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Issued 12/12/1900 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY TBE XECRE3”ARIES. VOl. 16. No.229. December 6th, 1900. Professor THORPE,C.B., F.R.S., President, in the Chair. The following certificates were read for the first time :-Messrs. Andrew Charles Aitken, Rio Marina, Isola d’Elba, Italy ; Thomas Stewart Barrie, ’77, Sinclair Drive, Langside ;John Cardew Bedwell, 65, High Street, Colchester ; Herbert John Bult, 165, Brixton Hill, S.W.;Gilbert Howard Daniel, 21, Church Walk, Ulverston; Frederick George Donnan, Chemical Laboratory, University College, Gower Street, W.C. ; John Alfred Emery, Cinderford, Gloucestershire ; Bernard Farmborough Howard, Devon House, Buckhurst Hill, Essex ; Nicholas Henry Martin, ;Ravenswood, Low Fell, Gateshead ; Theodore Henry Page, 40, Wilson Road, Camberwell, S.E.;Thomas Slater Price, University College, Sheffield ; Lionel Guy Radcliffe, 6, Alma Terrace, Old Trafford, Marichester ; William Cecil Ramsden, 13, Eff ra Road, Rathmines, Dublin ; John Talbot, Tunstall House, Harrow ; James Waterhouse, Oak Lodge, Court Road, Eltham, Kent; William A. Wayland, 4, Harefield Road, Brockley, S.E. ; James Scott Wilson, Bradford Street, Walsall. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected :-Messrs. Bernard Cracroft Aston ; George L. Bennett, M.A. ;Hormasji N. Bilimoria, M.A., B.Sc.; Frederick Nisbet Binks ; Herbert James Singleton Boyes ; Theodore Ridley Burnett, Ph.D. ; John Henry Cheeseright ; Albert Walter Comber ;Alexander Davidson ;Arthur Louis William Fechtner ;Willie 204 Ludford Freeman, B.A.;William Gasson ; George William Gibbings ; John Gibson ; Walter Augustus Handcock ; William A. Hargreaves, M.A.; George Harker, B.Sc. ;Frank C. R. Hemingway ;John Brownlie Henderson ; Samuel Hewitt ; William Henry Hewitt, B.A. ; Edmund Foster Hudson, B.A. ; Adolf Japp6 ; Humphrey Owen Jones, B.A., B.Sc. ; George Washington Kilner, M.A. ; Morris Charles Lamb; George Druce Lander, B.Sc. ; William McCall ; Hans Meyer, Ph.D. ; T. Marginson Nightingale, B.Sc. ; Alexander Pardy ; John Paul ; Ernest Vivian Pearce ;Henry Ernest Stapleton, B.A. ;Arthur Lambert Thornton, B.Sc. ; F. Gerhard Wiechmann, Ph.D. ; Walter Bourne Woodbridge ; Herbert Edwards Wright, M.A.Of the following papers, those marked * were read :-*153. ('Santalenic acid." By Alfred C. Chapman, F.I.C. The author described the preparation of a crystalline acid by the oxidation of oil of santal wood with a neutral aqueous solution of potassium permanganate. flcuztcdenic acid has the formula C,,H,,O,. It crystallises from dilute alcohol in transparent plates possessing a brilliant pearly lustre, is insoluble in water, but dissolves readily in all the ordinary organic solvents. It melts at 76", boils without decomposition at 189" (corr.) under a pressure of 28 mm., and distils with steam. Its rotation has been determined and gives [a], = + 18.05". Many of its salts have been prepared and analysed.The inethyl estey is an oily liquid boiling at 232-234" (35 mm.), and has a sp. gr. = 1.0132 at 15"/15". In a 100 mm. tube at 20' it produces a rotation of -18'13'. "154. u Ammonium bromide and the atomic weight of nitrogen." By A. Scott. During a research having for its chief aim the determination of the hydrogen to oxygen ratio by comparing the equivalents of hydrazine, ammonia, and hydroxylamine, the author found that he could not obtain the same equivalent as Stas for ammonium bromide. The value given by Stas is 98.032, whilst that of the author is 97.996, his highest value being 98.003. This would lower the atomic weight of nitrogen from 14.046 to 14.010, a number much nearer that deduced from the relative densities of oxygen and nitrogen (16 : 14.003).The bromide used by Stas seems to have contained some impurity, probably platinum, as it turned greyish at ll5", and its greyness in-creased up to 