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Proceedings of the Chemical Society, Vol. 21, No. 298 |
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Proceedings of the Chemical Society, London,
Volume 21,
Issue 298,
1905,
Page 199-214
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?ssued 30/6/05 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 21. No.298. Wednesday, June 14th, 1905, Professor R. MELDOLA,F.R.S., Presi-dent, in the Chair. Mr. G. W. T. Horrod was formally admitted a Fellow of the Society. Certificates mere read for the first time in favour of Messrs. : Harry Dunlop, Cragdarroch Cove, Dumbartonshire. Eric Haydn-Morris, c/o Messrs. G. Mowling & Son, Footscray, Melbourne, Victoria. The PRESIDENTannounced that it had been decided by the Council that the ordinary meetings of the Society shall be held during the ensuing Session on the first and third Thursdays at 8.30 p.m. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected : Edward Williams Bealey, B.A. Ernest Lyle Carman Forster, &LA. William James Bees, B.Sc. Herbert Henstock, B.Sc. Joseph Bennett. William John Jarrard, B. Sc. William Robert Bousfield, M.A., Arthur Walter Mason, B.Sc. K.C., M. P. Frederick Wilson Montrose Ross. Eric William Campbell. James Steger, B.Sc. William Beaverly Cowie. William Bradshaw Tuck. William Walpole Day, B.Sc. John William White. Ralph Emerson De Lury, M.A. William James Wren. Robert Donald, KA., B.Sc., M.R.C.S., L.R.C.P. 2 00 Of the following papers, those marked * were read : *121. “Influence of various sodium salts on the solubility of sparingly soluble acids.” By James Charles Philip. That magnesium hydroxide is more soluble in ammonium chloride solutions than in pure water is due, according to one current explana- tion, to the formation of undissociated ammonium hydroxide and the consequent removal of hydroxyl ions, this leading to the solution of more hydroxide.If this is so, then conversely the solubility of spar-ingly soluble acids should be increased in the presence of sodium salts of weak acids. This is found to be actually thecase,and the influence of sodium formnte, acetate, and butyrate on the solubility of cinnamic, benzoic, salicylic, and o-nitrobenzoic acids has been determined at 26~4~.It is to be expected on theoretical grounds, and the expectation is confirmed by the experimental results, that the extent to which the solubility of a given sparingly soluble acid is increased by the presence of the sodium salt NaA will depend on the strength of the acid HA.If the concentration of the sparingly soluble acid in the saturated solution is plotted against the concentration of the added salt (NaA, NaA’, NaA“, Szc), it is found that the order of the curves so obtained is the order of strength of the acids HA, HA’, HA”, &c. Further, the increase of solubility of cinnamic acid (for example) in a solution of NaA of known concentration, as compared with its solu- bility in pure water, can be calculated in good agreement with experiment when the solubility product for cinnamic acid and the dissociation constant of the acid HA are known. “122. “ The dielectric constants of phenols and their ethers dissolved in benzene and m-xylene.” By James Charles Philip and Dorothy Haynes.Evidence was brought forward some time ago by one of the authors (Philip, Zeit. physikal. Chem., 1897,24, 18) showing that the dielectric constant of an alcohol calculated from the dielectric constant of its benzene solution decreases as the concentration of the alcohol decreases, and is in all cases less than the directly determined dielectric constant of the pure alcohol. This behaviour, connected probably with the associative tendency of the alcohol molecules, has now been observed also in the case of phenols. The phenomenon is well marked in the case of phenol itself, but less distinct in the case of the cresols; indeed, the dielectric power of o-cresol in benzene solution seems to be nearly independent of the concentration.The phenol ethers, in which the associative tendency has been got rid of by obliterating 201 the hydroxy-group, exhibit an almost normal dielectric behaviour in benzene solution. It is notevorthy that the introduction of a methyl group at any point in the ring lowers the dielectric constant of anisole, the lowering effect, however, of the methyl group being much greater in the ortho-position than in either themeta- or para-position. DISCUSSION. Sir WILLIAM inquired whether