferred regularly to the leaves, and there stored. 154. “On the non-existence of the gaseous sulphide of carbon dewxibed by Deninger.” By E. J. Russell and N. Smith. The authors have examined the gas prepared as Deninger describes (LJiir. Prak, Chemie, 1895,ii,51,346)and to which he gave the formula CS. Deninger prepared it (1) by heating together in a sealed tube chloroform and sodium sulphide, (2) by subjecting to the same treat-ment a mixture of iodoform and silver sulphide, (3) by the action of sodium on carbon disulphide mixed with aniline. The authors can find no evidence whatever of the existence of this gas.Sodium and carbon disulphide left in a closed apparatus fitted with a mercury gauge were found to produce no gaseous substance : a mixture of sodium, aniline, and carbon disulphide evolved hydrogen and hydrogen sulphide, and these gases in escaping carried over some carbon disulphide. Evidence that no other gas was present was obtained (1) by analysis, (2) by cooling the mixture and separating it into its constituents. On heating together in a sealed tube to 180’ a mixture of potassium sulphide and chloroform, the products were hydrogen sulphide, hydro- gen chloride, chloroform, a reddish-yello w liquid which was apparently an alkyl sulphide, and free sulphur.A mixture of iodoform and silver sulphide similarly treated yielded hydrogen, carbon disulphide, and the reddish-yellow liquid. Although owing to the complex nature of these products the authors can hardly assert that no new gas having the formula CS was present, they could find no indication of any such compound. 156. “Hydroxyoxamides. Part 11.” By R. H. Pickard, C, Allen W. A. Bowdler, and W. Carter. The authors described the following new hydroxyoxamides, namely : 0-, Pn-, and p-nitrophenyl-, o-tolyl-, and ethyl-hydroxyoxamides. These react as hydroxamic acids (T~~ans.,1901,79,841). The esters of hydroxy- oxamides are weak acids, and the hydroxyoxamides react with phenyl- hydrazine, forming phenylhydrazides.These and other reactions show 198 that the hydroxyoxamides behave like typical hydroxamic acids, and are therefore constituted according to the formula R*NH*CO*C(OH):NOH and not R*NH*C:(NOH)*CO,H,as suggested by Schiff (Annalen, 1902, 321, 357) and Holleman (12ec. trm. chiin., 1896, 15, 148). 156. ‘‘Isometric anhydrous sulphates of the form MSO,,RiSO,.” By F. R. Xallet. The author described the anhydrous salts MgS04,K,S0,, MgSO,,Rb,SO,, MnSO,, K,SO,, MnSO,,Rb,SO,, MnSO,,TI,SO,, NiSO,,K,SO,, and CoSO,,K,SO,, which all crystallise in tetrahedral forms, being allied in this respect to the sulphates 2M”SO4,R2’SO, previously described (Trans., 1900, 77, 216).They vary in their stability when exposed to the air, some remaining unaltered, whilst others are converted somewhat rapidly into the hexahydrated salts, MW04,R~S0,,6H,0. 157. The oatalytic racemisation of amygdalin.” By J. W. Walker. Much more amygdalin is dissolved by water containing a small quantity of alkali, of alkaline earth, or of alkali carbonate, than by pure water From polarimetric determinations of the rate of hydrolysis of the various substances involved, the author concludes that in alkaline solution the glucoside is rncemised by the catalytic action of the hydroxyl ions, and that amygdalinic acid is racemoid with respect to its asymmetric carbon atom. 158. On asymmetric optically active selenium compounds and on6‘ the sexavalency of selenium and sulphur.” By W.J. Pope, P.R.S., and A. Neville, B.Sc. NetAyZphenyl selenide, C,H,*Se*CH,, the first mixed a1kyl selenide which has been described, is obtained as a pale yellow oil boiling at 200-201° by the action of methyl iodide on the sodiophenyl selenide of Erafft and Lyons. Owing, apparently, to the highly basic character of selenium, it differs markedly from methylphenyl sulphide in that it combines readily with bromacetic acid to form the asym- metric mthylphenylselenetine bromide, C,H~>se<CH,.CO,H ; thisCH Br salt crystallises in colourless scales melting at 111’ and on treatment with silver d-bromocamphorsulpbonate, yields a mixture of the two following salts, which may be separated by crystallisation from alcohol.d-Methylphenylselenetine d-bromocamphorsulphonccte (d-B, d-A), Se(CH,)(C,H,)(CH2*C0,H)*C,oH,,BrOS0,,is the less readily soluble 199 and forms needles melting at 16s'; in aqueous solution, its rotations are [a]D = + 61 '26" and [MID= + 330.8'. 