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Proceedings of the Chemical Society, Vol. 21, No. 299 |
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Proceedings of the Chemical Society, London,
Volume 21,
Issue 299,
1905,
Page 215-245
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摘要:
Issued 10/11/05 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 21. No.299. The following are abstracts of papers received during the vacation and published or passed for publication in the Transactions. 139. ‘‘ Synthesis from glucose of an octamethylated disaccharide. Methylation of cane sugar and of maltose.” By Thomas Purdie and James Colquhoun Irvine. When a solution of tetramethyl glricose in pure benzene containing hj drogen chloride was heated at 105-1 15O, water was elirninatrd, and the rotatory PO\.Vrr increased. The product, when distilled under re-duced pressure, was a neutr.tl dextrorotittory syrup without multirota- tion, which was devoid of action on Fehling’s solution. The results of combustion and of m thoxyl estimation agreed with the composition of an octame thylated disaccharide.Moreover, tetramethylglucose, which was recovered by heating the compound with dilute hydrochloric acid, appeared to be the sole product of the hydrolysis. These results indicate that condensation had occurred between two molecules of tetramethylglucose in the y-oxide form, the product being an octa- methyl glucosido-glucoside, which appe trs to be the first example of a synthesised disaccharide of the non-reducing type, represented by cane sugar and trehalose. 140. iiStudies in the acridine series. Part 11. Action of methyl iodide on benzoflavine.” John Theodore Hewitt and John Jacob Fox. The authors have extended their work on 2-amino-3 :7-dimethyl-acridine (Trccns., 1904, 85,529) by an examination of benzoflavine 216 (2 :8-diamino-3 : 7-dimethyl-5-phenylttcridine). Acetylation with acetic anhydride and fused sodium acetate has furnished a diacetyE and small quantities of a tetracetyl derivative.Diace tylbenzoflavine gives a methiodide, C2,H,,02N31;ammonia acts on this giving a base C,,H230N3,one molecule of acetic acid being removed in addition to hydriodic acid. By completo hydrolysis (that is, a removal of both acetyl groups), salts are obtained of which the sulphte, (C22H21N3),,H2S0,,may be regarded as having a typical composition. The corresponding base does not contain oxygen, and since it lacks a carbinol hydroxyl its constitution must be regarded as para-quinonoid. 141. Note on certain derivatives of cyclopropene.” By David Trevor Jones.The diethyl ester of methylcplopropenedicarboxylic acid and the corresponding dimethyl ester both readily take up two atoms of bromine, ethyl dibromomethyltrimethylenedicarboxylatethus obtained being a liquid (b. p. 185’/30 mm.), whilst the dimethyl bromo-ester is a solid (m. p. 77”). When warmed with zinc and acetic acid, these additive products yielded the cyclopropene esters from which they were derived. When ethyl dibromomet hyltrimethylenedicarboxylate is condensed with two molecules of ethyl sodiomalonate, a non-volatile product is obtained, which, on saponification with potassium hydroxide, yields small quantities of a tribasic acid, C,H,O, (m. p. ‘232’). The intermediate non-volatile product appears to contain ethyl met hyldicyclotetranetetracarboxylate, the acid, C,H,O,, owing its formation to the splitting of a linking by potassium hydroxide with subsequent lactone formation.142. ‘‘Experiments on the synthesis of the terpenes. Part V. Derivatives of ortho-cymene.” By Francis William Kay and William Henry Perkin, jun. Terpenes belonging to the o-series have not previously been prepared, and the authors described a series of experiments by which many members of this group have been obtained, 217 143. “Experiments on the synthesis of the terpenes. Part VI. Derivatives of meta-cymene.” By William Henry Perkin, jun., and George Tattersall. The authors dealt with some hitherto unknown members of the nt-series of terpenes which havo been obtained from various derivatives of m-toluic acid with the aid of organo-magnesium compounds.144, ‘(Topic axes and the topic parameters of the alkali sulphates and selenates.” By Alfred Edwin Howard Tutton. The conception of “topic axes,” a combination of the crystallo- graphical axes with the molecular volume, introduced independently by &fiithmann in Germany and the author iu this country, has proved of great value as an expression of tlie fundamental morphological structure of ergs tals. The author’s surmise, published in 1894 (Trans., 65, 659), as to the existence of relatively large interspaces between the structural units has now been proved to bo a fact by tlie results of the determinations of the topic axes of the ammonium salts.The importance of correctly diagnosing the type of homogeneous structure present in a crystallised substance is emphasised, and the suggestion of Fedoroff (Zeit.Kryst. Him, 1902, 35, 129), that the type present in the crystals of the alkali sulphates and selenates is a pseudo-hexagonal one, is taken up and shown to be probably in ac- cordance with fact, although the symmetry is strictly rhombic; for the primary prism angle is less than 1’ removeJ from 60”, and the cry-tals frequently show a pseudo-hexagonal habit and form pseudo- hexagonal trip1 e ts. A new series of topic axes has therefore been calculated for these salts on the ahsumption of a pseudo-hexagonal space lattice, employing densities freshly determined with the aid of the suspension method for the calculdtion of the molecular volume involved.The results demon- strate even more elegantly the lams already published by the author, governing the relations of the morphological constants with the atomic weight of the alkali metal, and with that of the dominant negative element (sulphur or selenium) present, as also the rule regarding the position of ammonium near rubidium in the alkali series and the interesting corollary as to the existence of intermolecular and inter- atomic spaces. 218 145. '(The relation of position isomerism to optical activity. IV. The rotation of the menthyl esters of the isomeric nitrobenzoic acids." By Julius Berend Cohen and Henry Percy Armes. The previous observations on the effect of position isomerism on the rotation of menthyl benzoate have been confirmed.The p-nitro-group has the least, the o-nitro-group the greatest effect on the rotation, whilst the effect of the m-nitro-group lies between the two. The most striking difference in the effect of the nitro-group and that of the halogens previously studied (Trans., 1903, 83, 1313 ; 1904, 85, 1262) is that whereas the ortho-chlorine and -bromine atoms diminish the amount of deviation, the o-nitro-group enormously increases it, 146. ('Dinitroanisidines and their products of diazotisation." By Raphael Meldola and Frank George Coad Stephens. This paper is in continuation of former work on the elimination of a nitro-group on diazotisation and has been carried out in order to ascertain whether this elimination follows the ortho-para rule.The authors have found that when dinitro-o-anisidine is diazotised in presence of sulphuric acid and the product decomposed by heating with hydriodic acid there is obtained a mixture of a new iododinitroanisole (C,H,=OCH,*I*NO,*NO,= 1 :2 :4 :5), melting at 146-147O, and tl#e iodonitroresorcinol methyl ether (m. p. 115-1 16') formerly described. This result shows that under the conditions of diazotisation specified there results a mixture of a diazonium salt and a quinone-diazide (diazo-oxide). By the nitration of the monacetyl derivative of p-amino-phenol the authors have obtained, in accordance with the results recently published by Reverdin (Arch.2%. phys. ?zu,t,, 1905, 19, 353), the acetyl derivative of the isopicramic acid (C,K,*OH~NO,~NH,*NO,= 1 :2 : 4 :6) cd Dabney (Arrzer. Chem. J.,1883, 5, 33). On methylation, this acetyl derivative yields a new dinitroacetanisidide which, on hydrolysis, gives a new dinitroanisidine : O*CH, O*CH, N02f)N02 NO,f).NO, \/ \/'NH*CO*CH, NH2 M. p. 157". M.p. 212". I. 11. 219 OH O*CO*CH, N0,f)N02 NO,()NO, Al, p. 269-270". M. p. 259". 111. IV. The latter on diazotisation does not lose a nitro-group, but the methyl of the methoxy-group is eliminated with the formation of the dinitroqriinonediazide. The latter couples with P-naphthol in alkaline solution to form the azo-compound (ITI),the acetyl derivative of the latter (IV) being readily formed by heating the compound for a few minutes with acetic anhydride.The authors have also prepared the dinitroacetanisidide and dinitro- anisidine corresponding to the new dinitroaminophenol recently described by Reverdin. 