Dr. Philip's measurements RAMSAY threw any light on the fact that the molecular weight of alcohol in benzene solutions may rise as high as 230. Was this due to poly- merisation of the alcohol or to a compound of alcohol with benzene? Dr.PHILIPsaid that although the dielectric property of alcohol in benzene had been found to diminish with dilution in an analogous manner to the molecular weight, no evidence had been obtained bearing on the point referred to by Sir William Ramsay. *l23. LL Synthesis by means of the silent electric discharge." By John Norman Collie. When pure ethylene was submitted to the action of the silent electric discharge in a vessel cooled to -20", polymerisation occurred, and a liquid was produced together with some hydrogen gas. In one experi- ment, 210 C.C. of ethylene gave about 40 C.C. of hydrogen. Ten grams of the liquid produced by the polymerisation of ethyl-ene were fractionated. The fractions collected and their analyses were as follows : Distilled 100".100-150". 150-200". 200-250". Residue. residue. c ...... 83.4 85.3 85.8 86'0 87 -7 87-7 H... .. 16'0 15.3 14 *3 14.0 12'4 12'3 The first fraction was very small; most of the distillate collected in the two fractions 100-150" and 150-200°, the chief part boiling between 130' and 170". The residue left in the flask was a dark resinous substance, which, on heating, smelt of burnt india-rubber ; this product weighed 4 grams, or two-fifths of the whole. The decrease in hydrogen and increase in carbon in the above analyses is interesting ;olefinic hydrocarbons, C,H2, require C =85.7 ; €I= 14.3 ;C,oH,, requires C =87.7 ;H = 12.3 per cent. These various fractions were oxidised by means of potassium per- manganate solution in the cold.After filtering off the precipitated manganese oxide, the solution of potassium salts was acidified ;a strong odour of either valeric or caproic aldehyde was at once pro-duced in the case of the two fractions (100-150O) and (150-200°). These aldehydes were distilled in steam and oxidised with silver 202 oxide. The silver salt gave, on analysis, Ag =48 per cent,, which is equivalent to an acid of molecular weight 118, that of caproic acid being 116. Ethylene was also mixed with carbon monoxide and submitted to the silent electric discharge, when aldehydes were formed in small quantity. Formaldehyde and acrolein mere both probably present, ;but the chief condensation that occurred was that of the ethylene itself to form hydrocarbons having high boiling points.The facts that are of especial interest are that ethylene under the influence of the silent electric discharge at the ordinary temperature will not only unite with carbon monoxide, but will also polymerise, yielding a series of :complicated hydrocarbons ; the chief substances formed boil at about 150-160° and apparently approximate in com-position to C1,H,, ; moreover, further condensation means loss of hydrogen and the formation of compounds approximating both in properties and composition to the terpene derivatives. On oxidation, the olefinic hydrocarbons break down, yielding coinpounds containing about six carbon atoms in the molecule. DISCESSION. Mi-. HARCOURTreferred to experiments on ozone by Sir B.Brodie, in which the oxygen exposed in a Siemens tube to the silent discharge was mixed with a large proportion of carbon dioxide, the idea being that ozone might be protected during its formation by dilution with carbon dioxide and obtained afterwards in a concentrated form by absorption of the diluent. The resnlts, however, showed that carbon dioxide was decomposed and ozone formed from it ; moreover, a brown coating was deposited on the glass, this product being readily soluble in water. This experiment seemed to be an illustration of Dr. Collie’s view that the syntheses which plants effect under the influence of sunlight, forming complex products out of carbon dioxide and water, may be to some extent paralleled by the action of the silent discharge.Professor TILDENreminded the author that experiments of the same character and having similar results had already been carried out by Berthelot (Journ. Chem. SOC.,1876, ii, 596). The PRESIDENTconsidered that not the least interesting part of Professor Collie’s paper wa.s the fact that he had succeeded in obtaining a sufficient quantity of the synthesised products to enable him to give definite and quantitative information as to their nature. Most of the workers who had studied the