1-Methylphenylselenetine d-bromocamphorsulp~~on~te(LB, d-a), is much more soluble than the preceding salt, and is obtained in minute, white scales melting at 151'. Its rotations in aqueous solution am [a]D= +3S.81" and [MID = +209.6'. Since the d-bromocamphor- sulphonic ion has the molecular rotation [MID= +270°, the Come-bponding value for the optically active selenetine ion is [MID= +,60.6". The dextro-and Zcevo-methylphenylselenetine platinichlos-ides, [Se(CH3)(C,H5)(CH2-C02H)Cl]2PtC14,form yellow prisms melting ah 171" ;they have the molecular rotations [MI,= +55.0" and -54.3' respectively in acetone solution.The same optically inactive methylp,'LenyZselenetine mes*curiodid% Se(CH,)(C,H,)( CH2*C02H)I,Hg12,is obtained by precipitating either of the salts (d-12, &A), (Z-B?d-A), or methylphenylselenetine bromide with a solution of potassium mercuric iodide ;the mercuriodide forms white scales melting at 141-142'. The optical inactivity of this salt being remarkable, in view of the fact that the d-and E-benzyl- phenylallylmethylammonium ions preserve their optical activity during formation of the mercuriodides, it seemed desirable to ascertain if the same behaviour was exhibited during the formation of a ma- curiodide from an optically active thetine.The authors therefore prepared the optically active rnethylethyl- phenacylthetine salts of Smiles instead of the methylethylthetine com- pounds previously described by Pope and Peachey, owing to the greater optical rotations exhibited by the optically active ions of the former substances. It was then found that the d-methylethylphen- acylthetine d-bromocamphorsulphonate, (d-B, &A), had the molecular rotation [MI, = + 332*S0, whilst the corresponding salt, (2-B?&A), gave [l!t]D = + 210.6' ; the optically active methylethylphenacyl-thetine ion therefore has the molecular rotation [MID= +_61*1',a value about three times as great as [MI, = +, 19*4O, the molecular rotation deduced from Smiles' determinations. Eltchof theabove salts yields the same optically inactive mercuviodicle, S(CH3)(C2~,)(CH,*CO*C,H5)I,HgI,,melting at 128O, and nzerczcrichZoi*-ide, s(CH,)(C2H5)(CH2*CO*CGH5)C1,HgCI,,melting at 119'.They also give the same methylethylphenacylt~etine-d-merc~ri~romocan~~hora~lp~o~z-ate, S(CH,)(C2H5)(CH,*C02*U,H5)CloHl,BrOS03,Hg(CloH14BrOS03)2, which has a molecular rotation [&i]D = + 79g0, very nearly three times that of the d-bromocamphorsulphoiiic ion, and in which the sulphur atom does not seem to act, as a centre of optical activity. The authors conclude that the mercuri-compounds of the sulphonium and selenonium bases probably contain sexavalent sulphur and selenium, 159.‘‘ The transformation of acetylchloroaminobenzenes into the iso-meric chloroacetanilides.” By F. D.Chattaway and K. J. P. Orton. Owing :to the recent publication by Blanksma (Proc. K. Aknd. Wetensch. Amsterdam, 1902, p. 178) of measurements of the velocity of transformation of acetylchloroaminobenzene into p-chloroacetanilide, the authors wish to record the results of some preliminary experiments made by them two years ago (September, 1900) on isomeric changes of this type. These experiments were not published at that time, as Armstrong had previously stated (Trwns.,1900, 77,1053) that he was engaged on a similar investigation. To follow the course of the isomeric change, a 1per cent. solutionof the chloramine in glacial acetic acid or in 50 per cent.acetic acid was kept at a constant temperature in the dark, and the amount trans- formed estimated at intervals by titrating the iodine liberated from hydriodic acid by the unchanged substance. In the presence of an acid, such as hydrochloric or sulphuric, the isomeric chloroacetanilide is produced. When hydrochloric acid is added, the change starts at once and proceeds regularly ; with sulphuric acid, 011 the other hand, no transformation occurs at first, but after a short interval it begins and proceeds at a constantly increasing rate. At any period, however, during which isomeric change is taking place, hydrogen chloride can be recognised in the solution. The results of the authors confirm the observation first made by Armstrong (Zoc.cit.), that hydrochloric acid has a specific action in the transformation of phenylchloramines. The experiments were carried out mainly with acetylchloroamino-p- chlorobenzene, C6H,C1*NC1*Ac, not only because this substance is obtained somewhat more easily