147. '' Labile isomerism among benzoyl derivatives of salicyl-amide." By Arthur Walsh Titherley and William Longton Hicks. A conipound erroneously described by one of the authors (Trans., 1902, 81, 1533) as salicylbenzamide, OH*CGH,*CO*NH*CO*C,H,, melting at 120", which was obtained in the condensation of methyl-salicylate and sodium berlzamide, was shown to be a peculiar double compound of benzamide and salicylic acid, and AT-benzoylsizlicylaniide has not yet been isolated. There are, however, two o-benzoyl derivatives of salicylamide, one melting at 208", obtained in the above condensation, which is identical with the compound described by Gerhardt and Chiozza (Ann.Chim. Php., 1856, 46, 139), the other (m. p. 144') obtained by the authors by the wet benzoylation of salicy lamide by benzoyl chloride in presence of sodium carbonate. Neither gives any coloration with ferric chloride and there is strong evidence that in both compounds the benzoyl group is attached to phenolic oxygen. The more fusible isomerids is labile and passes with remarkable ease into the other, the transformation in most cases being quantitative. The change, however, is not reversible, and of the two it is the labile compound which must possess the ordinary amide structure, BzO*C6H,.CO*NH,, since only the stable form, o-benzoylsalicylimino- hydroxide, BzO C,H,*C(OH): N H ,yields metallic salts.Both forms on benzoylation in pyridine yield the same O-N-dibenzoyl- salicylamide, BzO*CGH,*CO-NHBz (m. p. 129'), the stable substance giving a theoretical yield, the labile isomeride furnishing a milch smaller proportion owing to simultaneous production of benzoyl- 220 salicylnitrile. There is evidence of the existence of two forms of the dibenzoyl derivative in equiiibrium when the stable form melting at 129’ is fused. On rapidly cooling, a brittle, amorphous g1:tss is obtained which melts at 55-60’, solidifies again at 85O, and then melts at 128O. 148. ‘(Preparation of benzeneazocoumarin ; its bearing on the constitution of p-hydroxyazo-compounds.” By Herbert Victor Mitchell.The existence, and extreme ease of formation, of benzeneazo-coumairin and the three nitrobenzeneazocoumarins favours the view that the p-hjdroxyazo-compounds are really phenolic in character AT)d not derivatives of quinonepheriylhydrszoiie. 149. ‘‘ The combustion of acetylene.” By William Arthur Bone and George William Andrew. The authors’ experiments proved that (1) the combustion of acetyl-ene does not involvc the preferential oxidation of either carbon or hydrogen. Separation of carbon or hydrogen, when it does occni-, must be entirely ascribed to secondary thermal decompositions. (2) Carbon monoxide and formaldehyde simultaneously arise at an early stage of the process, probably as the result of the decomposition C*OH of an unstable primary product C2H202,such as *** The forma-C*OH ’ tion of formaldehyde certainly precedes that of steam.The whole process may be represented by the following scheme : C*H CO +H*C:O -~ HO*C:O -+ HO*C:OE*H -+ [.*.C*OH] --+ C*OH H H 6H -*4-CO + H, CO +H,O CO, + H,O Stage 1. 2. 3. 4. Below the ignition point, the formic and carbonic acids produced at stages 3 and 4 respectively break down, forming steam and oxides of caibon, whilst above the ignition point the formaldehyde produced at stage 2 (or possibly also the dihydroxyacetylene at stage 1)is resolved into carbon monoxide and hydrogen. The explosive combustion ma,y therefore bo represented by the empirical equation C2H2+ 0, = 2CO +H2 (see Bone and Cain, Trans., 1897, 71, 26). (3) Below the ignition point, excess of oxygen ovep and above an equimolecular proportion always retards the combustion.This mas also shown to hold good above the ignition point by H. B. 221 Dixon in his experiments on the rates of explosion of acetylene-oxygen mixtures (Phil. Trans., 1893, 184, 183). (4)In contact with a hot catalysing surface, such as porous porce- lain, acetylene unites with steam, forming acetaldehyde. This action may take place even in presence of oxygen, and introduces a com-plication whenever the hydrocarbon is being burnt over a hot sur-face. In such circumstances, the secondary decomposition of acet-aldehyde might give rise to methane, or even carbon and hydrogen CH,.CHO =CH, + CO and carbon monoxide, thus : A (Bone and Smith, C + 2H, Ikatns., 1905, 87, 910).(5) Benzene is not produced in presence of oxygen below the ignition point. 150. Studies on the origin of colour-derivatives of fluorene.” By Ida Smedleg. Experiments were made with the object of throwing further light on the question, under what conditions in ketonic compounds can halogens play the part of oxygen in contributing to the formation of colonred substances. The results supported the view that the power of the carbonyl group to act as a chromophore is destroyed by re- placing the oxygen by two chlorine atoms; the effect of the other halogen atom requires further elucidation.Fluorenone chloride (m. p. 103’) mas prepared and was found to be colourless, but attempts to replace the chlorine by iodine atoms were unsuccessful. Fluorenone, fluorenone chloride, and 9 :9-dihydroxydiphenylfluorene (m, p. 223-224O) exhibit in a marked degree the property of “halo-chrornism ” when dissolved in concentrated sulphuric acid. The action of alcoholic potassium hydrosulphide on fluorenone chloride produced a colourless disulphide (m. p. 161’); the similar action of alcoholic potassium sulphide did not form a thio-ketone, as was expected, but produced the red hydrocarbon, bisdiphenylene-ethylene,and fluorenone. 151. “Note on the Zeisel reaction in the case of di-ortho-substituted phenolic ethers.” By David Runciman Boyd and John Edmund Pitman.Pyrogallol trirnethyl ether is readily decomposed by aqueous hydriodic acid (sp. gr. 1.6), giving the t,heoretical yield of inet,hyl iodide after heating for 45 minutes. Trichloroanisole and tribromoanisole, on the other hand, are left for the most part unaffected by such treatment. If, however, the aolu- 222 bility of these ethers is secured by employing, instead of aqueous hydriodic acid, a mixture of about equal volumes of hydriodic acid with glacial acetic acid, decomposition is complete after an hour’s heat- ing, and a theoretical yield of methyl iodide is obtained. 152. “The mechanism of the hydrogen sulphide reduction of nitro-compounds.’’ By Julius Berend Cohen and Douglas McCandlish. In the process of reducing different nitro-compound< with ammonium sulphide, or, as it is usually effected, with hydrogen sulphide in an alcoholic solution containing ammonia, great differences are noticeable in the rate of reduction, in the conditions under which reduction takes place, and in the niiture of the products formed.From a study of upwards of forty different nitro-compounds, the authors have laid down the following empirical rule : the i*ute of reduction is increased by the presence of acidic (NO, ,C0,Me ,C1) groups and diminished by that of basic grcups (CH, ,NH,), wad is further afected By steric Ihindrmce. The authors show further that the reduction occurs it1 at leust two well-defined steps, the first being attended by the formation of a hydroxylamine compound, which is ensily identified by its property of liberating iodine from potassium iodide.153. (( The arylsulphongl-p-diazoimides.” By Gilbert Thomas Morgan and Frances Mary Gore Micklethwait. The new series of arylsulphonyl-p-iliazoimides(Trans., 1905, 87, 74 arid 931) has been extended by the preparation and investigation of to1uene-p-sulpJhonyl-p-plLertyZened iazoinzide, 1;3-zyle,Le-4-sulpho?ayl-p-phenyletrediaxoirnicle, and the more complex benxe7l.e-1i 3-disulphon1J-bis-p-~l~a)LyZenediaxoina~~e,CGH,:[IV,].S0;~,H,.SO,‘ [N:J:C6H4. A detailed examination of the first of these compounds showed that (1) the molecular complexity of the arylsulphonyl-p-diazoimides corresponds with the simplest empirical formula for these sub~tances ; (2) cold mineral acids and even glacial acetic acid bring about a, disruption of the p-diazoimido-complex ; (3) the p-diazoimides readily yield azo-derivatives when condensed in an inert solvent with the phenols and the more reactive aromatic amines, and (4)when treated with caustic alkalis, preferably in alcoholic solution, the diazo- nitrogen of these diazoimides is eliminated and replaced by hydrogen.223 154. LL The reversibility of photographic development and the retard- ing action of soluble bromides.” By Samuel Edward Sheppard. It was shown experimentally that development is a reversible chemical reaction, and for ferrous oxalate the equilibrium factors mere determined quantitatively. The retarding action of bromides enabled the parts played by diffusion and chemical action to be defined, and a general theory of development on this basis was brought forward.155. (( Studies in chlorination. 