synthetical action of the silent electric dis- charge had hitherto only given qualitative results. With reference to the polymerising action of this discharge, he (the President) mentioned that some years ago, in conjunction with Rlr.R. J. Strutt, he had made some experiments having for their object the possible cornbina- tion of argon with acetylene, No combination mas observed, but the polymerising action of the discharge on the acetylene was very obvious, an accumulation of tarry and resinous products being obtained, but these mere not further examined, as practically the whole of the argon originally mixed with the acetylene was recovered at the end of the experiments, With respect to photosynthetic processes, he thought it might be of interest, in view of the modern developments of radio-activity, to call attention once again to the older work of Fay and of Seekamp, who state that photochemical decompositions are in many cases promoted by the addition of uranium salts to the solutions.This raises the question whether the energy, which must be supposed to be liberated on the ‘‘ disintegration” hypothesis of the uranium atom, may not play a part in such photochemical processes. *l24. ‘‘ The ultra-violet absorption spectra of aromatic compounds. Part I. Benzene and certain mono-substituted derivatives.” By Edward Charles Cyril Baly and John Norman Collie. The ultra-violet absorption spectra of benzene and of some of its mono-substituted derivatives were described. It has been found that benzene presents seven separate absorption bands, and it mas shown how the formation of these may be accounted for by attributing each one to a separate and distinct process of dynamic isomerism con-nected with the linking changes within the benzene molecule.In the case of the mono-substituted derivatives of benzene, it is shown how their absorption spectra may be arranged in types, and it appears that each type corresponds either to complete saturation or to the nature and position of unsaturated at,oms in the substituent group. The presence of an unsaturated atom in the a-,p-, or y-position in the side-chain thus produces a particular type of absorption. When t,he un- saturated atom is present in the &position, it is apparently removed too far from the nucleus to exercise any effect, with the result that the same absorption spectrum is obtained as if the side-chain were completely saturated. “125. LL The ultra- violet absorption spectra of aromatic compounds.Part 11. The phenols.” By Edward Charles Cyril Baly and Elinor Katharine Ewbank. The ultra-violet absorption spectra of anisole and phenetole are found to differ from that of phenol ;in the former cases, the single absorption band given by phenol is subdivided near its head into two bands. 204 The absorption band produced by the dynamic isomerism existing in solutions of acetylacetone and similar tautomeric substances of the aliphatic series occupies very nearly the same position as the band given by phenol. The existence of a similar type of dynamic iso-merism in the case of phenol would, therefore, explain the difference between the spectra of phenol and its ethers. The presence of this kind of tautomerism, that is, a labile hydrogen atom, in phenol is proved by the influence of acid and alkali on the spectrum of this substance.Just as in the case of certain aliphatic tnutomeric com-pounds, the position of the absorption band is shifted towards the red on the addition of sodium hydroxide, whilst the addition of acid tends to restrain the dynamic isomerism. The results obtained with the three dihydroxybenzenes, the three cresols, and p-aminophenol support the view that similar tautomerism exists in these substances. "126. '6 Association in mixed solvents." By George Barger. The association which many hydroxylated substances exhibit in some solvents (benzene, chloroform) does not occur in others (alcohol, acetic acid), probably because the latter form loose molecular com-pounds with the solute according to the law of mass action (Abegg, Zed.ccnorg. Chern., 1904, 39,330). In dilute solutions, the concentra- tion of the solvent is large compared with that of the solute, and if the solvent is dissociative its influence predominates, The present investigation deals with cases in which the concentration of the dis- sociative solvent was reduced by mixing it with an associative one. The dissolved substances were acids, alcohols, phenols, and oximes. Dilute solutions