in a pure state, but especially because it changes more slowly into the isomeric anilide than does acetylchloro- aminobenzene. The value of the velocity coefficient, calculated from the equation k = l/t log a/(. -x), increases with the amount of the catalytic agent and with the temperature, but decreases when the proportion of water in the solvent is increased. In any given experiment, it also begins to increase at some point in the course of the reaction, usually after the first 50 per cent.of the chloramine has changed. The following experiment shows the kind of results obtained : A 1 per cent. solution of acetylchloroamino-p-chlorobenzene in glacial acetic acid containing 0.023 per cent. hydrogen chloride was kept at a temperature of 16.5”, and the unchanged chloramine estimated at the end of 1, 2, 4,6, 8, 24, and 28 hours. Calculating the velocity co-efficient from the above equation, the values obtained are respectively 0*0100, 0.0104, 0.0106, 0.0105, 0.0107, 0.0109, and 0.0110; the mean value is 0.0106. 201 In a series of experiments carrried out in order to ascertain the effect of temperature and of variation in the percentage of hydrogen chloride present, and in the concentration of the acetic acid, the following results were obtained, Using a 1 per cent.solution in glacial acetic acid containing 0.023 per cent. hydrogen chloride, half the chloramine was transformed in 27.4 hours ; but in the presence of 0.069 per cent. hydrogen chloride, half was transformed in 5.33 hours, the temperature in each case being 16.5". With a 1 per cent, solution containing 0.023 per cent. hydrogen chloride, at a temperature of 35*9",half was transformed in 2.75 hours; the value of the velocity- coefficient in this case mas not constant, but rapidly increased. Using 50 per cent. acetic acid containing 0.023 per cent. hydrogen chloride as the solvent, 130 hours elapsed before half mas transformed at a temperature of 16.5". With 0.9 per cent, sulphuric acid, instead of hydrogen chloride, in glacial acetic acid, at a temperature of 16.5', no appreciable change occurred in 2 hours; but after 24 hours 8.9 per cent., and after S4 hours 50 per cent,., had changed.Hydrochloric acid, which could not be recognised in the solution after 2 hours, was found to be present after 24 hou1.s. Similar experiments made with acetylchloroaminobenzene, PhNCl*Ac, show that the isomeric change takes place at a greater rate when the chlorine can wander into the para-position than when it can only pass into the ortho-positions. Thus, in an experiment similar to those just described (HC1=0*023 per cent.), the time required for the transformation of half the chloramine was 2 hours instead of 27.4 hours. In connection with the transformation of phenylacylchloramines under the influence of hydrogen chloride, the following facts are worthy of note.Wben kept in the dark at the ordinary temperature, the titer of a solution iri glacial acetic acid of acetylchloroamino-2 : 4 di-chlorobenzene, which under these conditions cannot be transformed into the isomeric s-trichloroacetanilide, slowly falls, and at the same time a vapour (probably hypochlorous acid) is given off, which sets free iodine from potassium iodide. (A similar vapour is evolved from solu- tion of any chloramine in glacial acetic acid.) If small quantities of hydrogen chloride or sulphuric acid be present, the titer decreases more rapidly ; thus with a solution of the last-mentioned chlorarnine con-taining 0.069 per cent, of hydrogen chloride, the titer fell 23 per cent.at 16.5"in eight days, whilst in the presecce of 0.36 per cent. sulphuric acid the titer fell 8 per cent. 01 the initial amount in the same period. In both cases the solutions, which mere kept in the dark, acquired a yellow colour. Possibly these changes are due to the hydrolysis of the chloramine; the acetic acid contained 1.8 per cent. of water. 