111. The progressive chlorination of benzene in presence of the aluminium-mercury couple.” By Julius Berend Cohen and Percival Hartley. In the present paper a description is given OF the products obtained by the progressive chlorination of benzene from the monochloro- to the pentachloro-derivative. The results confirm the general rule which has been found to obtain in the case of the chlorotoluenes and the chloronitro-derivatives of benzene and toluene (Trans., 1902, 81, 1326, 1345 ; 1904, 85, 1276; 1905,87, 320), and which may be expressed as follows : The third substituent (chlorine atom or nitro-group) entering the dichloro-or chloronitro-benzenesor the monochlorotoluenes occupies the unsymmetrical position, forming a 1:2 :4-compound ; the fourth substituent (C1 or NO,) occupies position 5.In all the vicinal (I :2 :3) chloro-or chloronitro-derivatives of benzene and toluene, the fourth substituent (C1 or KO,) is adjacent to the other three. There is no marked exception to this rule, which, in the majority of cases, has reference to the only product of the reaction in question ;in a fern cases to the main product. 156. L‘ The interaction of sulphuretted hydrogen and arsenic pent- oxide in the presence of hydrochloric acid.” By Francis Lawry Usher and Morris William Travers. It has been found that in absence of hydrochloric acid, or in presence of very small quantities of that reagent, arsenic pentoxide is rapidly reduced, so that the reaction results in the formation of the trisulphide.With increasing concentrations of the acid, up to 25 per cent. strength, the product is the pentasulphide. In the case oE the reaction between arsenic pentoxide and sulphur dioxide in solution, hydrochloric acid exerted a similarly marked influence in retarding the rate at which the reduction took place. In presence of concentrated hydrochloric acid, the reaction results ill the formation oE the trisulphide. It was proved that in this case one has to consider the reaction of the arsenic pentoxide with the hydro- chloric acid as taking place much more rapidly than that which would result in the formation of the pentasulphide.The reaction of tlle arsenious compound and the chlorine with the sulphnretted hydrogen is practically instantaneous. 157. ‘(Studies in asymmetric synthesis. 111.. The asymmetric synthesis of I-lactic acid. The optical activity of fermentation lactic acid.” By Alexander McKenzie. Samples of fermentation lactic acid from various firms were examined polarimetrically and found to be sometimes dextrorotatory and some- times Ia?vorotatory. The author supposed that a mixture of unequal amounts of d- and I-lactic acids is invariably produced in the produc- tion of lactic acid from sugar by bacterial agency. Active lactic acid is not so readily racemised by alkali as is active mandelic acid.The asymmetric Synthesis of I-lactic acid was accomplished by reduc- ing I-menthyl pyruvate with aluminium amalgam, when a mixture of unequal amounts of I-menthyl d-lactate and I-menthyl 2-lactate, contain- ing an excess of the latter, is formed. When this mixture is hydrolysed by an excess of alcoholic potassium hydroxide and the I-menthol removed, a dextrorotatorg potassium salt, containing an excess of I-lactate over d-lactate, is produced ; this mixture, on acidification by a mineral acid, becomes lsvorotatory and forms a dextrorotatory zinc salt. 158. “The action of phenylpropiolyl chloride on ketonic corn pounds.” By Siegfried Ruhemann and Richard William Merriman. By the action of phenylpropiolyl chloride 011 the mono-sodio-deriv- ntive of ketonic compounds, the acetylenic ketones are not formed, but cornporincls which are shown to be derivatives of dihydrofurfuran. With the acid chloride, thus mono-sodioacetyhcetone yields acetyl- benzylidenemethylketodihydrofurfuran (m.p. 152-153’). Although insoluble in alkali hydroxides or carbonates, this compound is readily decomposed by these reagents. In secondary bases, such as piperidine, it dissolves with development of heat to yield deep blue solutions, from which hydrochloric acid precipitates an isomeric substance, 2-acetyl-5-hydroxy-4-phenyl-3-methyl-l-ketocycZopentadiene (m. p. 170”), crystallising from alcohol in red plates. This red isomeride has acidic properties, dissolving in piperidine and 225 alkali hydroxides or carbonates, yielding blue solutions, in which, how- ever, it is very unstable, the colour changing to yellow, slowly in the cold but readily on warming.The solution then yields, with hydro- chloric acid, the colourless ace tylphenylme thylcyclobutadienecarboxylic acid, also isomeric with the former compounds. Under the influence of cold concentrated sulphuric acid, the acid is transformed into an orange compound (m. p. 216-21 7”), to which the name indonecyclomethyl-acetoethylene has been given. This substance dissolves in aqueous alkalis, especially on warming, yielding violet solutions. Ethyl 5-benzylidene-2-methyl-4-ketodiliydrofurf uran-3-carboxylate, the product of the action of phenylpropiolyl chloride on ethyl monosodioacetoacetate, is analogous to the yellow componnd, C1,Hl,Oa ; it also dimolves in piperidine to yield a blue solution fram which hydrochloric acid precipitates a red solid similar in pmperties to tlie red compound, C14H1203.The action of phenylpropiolyl chloride on etliyl mono-sodionidonate furnished a yellow cornpound (m. p. 174--175”), which is either dicarboxylic acid. 159. (‘The influences regulating the reproductive functions of Saccharonqces cei*evisict.” By Adrian John Brown. The paper described the results of a continued investigation of phenomena associated with the reproductive functions of the yeast-cell to which attention had been previously called by the author (Trans., 1893, 61, 369 ; and 1894, 65, 911).160. ‘‘ Molecular refractions of some liquid mixtures of constant boiling point.” By Ida Frances Homfray. Nixtures of aldehyde and water give values of specific refractioii less than those calculated from the constituents, and these differer,cts form a regular series passing through a maximum. The iiiolecular refraction of aldefiydrol, CH;CH(OH),, hhould be less than that of acetaldehydeplus water, on account of the change of tlie oxygen atom from the carboxylic to the hydroxylic condition. The presence of aldehydrol, together with free aldehyde and water, is therefore coil-firmed, and an approximate estimate of the relative amounts has been made. Formic acid and water do not appear to combine at the ordinary temperature to form orthoformic acid.Acetone and water show a partial, but only slight, tendency to combination as CH,*C(OH),*CH,. Gautier has given reasons for considering that a definite chemical compound is formed, consisting of one molecule of ethyl cyanide and three of alcohol, and that this is the distillate obtained in preparing ethyl cyanide by Pelouze’s method. The refractive indices of a number of mixtures of different concen-trations have now been measured and the experimental curve so constructed used to determine the composition of the distillates under atmospheric pressure and under a series of lower puessures. In the former case, Gautier’s result is confirmed, but when the pressure is reduced, the distillate contains more cyanide.The density and specific and molecular refractions of the mixture agree with those calculated from the constituents. The conclusion is, therefore, that no compound is formed, and that this is a case of mutually soluble liquids of maximum vapour pressure. Cryoscopic determinations in benzene gave normal depression in the case of ethyl cyanide, but small values for dcohol and for the mixture of constant boiling point. Reasons are, however, given for attri-buting this, in both cases, to reduction of osmotic pressure rather than to molecular association or combination. -161. ‘(Molecular refractions of dimethylpyrone and its allies, and the quadrivalency of oxygen.” By Ida Frances Homfray. In most cases of associated compounds containing oxygen, the quadrivalency of that element is probable, and the observed mole- cular refractions are always in excess of those derived from the additive constants.The inference is that the atomic refraction of quadrivalent oxygen is greater than the highest of the values for the bivalent atom. No satisfactory data have been published for the determination of this constaut, and the compounds which appear to afford the best opportunity for such investigation are dimethylpyrone and its allies and derivatives. Accordingly, the molecular refractions of the following