of these were made in mixtures of toluene, benzene, chloroform, or carbon tetrachloride with one of the following dissocia- tive solvents : pyridine, acetic acid, ethyl acetate, methyl acetate, ethyl formate, ethyl alcohol, methyl alcohol, and acetone.The mole- cular weight of the solute was determined by the author's microscopic method (Trans., 1904, 86,286), this process being particularly suited for work with mixtures. The results are in general agreement with what might be expected from mass actlion according to the above theory. The molecular weight is normal in nearly all the mixtures, and association only persists when the percentage of the dissociative solvent is very small. The esters are the least powerhl of the dissociative solvents exam- ined, which is in accordance with their behaviour in other respects. For instance, as the result of a study of the boiling points of homolo-gous series, Young places the esters between associated and non-associated liquids (Phil.Mag., 1905, [vi], 9, 1). According to Lachman (J.Amer. Chem. Soc., 1903, 25, SO), brown solutions of iodine owe their colour to the formation of loose moleclilar compounds between solute and solvent. If equal volumes of an alcoholic and a chloroform solution containing equal quantities of iodine are mixed, the colour of the mixture is not intermediate between that of the component solutions, but is more like that of the alcoholic solution. This experiment serves to illustrate the mass action effect of the solvent. “127. ‘‘ Synthesis of substances allied to epinephrine.” By George Barger and Hooper Albert Dickinson Jowett. The authors have attempted to synthesis0 a compound having the f orrnula OH ()OH \/YH-OH CH,*NHMe which was proposed by one of them (Trans., 1904, 85, 192) for epinephrine (adrenaline), the active principle of the suprarenal gland.Although the methylene and dimethyl ethers were prepared, the dihydroxy-base could not be isolated. The constitution of the ether bases was proved by their oxidation to piperonylic or veratric acid respectively. The dihgdroxy-base could not be obtained from the ethers, although indications of the formation of a substance having the chemical and physiological properties of epinephrine were obtained by the action of dilute hydrochloric acid at 150’ on the methylene ether. The following compounds were prepared and described : a-3 :4-methylenedioxyphen yl-ap-dibromoethane, CH2:02:C6H3*CHBr-CH2Br, needles, m.p. 82-83’ ;a-3 :4-methylenedioxyphenyl-/3-bromo-a-hyclroxy-ethane, CH,:O,:C,H,*CH(OH)*CH,Br, long needles, m. p. 107-108” ; p-3 :4metl~yleneclioxy;vhenyZ-/3-hydroxyethylmethyl~minepicrate, CH,: 0,:C6H3*CH(OH)*CH,*NRMe,C6H307N3, yellow needles, m. p. 178’ ; the corresponding base and pkltinichloricle are amorphous : 3 :4-dimethoxystyren,e,(CH30),:C6H,*CH:CH,,colour-less liquid boiling at 120-125’/10 mm. a-3 :4-dimethoxyphenyl-ap-dibromoetiiane, (CH,O),: C,H,*CHBr*CH,Br, needles, m. p. 102’ ; a-3 ;4-dimetl~oxyphenyb-/3-bromo-a-hydroxyethane, (CH,O),:C,H,* CH(OH)*CH,Br, long needles, m. p. 68O. 206 The corresponding methylamine base could not be crystallised, nor could any crystalline salt be obtained.The piperonyldibromide (m. p. 160') described by Mameli (Gaxzetta, 1904, 34, [i], 358) is really the dibromohydrin, CH,:O,:C,H,Br.UH( OH) CH,Br, and has been obtained by the action of bromine water on the bromo- hydrin and also by the action of phosphorus pentachloride on the dibromide. "128 The determination of melting points at low temperatures."'I By Leo Frank Guttmann. A method has been worked out for readily determining melting points at low temperatures by means of a constantan-copper couple connected to a delicate galvanometer. The couple was calibrated by immersion in substances of known melting point ; ice, chloroform, ether, liquid air, and a mixture of solid carbon dioxide and alcohol being chosen. The melting point of ethyl bromide had been deter- mined by a previous observer to be -129.5', and it is now shown to be -118O, the low number formerly obtained being due to an ad-mixture of ether.The melting point of some very pure toluene was also found to be higher than that of ordinary pure toluene, to which the melting point -97" to -99' had been ascribed. The melting points determined were methyl alcohol, -98" ; ethyl alcohol, -117.3O; methyl iodide, -64'; ethyl chloride, -142O ;ethyl bromide, -118' ; ethyl iodide, -109" ; toluene, -92"; m-xylene, -55O ;ethylbenzene, -93". Ethyl