202 Further, when a solution of hydrogen chloride in dry petroleum is added to a solution of acetylchloroamino-p-chlorobenzene in the same solvent, p-chloroacetanilide, vhich is insoluble in petroleum, immedi- ately separates, Blanksma (Zoc. cit.) has drawn attention to the action of light in effecting this isomeric change, and has observed the transformation of the solid substances under its inflaence. On exposing any chloramine dissolved in chloroform or in acetic acid to sunlight, the originally colourless solution in a few minutes becomes yellow nud acquires a chloroxs smell ; in all cases the solution then gives a, precipitate with silver nitrate.If a phenylncylchloraruine, which is capable of isomeric change, is so treated, transformation follows. Thus after two hours’ exposure to sunlight, acetylchloroamino-p-chlorobenzeneis changed into the isomeric anilide to the extent of 31 per cent. when dissolved in chloroform, but only to the extent of 12 per cent. when dissolved in acetic acid. The light is probably active by virtue of the fact that it induces decomposition, in the course of which the catalytic agent is formed.These results shorn that in the presence of hydrogen chloride the transformation of phenylacylchloramices in to chloroanilide is c6ppre~at7y a monomolecular retctioa, and in this may resembles other similar isomeric changes; but it must not lie forgotten that in measuring the speed of a chemical reaction the velocity of the slowest of the series of simple changes which constitute the complete transfortnation is alone. measured. ADDITIONS TO THE LIBRARY. I. Boncbtions. Atwater, Wiebur Olin : Benedict, Francis Gano : arid others. Experi- msnts on the metabolism of matter and energy in the human body. 1898-1900. (U.S. Dept. of Agriculture, Office of Experiment Sta-tious.Bulletin No. 109). Washington 1902. Cross, C. F., and E. J. Bevan. Researches on cellulose, 1895-1900. pp. xii + 180. London 1901. From the Publishers. Emmerling, 0. Die Zersetzung stickstoff freier organischer Sub-stanzen durch Bakterien. pp. 141. Braunschweig 1903. Ill. From the Yublishers. PitzGerald, George Francis. The scientific writings of. Collected and edited with a historical introduction by Joseph Lsrmor. pp. lxiv +576. Dublin 1902. Ill. 203 Heusler, Friedrich. The chemistry of the terpenes. Carefully revised, enlarged,tand corrected. Authorised translation by Francis J. Pond. pp. 457. London (American printed) 1902, From the Publishers. Hoff, J. H. vim’t, Acht Vortrage uber Fhysikalische Chemie gehalten auf Einladung der Universitat Chicago, 20 bis 24 Juni, 1901.pp. 81. Braunschweig 1902. Ill. From the Author. Rlacbride, David, Experimental essays on medical and philosophical subjects : particularly on (1) the fermentation of alimentary mixtures and digestion of the food ; (2) the nature and properties of fixed air ; (3) the respective powers and manners of actingof the different kinds of antiseptics; (4) on the scurvy; (5) on the dissolvent power of quicklime, and a further investigation of the properties of fixed air. Second edition, enlarged and corrected. pp. xiv + 296. 111. London 1767. From the Librarian, Marignac, Jean Charles Gslissard de. Oeuvres complAtes. Hors-shie des M6moiyes de la soci6t5 de physique et d’histoire naturelle de Gendve.Vol. I. 1840-1860. Geneva 1902. From the Family. Merck, Emmanuel August. Merck’s Index. 2nd edition (no. 193). Darmstadt 1902. From the Author. Morgan, John James. Aids to the analysis and assay of ores, metals, fuels, &c. pp. 112. London 1902. Ill. From the Publishers. Munroe, Charletj E., and Chatard, T. M. Chemicals and allied pro- ducts. With a digest of United States patents relating to chemical industries. (Twelfth Census of the U.S. Census Bulletin No. 210. June 25th, 1902.) From the Department. Rhead, E. L., and A. Humboldt Sexton. Assaying and metallur- gical analysis for the use of students, chemists, and assayers. pp. sii+431. 111. London 1902. From the Publishers. Tilden, William A. A manual of chemistry, theoretical and practical (based on Watt’s edition of Fownes manual).Ill. pp. xvi +599. London 1897. From the Publishers. Tilden, William A. Introduction to the study of chemical philo- sophy. The principles of theoretical and systematic chemistry, Tenth edition (fourteenth impression). London 1901. From the Author. Wait, Charles E. Experiments on the effect of muscular work upon the digestibility of food and the metabolism of nitrogen. (U.S. Dept. of Agriculture, Office of Experiment Stations. Bulletin No. 117). Washington 1902. From the Department. Wolfrum, August. Chemisches Praktikum. I. Teil. Analytische Ubungen. pp. xviii +562. Leipzig 1902. From the Publishers. 