easily purified substances have been determined, and all data are given. Dimethylpyrone and its hydrochloride, the compound of dimethylpyrone and alcohol, diacetylacetone, pyrone and its hydro- chloride, pyromeconic acid, ethyl chelidonate, ethyl xanthochelidonate, and dehydracetic acid.Measurements were made in solution in various solvents, the specific refraction of the solute being deduced in the usual way. The possible error is estimated at about one per cent. When the usual formulae, not involving quadrivalent oxygen, are used, the calculated molecular refractions are in all cases con- siderably too low. The modified formula for dimethylpyrone proposed 227 0 /I\by Professor Collie is CH,*y I C*CH,, and all the other campounds c 0b examined here may be expressed by analogous formule. The atomic refraction of quadrivalent oxygen for the D-spectral line required by these formulae to satisfy the experimental numbers has been found by subtraction in each case, and a good agreement between these values is obtained, the mean being 2-73, The molecular refractions recalculated with this number for quadri- valent oxygen agree in most cases with the experimental to within the limit of accuracy of measurement.162, ‘6 The alkylation of mannose.” By James Colquhoun Irvine and Agnes Marion Moodie. a-Methylmannoside has been alkylated in methyl-alcoholic solution by means of silver oxide and methyl iodide with the production of a crystalline tetramethyl a-methylmannoside, and this compound, when hydrolysed by means of dilute hydrochloric acid, was converted into tetra methyl mannose. The alkylnted sugar proved to be a colourless syrup, and when heated with methyl alcohol containing 0.25 per cent.hydrochloric acid it behaved like mannose, producing only the a-modification OF the corresponding mannoside. Consequently the crystalline te tramethyl a-methylmannoside was the sole product of the reaction. When the alkylation was effected by means of silver oxide and methyl iodide, however, a different result was obtained. The product was a colourless, laevorotatory liquid, and this was shown to consist of a mixture of the a-and P-modifications of the fully methylated methylmannoside. The /3-isomeride differs from the a-form in its laevorotstion and in its ready hydrolysis by means of dilute hydrochloric acid or by the action of ernulsin. 163. The interaction of acridines with magnesium alkyl halides.” By Alfred Senier, Percy Corlett Austin, and Rosalind Clarke. By the application of Grignard’s reaction to acridine and its homologues, a series of coloured crystalline c3mpoun Is has been obtained.Endeavours to replace the metal magnesium by calcium were, however, unsuccessful, for. in attempting to prepare calciuin alkyl and aryl halides a change resembling Fittig’s rea..tion always 228 occurred almost exclusively (compare Beckmann, Be,,., 1905, 38, ‘304). The magnesium compounds, although readily formed, were very ditficult, to obtain in a pure state on account of their insolubility in inert solvents, and they were decomposed by glacial acetic acid, alcohol, and chloroform, the alcoholic solution yielding the original acridine. On employing as solvents for the reagents ethers of high boiling points, such as anisole and phenetole, or mixtures of either of these with ordinary ether, compounds of definite composition slowly crystal- lised.These products, which frequently change in colour on drying, retain variable proportions of ether, but this can be entirely removed by drying at 110-115°. Most of the compounds examined mere of the type of the diacridine hexahalidea previously described (~’Y~ZS.,1904, 85, 1199), and consist of two molecules of the base united with three molecules of the 6‘ reagent.” In the case of hexamethplacridine, however, the type is that of the tetrahalides, one molecule of base combining with tn70 of the (( reagent .” 164.‘‘ New method of determining molecular weights.” By Philip Blackman. Isotonic solutions of different substances in the same solvent havitig equal vapour pressures, it follows that if two solutions connected by vapour be allowed to athain equilibrium, their final volumes (cl,v,) will be inversely proportional to the number of dissolved molecules. 7)2 w1 v2 -This state of equilibrium is represented by the equation -* = nLd w2 ‘P, (where ml, m2, are tlie molecular weights of the substances, the weightg, wl,wp,of which are dissolved in the volumes, q,v2,of the same solvent). The apparatus consist’s of two graduated test-tubes connected by a T-piece, with a bulb in each of the limbs of the U-piece. The sub-stances are introduced into the test-tubes, the solvent added, and the solutions boiled.After a time, several readings of the volumes (vl, v2) are taken, and the molecular weight calculated from the fore- going equations. With careful boiling, good results can be obtainetl in remarkably short times. 165. Benzylphenylallylmethylammonium compounds. A com-plete series of four optically active salts.” By Alfred William Harvey. E-Benzylphenylallylmethylltmmonium I-camphorsulphonate has been prepared, having a inolecular rotatory power of an equal arithmetical value to that of its dextro-isomeride, and a series of s~ltsof the optically active base combined with optically active camphorsulphonic acids have been obtained of the type : dBdB ; ZBZA ; dBZA ; IBdA.The method of effecting the resolution of the iodide of the externally compensated base has been somewh,tt modified, whereby the difficulties previously experience1 have been obviated (compare Tra?as., 18119, 75, 1127, and 1901, 79, €328). 166. ‘‘ Solid solutions.” By Reinhold Frederick Korte. Experiments were made to determine whether barium sulphate precipitated in presence of a ferric salt forms a solid solution of ferric iron, or whether a ferrisulphate of barium is produced. The results showed that the amount of iron carried down with the barium sulphate does not increase in weight above a very small amount (about 1.3 per cent.), however much of the ferric salt be present ; also that there is R loss on ignition, implying the decomposition of an iron sulphate.Yrobably the point of saturation of barium snlphate with ferric iron is one in which the latter is present to only a minute extent, and it is also not impossible that the state of the ferric salt is that of :t ferric sulphate. The precipitation of calcium as oxalate in presence of SitltS of iiiagnesium was next examined. Here, when the proportion of mag-nesium to calcium oxide exceeds 36MgO to 5C/a0, a sudden rise in the proportion of magnesiiini to calcium takes place, from about 4.7 to 13.7 per cent. The magnesium is evidently present in the state of solid solution, and, although magnesium oxalate is an easily soluble salt, yet it canuot be removed from the calcium ovalat: precipitate by was11ing.In precipitating ferric hydroxide with aminoniLz in preseiiae of :L manganous salt, saturation of the ferric hydroxide with manganese takes place, when the proportion between Fe,O, and NnO in solntion is 5 : 1. A larger proportion of manganese in solution proluces no change in the amount retained by the ferric precipitate, namely, 2 per cent. The absorption of small amounts of manganese by iron is nearly complete, beiug as much as 95 per cent. From this it follows that on redis-solving and reprecipitating a ferric precipitate containing only a sinall proportion of manganese, little change in its composition takes place. Ferric hydroxide also dissolves nickelous oxide, and R saturhted solution is produced when the proportion between Fe,O, and NiO in solution is 5-9 to 1.230 Although manganous and nickel oxides are carried down with aluminium hydroxide, no regularity could be ohserved ; solid solution appears not to take place, but merely mechanic.il absorption by the gelatinous alumina. Lrad sulphate, precip;tnted in presence of other salts, does not carry down any metals in solid solution. 167. (‘The bromo-derivatives of camphopyric acid.” By John Addyman Gardner. When cis-camphopyric acid is treated with bromine in the presence of phosphorus penta .hloride and the mixture p )rirrd into water, the chief products are cis-bromocamphopyric acid and cis-brornocnmphopyric anhydride, a small quantity of trans-bromocamphopyric acid being also formed. IF, however, camphopyric anhydride is used instead of camphopyric acid, the chief products are trans-bromocamphopyric acid and bromo- camphopyric anhydride, little or no cis-bromocamphopyric acid being produced.truns-Camphopyric acid, treated in a similar way, using phosphorus trichloride instead of pent tchloride, yields mainly cis-bromocampho- pyric acid, a little anhydridp, but no trans-bromo-acid. The cis-acid is readily convertible into its anhydride by the action of acetyl chloride, but the truns-acid is not affected by this reagent. On the other hand, cis-hromocamphopyric anhydride, on boiling with water, is converted into a mixture of truns-bromocamphopyric acid arid decomposition products, probably of the cis-acid. The bromine atom is readily replaceable. By the action of nascent hydrogen, trans- bromocamphopyric acid yields trans-camphopyric acid, whilst both cis-bromocamphopyric acid and cis-bromocamphopyric anhy- dride give ordinary camphgpyric acid.Under the influence of alkalis, the bromine atom in both acids may be replaced by hydroxyl. 