alcohol was found to have the property of supercooling to a remarkable degree, It could be frozen to a clear, transparent glass by immersion in liquid air, and if it was then allowed to warm up slowly to -135O, crystallisation set in explosively, the temperature rising about 20' in 10 seconds and a white, opaque mass of crystallised alcohol being formed.29. "The action of water on diazo-salts. A preliminary note." By John Cannell Cain and George Marshall Norman. One of the authors has shown (Trans., 1903, 83,688) that little or no hydroxy-compound is obtained by boiling certain ortho-substituted diazo-salts of the diphenyl series with dilute acids, but that qcinonoid derivatives resulted. AS there are a large number of similarly sub-stituted compounds belonging to the benzene series which are said not 207 to yield the corresponding phenols on boiling with water or acids, it appeared to be of interest to examine these with the object, if possible, of elucidating the course of the reaction.s-Tribrornoani1ine.-Silberstein (J.pr. Cliern., 1883, 2’7,98) was unable to obtain any phenolic derivative by boiling s-tribromobenzene- diazonium sulphate or nitrate with dilute acids, and Orton, in a recent communication (Proc., 1905, 21, 168), obtained no trace of the phenol either with dilute or strong sulphuric acid. By using the method described in the German Patent 95339, which consists in heating the diazo-solution with a mixture of dilute sulphuric acid and sodium sulphate (applied in the patent to the production of guaiacol from o-anisidine), we have been able to isolate the corresponding s-tribromo-phenol (m. p. 92-93’), although the yield is small. The failure of other observers to obtain this product is no doubt explained by the facts that the decomposition point of this very stable diazo-salt is considerably above looo, and by using more concentrated sulphuric acid in order to reach a higher temperature a very consider- able retarding influence is introduced.This retarding influence can be measured by determining the (( coefficient of decomposition, C,” according to the method described by one of the authors (Trans., 1902, 81,1412). Thusin the caseof diazo- benzene chloride, the value of C in the case of the chloride is 0.0298 (Zoc. cit., p. 1420). A blank experiment in which an equivalent quantity of sulphuric acid was substituted gave exactly the same number, the diazo-solution containing 0.7 per cent.of H,SO,. When, however, the amount of sulphuric acid is increased until the solution contains about 35 per cent. of the acid, the value of C becomes 0.0191. It follows, there- fore, that an increase in the quantity of sulphuric acid produces an increase in the stability of the diazo-compound (compare Ber., 1890, 23, 2994). s-Trichloroani1ine.-Hantzsch (Ber., 1895, 28, 685) prepared a solution of the diazo-chloride of this substance, and was unable to detect the formation of the corresponding phenol by the action of heat. He says, ‘‘Trichlordiazobenzolchlorid lasst sich mit Wasser, ja selbst mit Salpetersalzsaure kochen, ohne Stickstoff zu entwickeln oder sich iiberhaupt zu veriindern.” The authors have found that under the usual conditions of boiling a brown substance is formed, but only by adopting the same method as in the foregoing instances can a small yield of s-trichlorophenol (m.p. 68”) be obtained. o-Anisidine.-Several workers have been unsuccessful in obtaining guaiacol from the diazo-compound of o-anisidine. Thus Limpach 208 (Be?*.,1891, 24, 4136) passed a current of steam through the solution, but could detect no guaiacol (compare also Gattermann, Ber., 1899, 32, 1136). By passing steam through a strongly acidified solution of the diazo- sulphate for several hours, the authors obtained guaiacol, a still better yield being afforded by the foregoing method. In addition to this product, a small yield of a second substance was isolated; this product crystallised in flat, square tables (m.p. 89’; b. p. 310--312”), giving analytical numbers corresponding with those for the mono-methyl ether of o-dihydroxydiphenyl, OH*CGH,*C6H,*OCH,. 3-Bromo-p-toZuidine.-Wroblewski (Ber., 1874, 7, 106 1 ;Annalen, 1873, 168, 147) describes several halogen derivatives of aniline and toluidine, the diazo-compounds of which do not yield halogenated phenols, but give rise to the corresponding substituted hydrocarbons. In a later paper (Ber., 1884, 1’7,2704)’ he attributes this abnormality to the presence of a small quantity of alcohol in the diazo-derivative. As regards the above compound, this is probably a correct explanation, as a good yield of! the bromo-cresol (b. p.214’ ; Ber., 1884, 17, 2530) is readily obtained by passing steam through an acid solution of the sulphate. 