204 11. Bg Purchctss. Bibliographie der deiitschen naturwissenschnftlichen Litteratur , herausgegeben im sufrage des Reichsamtes des Innern vom deutschen Bureau der internationalen Bibliographie in Berlin.Vol. I. 1901-2. Jena 1902. [Egregius Christo.] Anccgrnmfor George Stnrkey 1 Edited by Eirenaeus Philoponos Philalethes. A true light of alchymy, contain- ing (i) a correct edition of The Marrow of Alchyny, being a celebrated experimental treatise, discbvering the secrets and most hidden mystery of the philosophers’ elixir, both in theory and practice. (ii) The errors of a late tract called, A short discourse of the Quintessence of Philoso-phers; wherein is pretended to be set forth how one select person might be made partaker of it by the author’s means, and others rightly directed in prosecuting that study.(iii) The methods and materials pointed at composing the Sophick Mercury and transmutating elixir, in plain terms free from all enigmas. The like never beFore emitted to the world. Pp. vi+98. Printed for the author. London 1709. International Catalogue of Scientific Literature. First Annual Issue. D. Chemistry. Part 1. 1902 June. London 1902. Kobert, Rudolf. Lehrbuch der Intoxikation. Band I. Allgemeiner Theil. 2nd edition. pp. xxiv + 302. 111. Stuttgarli 1902. Kolbe, Hermann. The electrolysis. of organic compounds (1845-1868). Alembic Club Reprints, no. 15. Edinburgh 1900. Mennicke, Hans. Zur Verwertung speziell der Wiedergewinnung des Zinns von Weissblechabfallen (Xmnmlung, Bd. vii). Stuttgart 1902. Philosophical Transactions.Vol. XV. (for 1665). Oxford 1686. Schultz, Gustav, u. Julius, Paul, Tabellarische Ubersicht der im Handel befindlichen kiinstlichen organischen Farbs tofEe. Vierte urn-gearbeitete und stark vermehrte Auflage. pp. xvi + 210. Berlin 1902. Stange, Alb. Einfuhrung in die Geschichte der Chemie. pp. 308. Ill. Miinster (Westf.) 1902. Stark, Johannes. Die Elektrizit’at in Gasen. pp. xxviii +509. Mit 144 Abildungen. Leipzig 1902. Valentine, Basil. Translated by J. W. The last will and testa- ment of Basil Valentine, monke of the order of St. Bennet, which being alone, he hid under a table of marble, behind the high altar of the cathedral church in the imperial city of Erford : leaving it there to be found by him whom God’s providence should make worthy of it.To which is added two treatises. The first declaring his manual opera- tions. The second showing things natural and supernatural. Never 205 before published in English, Ill. pp. lxviii + 48-534. London 1670. (This copy wants pp. 31 3-342, apparently a philosophic work upon Sol.”) Vanino, Ludwig and E. Seitter. Die Patina. Ihre natiirliche und kunstliche Bildung auf Kupfer und dessen Legierungen. pp. 63. Wien 1902. Witt, Otto Nicolaus. Die chemische Industrie des deutschen Reiches im Beginne des zwanzigsten Jahrhunderts. Eine Festschrift zum funfundzwanzigjahrigen Jubilaum der Begrundung des Vereins zur Wahrung der Interessen der chemischen Industrie Deutschlands. pp. 229. Berlin 1902. 111. PamphZets. Ag&ulturccl Students’ Gazette.Vol. x, part 2, Dee., 1900 ; and vol. x, part 6, April, 1902. From Professor Kinch. RESEARCH FUND. A meeting of the Research Fund Committee will be held in December. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on or before December 8th. At the next meeting, on Wednesday, November 19th, at 5.30 p.m., the following papers will be communicated : ‘I The dynamic isomerism of thiourea and ammonium thiocyanate.” By J. E. Reynolds and E. A, Werner. ‘‘ Isomeric partially racemic salts containing quinquevalent nitrogen. Part VIII. Resolution of the hydrindamine bromocamphor sul- phonates.” By F. S. Kipping. 6LIsomeric compounds of the type NR,R,H,.” By F. S. Kipping.‘‘ The synthesis of aa-dimethylglutaric acid, of P-hydroxy-au-di-methylglutaric acid, and of the cis-and trans-modifications of aa-di- methylglutaconic acid.” By W.H. Perkin, jun., and Miss E. Smith. 206 “A reaction of some phenolic colouring matters. Part 11.” By A. G. Perkin and C. R. Wilson. “ The vapour pressures and boiling points of mixed liquids. Part 11.” By S. Young and Miss E. C. Fortey. “The vapour pressures and boiling points of mixed liquids. Part 111.” By S. Young. ‘(Note on mixtures of constant boiling point.” By S. Young.(‘Note on the condensation points of the thorium and radium emanations.” By E. Rutherford and F. Soddy.‘(The oxime of mesoxamide and some allied compounds. Part 11. Disubstituted derivatives.” By Miss M. A. Whiteley. RICHARD CLAY AND SONS, LIMITED, LONDON AND BGNQAY.
ISSN:0369-8718
DOI:10.1039/PL9021800179
出版商:RSC
年代:1902
数据来源: RSC
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