168. ‘‘The reduction of metallic oxides by aluminium carbide.’’ By John Norman Pring. Alloys of aluminium can be prepared by direct reduction of the oxide by carbon in presence of many other metals, whereas without such auxiliary metals the product consists chiefly of aluminium carbide. These considerations led to a detailed study of the reactions between aluminium carbide and metallic oxides and metals. It was found that the carbide behaves as a strong reducing agent.Up to 1400°, both the aluminium and the carbon are simultaneously oxidised, forming alumina, carbon dioxide, and the metal of the oxide. At higher 231 temperatures, however, selective reduction becomes apparent, the reduction being more and more brought about by the carbon of the carbide the higher the temperature of reaction, the result being that alloys of aluminium and the reduced metal are obtained, the percentage of aluminium increasing with the temperature and, in the case of hen, finally reaching the limit demanded by the equation Fe,O, +Al,C, = 2Fe. 4A1+ 3CO. Calcium carbide was found to exhibit a similar behaviour, but to a le*s marked degree, interaction between lead oxide and excess of molten calcium carbide giving an alloy containing 2.6 per cent.of calcium. Aluminium carbide reacts with metals at temperatures above the melting point of platinum to form aluminium alloys with liberation of free carbon; at higher temperatures, the reaction takes place with violence and is complete. A study of the action of metallic calcium on aluminium carbide showed that calcium carbide is formed at all temperatures above the melting point of platinum, and as aluminium acts on calcium carbide producing aluminium carbide, the reaction is probably reversible. 169. “The rusting of iron.” By Wyndham Rowland Dunstan, Hooper Albert Dickinson Jowett, and Ernest Gonlding. A detailed account is given of the investigation on the rusting of iron, an outline of which has been already published (Dunstan, Proc., 1903, 19,150).170. “Studies in comparative cryoscopy. Part 111. The esters in phenol solution.” By Philip Wilfred Robertson. The molecular depressions of the esters in phenol solution tend to increase with the concentration. In many instances, however, thc re is an initial association, that is, the molecular depression first decreast s, so that under these conditions a minimum is exhibited in the mole-cular depression curve. The concentration at which the minimum occurs is a characteristic for each ester, but is greater in the case of esters of high molecular weight. The initial association of these cornpounds becomes nore rapid as the molecular weight increases. The ethyl esters of the normal fatty acids differ from odd to even members of the series, but each division forms a perfectly definite series.Thus, in the case of the compounds with an even number of carbon atoms, the initial rnoleciilar depression reaches a maximum at the sixth member, falls to a minimum at the twelfth, and then rises to a second maximum when bhe chain contains sixteen carbon atcrms. The esters derived from pdybasic acids are characterised by the following behaviour. (1) Their molecular depressions increase rapidly with the conccn- tration. (2) The minimum in the molecular depression curve is not alw;iys exhibited. (3) They have extremely high initial molecular depressions. ,The negative ‘‘ rate ” of association and the abnormally high mole-cular depressions of the esters are probably due to the great tendency of phenol to form molecular complexes, since, in the case of the su1)-stitutecl phenols, thymol, guaiacol, and o-nitrophenol, which are not so strongly associated, these irregularities tend to disappear.171. ‘‘ The iodides of copper.” By James Wallace Walker and Nary Violette Dover. When equivalent solutions of potassium iodide arid copper sulphate are inixed, the resulting precipitate seems to contain n definite poly-iodide of copper mixed witti the cuprous iodide, and not,, as has been hitherto assumed, free iodine. Treatment of this precipitate witli water gives A deep red solution, the analyses of which point to the formula CuI, for the solid polyiodide.From ;t study of the eyui- librium between this solution and cuprous iodide, the authors conclude that it contains an equiniolecular mixture of CuI, and CuI,. The limit of concentration of pure cupric iodide 8olntion is almost exactly 0.1 per cent., removal of the water even in the form of ice inducing the reaction 6Cu1, CuI, + 6CuI. Even higher polyiodides than these cm be obtained from alcoholic solittion. 172. ‘‘The interaction of alcohols and phosphorous halides.” By James Wallace Walker and Frederick Murray Godschall Johnson. The authors have studied the yield of alkyl halide obtained in the action of phosphorous chloride, bromide, and iodide on methyl, ethyl, and n-propyl alcohols, in the hope of finding a general equation snch as PX, + 3A-OH =Y(OA), -y(OH)u+ (3 -9)HX + yAX, applicable to the several cases.In this equation, X represents a halogen atom and A an alkyl group. In the production of methyl and 7z-propyl bi-omides and of ethjl iodide, the value of y is 2 ;in the case of ethyl chloride, it is 1. In the other instances, the above equation woulcl require to be doubled to express the results, The high degree of solubility of yellow phosphorus in methyl iodide suggested a ready method for the YO-duction of that substance in quantity. The theoretical weight of iodine is added to a 10 per cent. solution of phosphorus in melhyl iodide, and the equivalent amount of alcohol is slowly introduced. Enough phosphorus is then dissolved in the resultant liquid to pio-duce again a 10 per cent.solution and iodine and alcohol are added as before. By continuing this process a large quantity of meshy1 ioJide may be obtained in a short time, the yield being 94 per cent. of the theoretical. Only 65 per cent. of the theoretical yield of ethyl iodide was obtained by this method. Instead of employing the pliospliorn;; and iodine in the ratio required for the production of the tri-iodide, an almost equally good result is obtained by addiug enough iodine to produce the pents-iodide, tliis compound being much more soluble thnn the tri-iodide in methyl iodide. 173. “The electrical conductivities of some salt solutions in acet- amide.” By James Wallace Walker and Frederick Murray Godschall Johnson. The salts examined were mercuric chloride, potassium chloride, iodide, and cyanide.Of these, the first is tile only normal electrolyte, the others showing a maximum of moleunlar conductivity rtt about 30 or 40 litres, which then falls to about half value on dilution. Mercuric chloride is known to give a compound with acetamicle and potassinin iodide is found to yield the compound K1,6CH3.CO.NE€,. The rnig1-a-tion ratio of the iodion is found to be greater thnn in aqueons soli~tiori n, fact which points to combination of the ions with the solvent. 