3-C~iloro-p-toZuidi~e, the diazo-compound of which is said by Wroblewski (Zoc. cit.) to yield no corresponding phenol when treated in a similar way, gave rise to 3-chloro-p-cresol (m. p. 191”). 130. A precise method of ;estimating the organic nitrogen in potable waters.” By James Campbell Brown. Details were given of a process for the estimation of the whole of the nitrogen of organic matter in potable water and sewage effluents. The process is found to be as accurate for this purpose as Kjeldahl’s method is for larger quantities of nitrogenous matter, and it has many advantages over Kjeldahl’s process in convenience and speed, and in the absence of the liability to breakage and loss by bumping in glass vessels.The process essentially consists in the distillation to dryness and subsequent ignition of a mixture of a portion, ordinarily 200 c.c., of the sample, without previous evaporation, with potassium hydroxide and potassium permanganate. The operation is carried on either in a Jenn glass or in a copper retort, and the ammonia evolved is estimated by Nessler’s solution. The total carbon of the organic matter was also estimated as carbon dioxide in the residue remaining in the retort, but the results were not so accurate as in the case of the nitrogen, owing to the large amount of carbon dioxide found by blank experiments, which has to be deducted. The results obtained by this process on a variety of waters are com- pared with the corresponding values determined by the Frankland, Wanklyn, and Forchammer methods.131. '' Synthesis of 1 :1-dimethyl-A3-tetrahydrobenzene." By Arthur William Crossley and Nora Renouf. When 3-bromo-1 :1-dimethylhexahydrobenzene (compare Proc., 1905, 20, 242) is heated with alcoholic potash, it loses the elements of hydrogen bromide with formation of 1:1-dimethyZ-A3-tetra-hydrobenzene, which is a colourless, refractive liquid boiling at 117-117~5"/770 mm., and having an odour of turpentine. It combines with bromine to form 3 :4-dibromo-1:1-climethylhexahydro-benzene, and on oxidation with potassium permanganate yields PP-dimethyladipic acid, a fact which dofinitely proves its constitution.A mixture of concentrated nitric and sulphuric acids acts on the hydrocarbon very violently and does not give rise to an appreciable quantity of a nitro-derivative. The properties of the hydrocarbon are being compared with those of lauroleue and isolaurolene obtained from derivatives of cltmphoric acid. 132. ('Bromine in solutions of potassium bromide." By Frederick P. Worley. The solubility of bromine in aqueous solutions of potassium bromide has been determined over a wide range of concentrations at 18.5" and 26*5c. The curves obtained for concentrations below 0.1 gram-molecule per litre correspond with an additional absorption of two atoms of bromine for every molecule of potassium bromide in solution, probably due to the formation of KBr,.The curves for higher concentrations of potassium bromide deviate slightly on the side of increased solubility of bromine, probably indicating the formation of small quantities of compounds higher than KBr,. The application of the principle of mass action does not lead to any knowledge of the constitution of the polybromide formed in the case of solutions saturated with bromine, but with solutions containing varying amounts of bromine insufficient for saturation the results confirm the formation of KBr, with smaller quantities of a higher compound. The variation of the constants obtained, on the assumption that 210 KBr, alone is formed, may be due to the unequal ionisation of potassium bromide and KBr,.A simple process has been devised for the determination of the quantity of a volatile substance present in a system containing various substances in equilibrium, where estimation by chemical means is not possible. It possesses the great advantage over other similar methods of avoiding the presence of a foreign substance such as carbon disulphide. 133. ‘‘Tetramethylammonium hydroxide.” By James Walker and John Johnston. A solution of tetramethylammonium hydroxide may easily be prepared by mixing alcoholic solutions of tetramethylammonium chloride and potassium hydroxide. Potassium chloride at once separates and may be removed by filtration. Tetramethylammonium hydroxide may be isolated from this solution as the pentahydrate, NMe,*OH,5H,O, by addition of water and concentration in a vacuum.A trihydrate and a monohydrate are also described. Attempts to prepare the anhydrous hydroxide failed owing to decomposition of the monohydrate into trimethylamine, methyl alcohol, and water. 134. (‘Tetrethylsuccinic acid.” By James Walker and Annie Purcell Walker. Crum Brown and Walker isolated from the product of electrolysis of sodium ethyl diethylmalonate a crystalline substance having the com- position C,,H,,O,. This substance is now shown to be the anhydride of tetrethylsuccinic acid. It is attacked by alkalis only with great difficulty, but forms sodium methyl tetrethylsuccinate by direct addition with sodium methoxide. This ester salt may be saponified by boiling with aqueous alkalis, and from the salt obtained tetrethylsuccinic acid may be isolated.It is stable in the solid state, but passes in solution or on fusion into water and the anhydride. 135. (‘The ultra-violet absorption spectra of aromatic com-pounds. Part 111. Disubstituted derivatives of benzene.” By Edward Charles Cyril Baly and Elinor Katharine Ewbank. Hartley (Trans., 1885, 47, 6S5), in describing the ultra-violet absorption spectra of the three xylenes, showed that the broad absorption band given by the ortho- and meta-compounds mas divided into two in the case of the para-compound. p-Xylene therefore gives two absorption bands, whiIe the ortho- and meta-compounds only show one band. In the present paper, the following substances are dealt with, the absorp- tion spectra of the three isomerides being described in each case : the chlorotoluenes, the dichlorobenzenes, the tolunitriles, the chloro-anilines, and the toluidines, the last two compounds being examined in acid solution.In every case, the para-compound shows either more absorption bands than the ortho- and meta-isomerides, or the same number of bands with much greater persistence. It may therefore be concluded that the para-compound is always more symmetrical than its two isomerides, that is to say, the motions of the benzene ring, which give rise to the absorption bands, are less disturbed by the para- substitution than by the ortho- and meta-substitutions. 136. “Studies in chlorination. 11. The action of chlorine on boiling toluene. Preliminary notice.” By Julius Berend Cohen, Harry Medforth Dawson, and Percy Field Crosland.The object of the authors’ experiments was to ascertain if electro-lytic chlorine, evolved in presence of boiling toluene, entered the side- chain like ordinary chlorine or caused substitution in the nucleus. The results show that, under the conditions of the experiments, electro- lytic chlorine enters the nucleus only, and also that the rate of chlorination appears to be more rapid than that of ordinary chlorine evolved from pyrolusite and hydrochloric acid. The current was con-ducted through the mixture of toluene and hydrochloric acid by means of carbon electrodes, a special series of determinations being made to find whether the electrodes acted as carriers.No difference could be detected in the character of the products when ordinary chlorine was used, whether carbon electrodes were present or not. When ordinary chlorine was used, between 80 and 90 per cent. of the product was benzyl chloride, the remainder being a mixture of 0-and p-chloro- toluenes. The experiments are being continued. 137. ‘‘Purpurogallin.” By Arthur George Perkin. When purpurogallin is methylated by means of methyl sulphate, it yields, in addition to the trimethyl ether previously described (Trans., 1903, 83, 194), the tetramethyl compound, C,,H,O(OCH,), (found, C = 65.18 ;H =5.90 ; CH, = 21.57, pale yellow prisms, m. p. 93-94’). isoPurpurogallone, for which the formula C,,H,O, was suggested, is more probably C,,HsO, (found, C=60*08; H=3.54); it gives on digestion with sulphuric acid in the presence of acetic acid the anhydride, C,,H,O, (C =65.36 ;H = 2.80, minute, yellow prisms melt- 212 ing above 310°), the acetyl compound of which is identical with that prepared by the act.ion of acetic anhydride on isopurpurogallone (Zoc.cit.). is0PurogaZZone tetyamethyl ether, CllH40(O*CH3)4(found, C =65.57 ; H= 5.62, colourless needles, m. p. 211-213'), is prepared by the action of methyl sulphate. The acid obtained from purpuro- gallin trimethyl ether by means of alcoholic potash at 180' (Zoc. cit.! gives numbers (C = 62.87 ; H =5.07) corresponding with the formula C13H1205,and is probably a derivative of isopurpurogallone.From purpurogallin tetramethyl ether, a similar compound can be prepared, and further work in this direction is now in active progress. 