174. Contributions to our knowledge of the aconite alkaloids. Part XQI. Indaconitine, the alkaloid of Aconitunacl~nsnza)zthcn7.,’ By Wyndham Rowland Dunstan and Albert Edward Andrews. lndaconitine is EL highly poisonous alkaloid which has been obtained from the Indian plant known as “mohri,” at first, thought to be the same as the European AcoPzitum Nc6pellus, but now recognised as n distinct species, Aconitum chasrnc6nthwn~ In this paper a full account is given of the properties of the alkaloid and of its principal salts.Indaconitine (C,;H,70,,N) is a crystalline alkaloid very closely resembling aconitine from Acor~itunziVqveZlzcs in its general properties, but differing, however, in its habit of crystallisation and in msriy of its phpical properties. Most of the salts crystallise well and are distinct from the corresponding aconitine salts. Its physiological action has been shown to closely resemble that of aconitine and pseudaconitine (Cash and Dunstan, Proc.Roy. Xoc., 1905). Indaconitine undergoes hydrolysis in two stages, in the first of which an acetyl group is eliminated as acetic acid, with the formation of a base, indbenzaconine, which has not been crystallised, but furnishes crystalline salts. This hydrolysis is represented by the equation : C,,H470,,,N + H,O =C,H,02 +C32H45()9N. Indbenzaconine is practically non-poisonous. On further hydrolysis, indbenzaconine f urnibhes benzoic acid and pseudaconine identical mith the final hydrolytic product of pseudaconitine. Indaconitine is therefore of interest as representing a type of highly toxic alkaloid intermediate in its properties between the aconitine of the common European aconite (A.flapellus) and the pseudaconitine derived from the Indian aconite of Nepal.The discovery of this alkaloid and its proximate constitution has led the authors to change the formula of pseudaconitine from C,,H,,O,,N, the formula originally assigned to the alkaloid by Wright, to C36H51012N. 175. “ Contributions to our knowledge of the aconite alkaloids. Part XVII. Bikhaconitine, the alkaloid of Aconiturn spicaturn.” By Wyndham Rowland Dunstan and Albert Edward Andrews. This alkaloid, like indaconitine described in the previous com-munication, is highly poisonous, It has been isolated from a supposed variety of Aconitum ferox of India, which has now been proved to be a distinct species, Aconitum spiccdum. The vernacular name of the plant being ‘‘ bikh,” the name bikhaconitine is proposed for the new base.Rikhaconitine (C,,H,,O,,N) does not crystallise so readily as other ‘‘ aconitines,” and its physical properties are distinct. A number of its salts have been prepared, and most of them crystallise well. Its physio-logicnl action very nearly resembles that of the other sconitines : its toxicity towards warm-blooded animals is greater than t’hat of either aconitine or japacouitine, but is slightly inferior to that of pseudaconitine, which is the most poisonous alkaloid of the group. Bikhaconitine, like the other aconitines, undergoes hydrolysis in two stages. In the first of these, an acetyl group is eliminated as acetic acid, forming a new base (veratroylbikhaconine). This alkaloid does not crystallise, but furnishes crystalline salts.On further hydrolysis, veratroglbikhaconine furnishes veratric acid and bikh- aconine, which does not crystallise, but furnishes crystalline salts. This alkaloid differs from other ‘‘aconines ” previously described. The paper contains a full account of the properties of bikhaconitine, its salts and derivatives, and a comparison of their properties with those of the other aconitines which have been previously described. The formula of bikhaconitine differs from that of pseudaconitine by one atom of oxygen. l‘176. Contributions to our knowledge of the aconite alkaloids. Part XVIII. The aconitine group of alkaloids.” By Wyndham Rowland Dunstan and Thomas Anderson Henry. This paper gave a general account of the properties of the several closely allied “ aconitines ” which have been described in the course of the present investigation, and also of the non-poisonous alkaloids obtained from varieties of aconite.It is pointed out that now that it has been established that closely related Indian aconites f iirnish similar, but nevertheless quite distinct, toxic alkaloids, it is most desirable that a similar examination should be made of the European aconites of the type of Aeoniturn Napellus. The work of Wright, Jurgens, and other chemists, as well as that of the present inves- tigators, renders it highly probable that an examination of European plants commonly classed as Aconitzcm ATapeZZus will reveal the presence of alkaloid3 very closely resembling, but yet distinct from, aconitine.The evidence already recorded goes to show that the aconitine isolated by Wright from English plants and annlysecl by him and others, which was described in the course of the present in-vestigation, is a distinct substance from the aconitine of German origin which is now an article of commerce. Thursday, November Znd, 1905, at 8.30 p.m. Professor R.HELDOLA, F.R.S., President, in the Chair. Jlessra. W. B. Tuck, J. W. White, and E. W. Bealey mere formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Adam Lawson Kelly Adam, 296, Bath Street, Glasgow. C. Chester Ahlum, Lansdale, Pennsylvania, U.S.A. James Edward Alcock, 42, Gill Street, Moston Lane, Blackley.James Albert Allison, Luchana Laboratory, Apartado 45, Bilbao, Spain, George Henry Barbrook, Stowmarket, Suffolk. Marmaduke Barrowcliff, 25, Priory Road, Kew, Surrey. John Coggin Brown, B.Sc., Fairleigh, Cockton Hill, Bishop Auckland. Joseph Edward Coates, I3 Sc., Sunny Side, Oakatuoor, Stoke-on-Trent. Douglas Henry Bellars C Jwrnan, Heathville Corner, Gloucester. Arthur Angustine Ddlmen, Lyndhurst, Prospect Vale, Liverpool. John Llewelyn Davies, R.A., 8, Rugby Road, Nenth. John Doull, 8, Lauriston Place, Edinburgh. John Beaconsfield Gall, Knoxlnnd, Erith Road, Belvedere, Kent. Sidney Montague Haig, St. Edniuncl’s Ave., Port Hill, Stoke-on-Trent. Alfred Hart, AI.A.,B.Sc.,Norrnan Avenue, Hawksburn,Victoria, N.S.W.Jack Vernon Johnson Hitymnn, Tringhnrst, Cranleigh, Surrey. John Michael Higgios, 39, Queen Street, A‘lelbourne, Australia. William Basil Hill, Eastfield, Stockton Lane, York. Isaac Berkwood Hobsbauin, 79, Cluremont Road, Forest Gate, E. Cecil Hollins, 34, Beamsley Road, Frizinghall, Yorks. Maurice Brooks Jack, 66, Burma Road, Clissold Pctrk, N. Edward Towyn Jones, B.Sc., 17, Rloomsbury Square, W.C. Rudolph Lyon, 400, Huddersfield Road, Halifax. Williani NcClenry, 61, Station Road, Pendlebury, Manchester. Kobert Drystlale MscICechnie, c/o Xessra. A. Boake, Roberts and Cu., Ltd., Stratford, E. Harry Martin, 14, Hardman Street, Liverpool. Harry GeorgeFletcherXicklewright,B. A., 116, St. James’s Rd.,Croyclou. Edalji RIanekji Nodi, opposite Grant Road Station, Bombay.John Motion, Edgewvater, New Jersey, U.S.A. Henry Allen Dagdale Neville, B.Sc., 81, Revidge Road, Blackburn. Francis Richard Penn, Highthorne Terrace, Shadwell Lane, Moortowu, Leeds. Hugh Donald Perkios, Dodwell, Cursledon, Hants. Percy Barker Phipson, c/o J. Staples and Co., Ltd., Wellington, N.Z. Frederick John Pooler, B.Sc., The Boys’ High School, Grahamstown, Cape Colony, South Africa. James Frederick Fothergill Rowland, B.A., 5,St.James’s Yk.,Croydou. Harold Marmion Roylc, 12, Barfield Villas, George Lane, 8. Woodford. Harry Nestor-Schuurmanri, Corinth House, Cheltenham. Douglas Temple Setterington, 45, Regent Road, Blackpool. John Booty Tillott, 55, Woocl Street, Westminster, S.W. Flank Tutin, 19, The Avenue, Kew, Surrey.George Stanley Walpole, 349, Queen’s Road, Battersea Park, S.W. JohnLedger White, D.Sc., 73, Cambridge Mansions, B tttersea Pk.,S.W. Gerard William Williams, B.A., P.O. Box, 21, Germiston, Trausvaal, S. Africa, 237 The PRESIDENTreferred to the loss sustained by the Society in the death of Professor P. T. Cleve, who was elected an Honorary and Foreign Member in February, 1883, and who died on June 18th’ 1905 ; also in the death of hlr. G. I;. Buckton, F.R.S., who was electelf :L Fellow in &larch, 1852. Of the following papers, those marked % were rend : *177. ‘(Molecular conductivity of water.” By Philip Blackman. The molecular conductivity of water may be represented by K arid calculated from the equation The value of K is dependent on (1) temperature, (2) molecular conceu- tration, and (3) nature of the acid (puIlx, punflOII, representpuuMlx respectively the molecular conductivities, measured at the same teiii- perature and molecular concentration, u, of the acid HX, the base M,OH, and the salt MIX).The conclusion is drawn that the greater the value of lithe stronger is the acid (taking into consideration (I) the temperature and (2) the molecular concentration). This furnishes a method for de4 eimining the relative strengths of acids. “178. ‘;The stereoisomerism of substituted ammonium compounds.” By Humphry Owen Jones. The existence of Wedekind’s isomeric a-and P-phenylbenzyliiiethyl- allylammonium iodides is so difficult to reconcile with the absence of isomerism in all the other compounds of the same type that the author has examined these compounds in the hope of obtaining some informa- tion about this unique example of isomerism, and has found that the two compounds are not isomerides, but different compounds.The P-compound dissociates partially into benzyl iodide and tertiary nmine in chloroform solution, but is not transformed into the a-coru-pound ; it is also completely converted into phenyltrimethylammonium iodide when heated at 100” with methyl iodide in molecular proportions, whereas the a-compound requires twice as much methyl iodide to con- vert it into phenyltrimethylammonium iodide and benzyl and ally1 iodides. Analysis and a comparison of properties prove