138. ('The electrolytic oxidation of hydroxybenzoic acids," By Arthur George Perkin and Frederick Mollwo Perkin. Twenty grams of gallic acid were dissolved in 100 C.C. of concen-trated sulphuric acid, and the solution then diluted with about one- third its volume with water and electrolysed in the anode compnrt- ment of an electrolytic cell, when about 30 per cent. of a colouring matter was obtained which had the appearance of, but was not identical with, ellagic acid; it gave an acetyl compound melting at 313-316'. Protocatechuic acid, when treated in a similar manner, gave catel- lagic acid, C,,H,O, (the yield being about 25 per cent.), the acetyl compound, C,,H,0,(C,H30),, melted at 322-324O.The electrolytic conditions employed were such as are generally used for preparing persulphuric acid, namely, moderately concentrated sulphuric acid and a high anode current density. By the electrolytic method, the catellagic acid obtained is purer than when potassium persulphate and sulphuric acid are employed. The reaction is being further studied, and will be extended to other hydroxybenzoic acids. ADDITIONS TO THE LIBRARY. I. Doncctwns. Prolich, 0. Die Entwickelung der elektrischen Messungen. pp. xii + 192. Braunschweig 1905. (Becd. 6/6/05.) From the Publishers. Jenkins, J. H. B., and Riddick, D. G. Photographs to illustrate Messrs.Jenkins and Riddick's paper on ''The microscopic examination 213 of metals.” Published in “The Analyst ” of January, 1905. (Recd. 5/6/05.) From the Editorial Committee of “Tho Analyst.” Nobel. Les Prix Nobel en 1902. pp. 181.. ill. Stockholm 1905. (Recd. 6/6/05.) From the Royal Academy of Sciences, Sweden. 11. By Purcltuse. Davy, Sir Humphry, Bart. Fragmentary remains, literary and scientific, with a sketch of his life and selections from his correspond- ence, edited by his brother John Davy. pp. viii + 330. London 1858. (Red 2/6/05 .) Pelbriick, M., und Schroho, A. Hefe, Garung und Faulnis. Eine Sammlung der grundlegenden Arbeiten von Schwann, Cagniard-Latour und Eutzing, sowie von Aufsatzen zur Geschichte der Theorie der Garung und der Technologie der Garungsgewerbe.pp. 232. ill. Berlin 1904. (Recd. 9/6/05.) Groth, P. Physikalische Krystallographie und Einleitung in die krystallographische Kenntnis der wichtigsten Substanzen. Vierte Auflage. pp. xiv + 820. Leipzig 1905. (Recd. 9/6/05.) Jiiptner, Hams von. Lehrbuch der physikalischen Chemie fur technische Chemiker und zum Gebrauche an technischen Hochschulen und Bergakademien. I Teil. Materie und Energie. I1 Teil. Chemisches Gleichgewicht und Reaktionsgeschwindigkeit. pp. 194, 358. Leipzig 1904, 1905. (Recd. 6/6/05.) 111. Pumphlets. Attwood, George. Plant for the handling and treatment of ores at the Silver Cup and Nettie L. Mines, British Columbia. (From the Minutes of Proc. Inst. of Civil Engineers, 159, 1904-1 905.) Cameron, Alexander T.The constitution of complex salts. I. Derivatives of the sesquioxides. (From the Proc. Roy. Soc. of Edilz-burgh, 25,1905.) Dixon, Harold B. The nature of explosions in gases. (From the J. Oxford G-niversity Junior Xcient$c Club, June, 1903.) Menschutkin, Boris N. AT. W. Lomonossow, der erste russische Chemiker und Physiker. (From the AnnuZen der NaturphiEosophie, 4, 1905.) Thomsen, Julius. Ueber den relativen Wert der zur Bestimmung der Verbrennungswarme fluchtiger organischer Verbindungen ben- utzten kalorimetrischen Methoden. (From the Zeit. phy8ikaZ. Chemie, 51, 1905.) Thomson, R. T., and Dunlop, H. On the examination of cod liver oil and other fiah liver oils. Glasgow 1905. 214 LIST OF FELLOWS, 1905. The List of Fellows for 1905 is now in active preparation, and no change of address received after July 31st, 1905, can be included in it. THE LIBRARY. The Library will be closed for Stock-taking from Monday, August 14th, until Saturday, August ZGth, 1905, inclusive. Fellows are particularly requested to return all books belonging to the Library, not later than Wednesday, August 9th. R. CLAY AND SONS, LTD., BREAD ST. HILL, E.C., AND HUNCAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9052100199
出版商:RSC
年代:1905
数据来源: RSC
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