conclusively that the P-compound is phenylbenxyZ~i.nzethylccnz~~zoniunziodide. The analyses of the compound previously given by Wedekind arid by Hantzsch and Horn are incorrect, and the reactions described 238 by the last-mentioned chemists can only have been obtained with impure material.The reaction between benzylallylaniline and methyl iodide in the cold is expressed by the equation C7H,*NPh*C,H,+ 2CH$ = NPhMe,(C,H7) I + C,H,I, and at 100" by the equation C7H,*NPh*C3H, + 3CH31=WPhMe31+C3H,I+ C,H,I. At present optical activity is the only evidence of stereoisomerism of quinquevalent nitrogen compounds of the type NabcdX, and, since the search for isomerides has been so thorough, it is concluded that no isomerides can be produced by the union of tertiary amines and alkyl iodides.The hypothesis suggested by the author (Tvcms., 1903, 83, 1403) to account for the non-formation of isomeric quinquevalent nitrogen derivatives from tervalent compounds is now adequate to explain all the known facts and has been further devcloped. DISCUSSION. Mr. A. W. HARVEYstated that he had prepared considerable quantities of benzylphenylmethylallylammoniumiodide, and that when the compound is produced by mixing molecular quantities of carefully purified benzylmethylaniline and allyl iodide in an equal volume of mixed methyl and ethyl alcohols (1-9) no trace of Wedekind's P-compound is formed ; the reaction goes quite quantitatively, and yields a clean and pure solid product.Dr. JONES,in reply, said that the /?-compound was not produced together with the a-salt when allyl and benzyl iodides were added to the corresponding tertiary amines, but only when methyl iodide was used. In reply to a question by Dr. Lapworth, the author stated that the evidence for the replacement of allyl by methyl in benzylallylaniline by the action of methyl iodide in the cold was quite conclusive, the benzyl group being only removed on heating. "179. (( Note on the fluorides of selenium and tellurium." By Edmund Brydges Rudhall Prideaux. The fluorides of selenium and tellurium are both gaseous substances prepared by the action of fluorine on the elements, their densities corresponding to the formulz SeF, and TeF, respectively.They are easily condensable by cold alone, forming white, snow-like solids, the vitpour pressure curves of which will be published shordy along with an account of the other properties of the gases. 239 DISCUSSION. Mr. BLISSasked whether the author could give any further informa- tion as to the nature of the solid fluorides isolated by Moissan. Mr. PBIDEAUX,in reply, said that the solid fluoride of tellurium left in the reaction tube may be the tetrafluoride, TeE’,, described as being obtained by the action of hydrogen fluoride on tellurous acid, but is more probably an oxyfluoride. *180.L6 The constitution of glutaconic !acid.” By Jocelyn Field Thorpe. The ‘‘ double bond ” in glutaconic acid, CO2H*CH,*CH:CH*CO2H, is apparently not fixed, since the reactions of this substance clearly indicate that it possesses a symmetrical structure.Thus ap-dimet hylglutaconic and by-dimethylglutacanic acids, prepared by methods which leave no doubt as to their constitution, are not isomeric but identical. a-Methyl-P-ethylglutaconicacid and P-methyl- y-ethylglutaconic acid are also identical. Derivatives of glutaconic acid are produced when ethyl cyanoacetate or its monoalkyl derivatives react with ethyl acetoacetate or its mono- alkyl derivatives, the ethyl salts formed yielding either (1) det ivatives of glutaconic acid or (2) derivatives of 2 : 6-dioxypyridine, according 1o the nature of the hydrolysing agent and the constitution of the salt. “181. (‘Some alkyl derivatives of glutaconic acid and of 2 :6-dioxy-pyridine.” By Harold Rogerson and Jocelyn Field Thorpe.Methods for the preparation of all the methyl derivatives of glutaconic acid are detcribed, as well as the modes of preparation and properties of the corresponding derivatives of 2 :6-dioxypyridine, *182. “Note on the formation of P-methylglutaconic acid and of ap-dimethy lglutaconic acid.” By Francis Vernon Darbishire and Jocelyn Field Thorpe. By the elimination of hydrogen bromide from ethyl a-bronio-/3-methyl- glutarate a mixture is obtained from which P-methylglutaconic acid can be isolated, the residue consisting of the lactone ethyl salt and the corresponding acid of the trimethylene ring. From ethyl a bromo-up-dimethylglutarate,similar products are formed, only in this case a much larger quantity of the glutaconic acid (up-dimethy lglutaconic acid) can be obtained.240 "183. The influence of water and alcohols on the boiling point of esters. I. A modification of Markownikoff's method of preparation." By John Wade, Ethyl acetate forms binary and ternary mixtures of minimum boil- ing point with ethyl alcohol and water. The ternary mixture, which contains 9 per cent. of alcohol and 8 per cent. of water, boils constantly at 70*3", whilst the binary mixtures, which contain respectively 8.6 per cent. of water and 30.6 per cent. of alcohol, boil constantly at 70.5' and '71.8". Most esters form such mixtures with their con-stituent alcohols and water, and in 'preparing esters from acids and alcohols by MarkownikoE's method of continuous distillation in presence of sulphuric acid (Bey., 1873, 6, 1177), ternary mixtures are therefore usually obtained.As the Markownikoff interaction, unlike the et herificntion process on which it is based, now proves on investigation to proceed in most cases readily at loo", and in presence of any strong acid, it may be modified to afford a general and practically automatic method of preparing these ternary mixtures and their constituent esters in quantity. The lower alkyl esters of formic, acetic, propionic, and butyric acids have been made in this way under ordinary pressure, and various less volatile esters at the samo temperature under somewhat reduced pressure.Owing to the peculiar relation of the binary to the ternary mixtures the excess of alcohol may ciften be removed from these products by distillation with water and fractionation. "184. "Note on bromine fluoride." By Edmund Brgdges Rudhall Prideaux. Fluorine when passed over bromine combines with it, as stated by Moissan, who has described t,he appearance of the reaction (" Le Fluor et Ses Compost%"), The product, which is more unstable than iodine fluoride and decomposes water with great violence, has not been described. It is a pale yellow liquid with a specific gravity less than that of bromine, and freezes to a white solid which melts at -2O. The analysis of this fluoride leads to the formula BrF,, and this compound appears to be the only definihe fluoride of bromine.185. '' Solution and pseudo-solution. Part IV." By Ernest Linder and Harold Picton. The authors have completed, so far as they are able, the study of solution and pseudo-solution originated by them in 1893 (Trmzs.,81, 114-148). The resnlts are arranged in three sections. 241 Section I. The Phgsicul and Chemical Properties of Colloidal Arsenious Su?phide.-The precipitates, which separate when arsenious sulphide is coagulated by metallic salts, are regarded as metallic derivatives of a complex hydrosulphide formed by interchange of hydrogen for metal. Thus, xAs,S3,H,S +BaC1, =xAs,S,,BaS +2HC1. The coagulation process for salts of uni-, bi-, and ter-valent metals is reviewed in the light of this hypothesis.Quadrivalent metals, such as platinum and zirconium, are found to be non-coagulants of arseni-ous sulphide in dilute solution. The aggregation and de-aggregation phenomena of arsenious sulphide have been studied microscopically. Section 11. Yhe I’lqsical and Chemical Properties of Colloidal Ferric Hydroxide.-Various ‘(grades ”of colloidal ferric hydroxide have been prepared by dialysis. The physical and chemical properties of certain of these solutions and the coagulation phenomena of the colloidal hydroxychloride have been studied by methods similar to those applied in the investigation on arsenious sulphide. &&on 111. Dyeing, a Phase of Coagulation.-The kc substantive dyeing ” of colloidal ferric hydroxide and arsenious sulphide by methyl- violet and aniline-blue is shown to exhibit phenomena which are pre- cisely analogous to those occurring when these colloids are coagulated by metallic salts.186. “The influence of very strong electromagnetic fields on the spark spectra of ruthenium, rhodium, and palladium.” By John Edward Purvis. The experiments were made with a 21-foot concave grating spectro- scope. The spark passed between electrodes of the metals which were firmly held between the poles of a magnet. The strength of the field between the poles of the magnet was 40,000 units with a current of 21 amperes. The nature of the vibrations was analysed by a calcite prism. The general results showed that (1) most of the lines are divided into triplets, and that there is a periodic or rhythmic change in the direc- tions of the vibrations of the constituents of the triplets.(2) Some lines become quadruplets, and within certain definite regions of the spectrum their constituents also change the directions of their vibrations. (3) Other lines become doublets. (Only a very few lines are not affected when vibrating in the magnetic field.) (4) The inner member of the triplets is usually the strongest ;but this is not always the case. The two outer inembers of a triplet may be stronger than the inner one; and all three are sometimes equally strong. 242 (5) The strongest spectral lines are not the most widely separated when vibrating in the field. Weak lines are usually more widely separated than strong ones.(6) The decrease in the width of the triplets does not proceed pari passu from the less refrangible to the more refrangible end of the spectrum. 187. ‘‘A volumetric method of estimating the cinchona alkaloids by means of their double thiocyanates.” By Philip Wilfred Robertson. Skey has pointed out that many alkaloids give precipitates with ammonium thiocyanate in the presence of a zinc or mercury salt. Many other metals act in a similar manner; zinc, however, forms the most insoluble precipitates. The alkaloids most sensitive to this reaction are quinine and the cinchona alkaloids. Thus in the presence of excess of zinc sulphate and ammonium thiocyanate, one part of quinine gives a distinct turbidity in 50,000 parts of water.These precipitates prove to be double salts of considerable complexity, as is the case with the compounds of many alkaloids, more especially quinine and its allies. Thus cinchonine ammonium zinc thiocyanate has the following com- position : 4Cl,H220N2,3Zn(CNS)2,2NH,CNS,4HCNS. This formula corresponds closely with that of herapathite or iodo-quinine sulphate, 4C,,,H2,0211rj2,3H,S0,,2HI,412,3Aq. Notwithstanding the complexity of these double salts, the determinn- tion of the amount of thiocyanate removed from solution by the alkaloids forms an accurate and speedy volumetric method of estimating quinine in the commercial drugs and in the assay of the crude cinchona bark. 188. (‘The osmotic pressure of sugar solutions in mixtures of alcohol and water.” By Percival Smith Barlow.Some experiments have been made with copper ferrocyanide membranes and solutions of sugar in a mixed solvent of alcohol and water, which confirmed Tammann’s observation that an osmotic current cannot be obtairred with these membranes and alcohol. The author’s experiments mere spread over a considerable time, in some cases mont,hs being allowed to elapse, so that every opportunity might be afforded for the pressure to show itself. For membranes perineable to water only, the van’t Hoff value of the osmotic pressure is very much diminished by the presence of the alcohol, but no idea has been obtained as yet of any relation between the amounts of alcohol present and the amount of the reduction in the pressures; below a certain strength of sugzr solution there is no direct evidence of osmotic pressure, the alcohol present quite overshadowing the effect of the 243 sugar. There are indications that the membrane is rendered permeable to the sugar by the presence of alcohol.For a membrane permeable to the alcohol only, the pressure set up is very much less than above, and is produced extremely slowly. Whatever molecular aggregates are formed in connection with the sugar, it seems that the alcohol molecules take much less part in them than the water molecules. ADDITIONS TO THE LIBRARY I. Donations. Baumhauer, H. Die neuere Entwickelung der Kristallographie. pp. viii + 184. Braunschweig 1905. (Recd. 29/7/05). From the Publishers.Berthelot, Marcellin Pierre Eughe. Trait6 pratique de calorim6r rie chimique. Deuxikme Qdition. pp. xiii + 317. ill. Paris 1905. (Reccl. 14/8/05.) From the Author. Day, Arthur L., Allen, E. T., and iddings, J. P. The isomorphism and thermal properties of the feldspars. (Carnegie Institution of Washington, Publication No. 31). pp. 95. ill. Washington 1905. (Recd. 18/7/05.) From the Autt,ors. Dunstan, A. E. Elementary experimental chemistry. pp. viii + 173. ill. London 1905. (Reccl. 26/9/05.) From the Autlior. Francesconi, Luigi. Santonina e suoi derivati. pp. lS4. Rome 1904. (Kectl. 4/7/05.) From the Author. Geitler, Josef Ritter von. Elektromagnetische Schwingungen und Wellen. pp. viii + 154. Braunschweig 1905. (12ecd. 29/7,05.) Froin the Piib1ishei.s.National Physical Laboratory. Collected researches. Vol. I. pp. 279. ill. [London 1905.1 (Recd. 28/7/05.) From the National Physical Laboratory. Trait6 de chimie minkrale. Publik sous la direction da Henri Moissan. Tome 11, Fasc. 2. Tome IV, Fasc. 2. pp. 258, 471. Paris 1905. (Reference.) From Professor H. Xoissan. United States. Changes in the Pharmacopoeia of the United States of America. Eighth decennial revision. By Reid Hunt and Murray Galt Motter. pp. 122. Washington 1905. (Eecd. 4/10/05.) From the U.S. Treasury Department. 244 Werner, A. Neuere Anschauungm auf den1 Gebiete der anorgan-ischen Chemie. pp. xii + 189. Braunschweig 1905. (Recd. 29/7/03.) From the Publishers. Whiteley, R. Lloyd. An elementary text-book of inorganic chemistry.pp. viii + 245. ill. London 1905. (Recd. 24/10/05.) From the Publishers, 11. By Yurchuse. Landolt, Hans Heinrich, BGrnstein, Richard, uncl Meyer hoffer, Wilhelm. Physikalisch-chemische Tabellen. Uritte Auflage. pp. xvi + 861. Berlin 1905. (Eefevence.) Haly, E. C. C. Spectroscopy. ill. pp. xi+568. London 1905. (fiscd. 11/7/05.) Seeker, George F., and Day, Arthur L. An interesting pseudo- solid. (From the Proc. lVasl>o?t Acucl. of Sci.,7,1905.) -The linear force of growing crystals. (From the I’YOC. Wccshington Acad. OJ Xci., 7, 1905.) Clarke, F. W. On basic substitutions in the zeolites. (From the Proc. TVashington ACCC~.of Sci.,7, 1905.) Corlette, Cyril E. A review of the subject of starch digestion in young infants.(From the Australasian Medical Gazette, 24,1905.) Fleckenstein, A. Eigenschafteo von S;ilzliisungen in Gemischen von Alkohol und Wasser. (From the Z’hysikaZische Zeitschrift, 6, 1905.) Gebharilt, A. Uber den Dampfdruck von Quecksilber und Natrium. (From the Veihmadl. d. Phys, Ges., 7,1905.) Gray, George. On the retrogression of soluble phosphates in mixed manures. (From the Trans. Australasian Assoc. Adv. Sci., 1904.) Hesa, a. Methode zur Bestimmung der Volumeniinderung beim Schmelzen. (From the PhysikaZische Zeitsclwift, 6, 1905.) Hirt, W. B., and Steel, IF. W. A rapid volumetric method for the determination of phosphoric acid. (From the Proc. Soc. Chem. Imd. Victoria, May, 1905.) Matthies, W. Uber Potentialmessungen im Joddampf.(From the Sitxungsber. physikal. -metZiziw. Sox. Edangem, 37, 1905.) Reade, T. Mellard, and Holland, Philip. Sands and sediments. (From the Proc. Liverpool Geol. SOC.,1903-1905.) Thwaite, B. H. Accidents clue to asphyxiation of blast-furnace workmen. (From the J. Iron mzd Steel hst., 1905.) Wiedemann, E. Uber Darnpfdrucke, besonclers solche von festen 24.5 Korpern, uach Unterauchungen voii K. Stelzner und G. Niederschulte. (From the Verhundl. d. Phys. Ges., 7, 1905.) Yorkshire Geological and Polytechnic Society. The undergrouiid waters of North-West Yorkshire. Part 11. The underground waters of Ingleborough. (From the Proc. Forks. Geol. and Polytech. Xoc., 15, 1904.) RESEARCH FUND. A Meeting of the Research Fund Committee will be held in December next.Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on or before Monday, December 1I th, 1905. At the next Ordinary Meeting, on Thursday, Xovember 16th, 1905, at 8.30 p.m., the following papers will be communicated : ‘‘Silicon researches. Part IX. Bromination of silicophenyl imide and amide, and formation of a compound including the group (SIN).” By J. E. Reynolds.‘‘Condensation cf ketones with mercury cyanide.” By J. E. Marsh and R. de J. F. Struthers. ‘‘Application of the microscopic method of molecular weight deter- mination to solvents of high boiling point.” By G. Barger and A. J. Ewins. “ Green compounds of cobalt produced by oxidising agents.” By R. G. Durrant. ‘‘Synthesis of tertiary menthol and of inactive menthene.” By W. H. Perkin, jun. “Optically active reduced naphthoic acids. Part I. Dextlo-A(2Or 3)-dihydro-1-naphthoic acid.” By R. H. Pickard and A. Neville. 1;. CLlY AXD SOPjS, 1,131ITJLL)~ BRElD ST. HILL, E.C., ASL) BUSGAY, SUYkOLh.
ISSN:0369-8718
DOI:10.1039/PL9052100215
出版商:RSC
年代:1905
数据来源: RSC
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