180'; he was unable to sublime it even in ammonia 205 without its becoming yellow. The ammonium bromide of the author retains its whiteness at 180° and has been sublimed in ammonia, in a mixture of hydrogen with ammonia and in a vacuum, giving the same results before and after sublimation. The silver bromide had the same composition as that of Stas (57.445 per cent. of silver). The equivalent for ammonium chloride was also determined, and found to be 53516, as against 53.532 (Stas) and 53.486 (Narignac). The silver used was prepared by the reduction of silver nitrate by means of ammonium formate, and was notably better than a sample prepared with the utmost care by the well-known cuprous ammonium sulphite process, To test the purity of the silver in the severest way, the precipitated silver bromide was reduced by hydrogen, when identical results were obtained with the silver so prepared.“165. Relationships of oxalacetic acid.” By Henry J. Horstman Fenton, F.R.S., and Humphrey Owen Jones, B.A., B.Sc. The authors have continued their investigations on the properties and relationships of free oxalacetic acid, obt,ained by the oxidation of malic acid in presence of ferrous iron. The behaviour of the acid towards ammonia, aniline, hydrazine, phenylhydrazine hydroxylamine and urea was discussed as well as the relation of the acid to dihydroxymaleic and dihydroxytartaric acids.It was also shown that the hydrazone of oxalacetic acid readiIy loses carbon dioxide when heated with water, yielding the hydrazone of pyruvic acid, but that by a sufficient concentration of hydrogen ions this change is prevented, the hydrazone losing water instead and giving Wislicenus’ phenyl-pyrazolone-carboxylicacid ; a simple method based upon these changes has been devised for comparing the ‘strengths ’ or ‘aEinities ’ of various acids. W6.(‘The alkaloids of Corydalis cava.’ The conversion of corybul-bine into corydaline.” By James J. Dobbie, D.Sc., M.A.,Alex. Lauder, B.Sc., and Photios G. Paliatseas. Corydaline, C18H,,N( OCH,),, differs from corybul bine, C,,H,,NO(OCH,),, by CH,, and contains four methoxyl groups, whilst the latter alkaloid contains only three (Trans., 1895, 67, 25).The authors have now proved that corybulbine contains a hydroxyl group and forms a mon-acetyl derivative, C,8Hi5N(OCH,),0*C,H30. By treatment with concentrated hydrogen iodide the two alkaloids yield the same phenolic derivative, C1,H15N(OH),,HI. Corybulbine can be readily converted in to corydaline by treatment with equivalent 206 quantities of methyl iodide and potassium hydroxide in methyl alcohol solution. The artificial corydaline agrees in melting point, solubility in various reagents and specific rotation with the natural alkaloid. The platinichloride, ethyl sulphate and hydriodide of the natural and artificial substances have been compared and found to be identical.*157. u The inversion of the optically active ac-tetrahydro-p-naphthyl-amines, prepared by the aid of dextro- and levo-bromocam-phorsulphonic acids." By William Jackson Pope and Alfred William Harvey. Dextro-ac-tetrahydro -P-naphthylamine dextrohromocamphorsul-phonate has been previously prepared from racemic ac-tetrahydro-p- naphthylamine hydrochloride (Proc., 1899,15, 170) ;it was now shown that on treating the hydrochloride extracted from the mother liquors with ammonium kevobromocamphorsulphonate, a precipitate of 1-tetra-hydronaphthylamine 1-bi-onzocamphorsulphonate falls and may readily be obtained in a pure state. The new salt gives [a], = -86.2" in solu- tion in absolute alcohol, as against [a], = +86.5" for its optical antipodes.It has been shown that in preparing the benzylidene, benzoyl and acetyl derivatives of d-tetrahydronaphthylamine the major portion of the base undergoes optical inversion (this vol., 74); on liberating the base from its salts by soda and preparing the hydrochloride consider- able racemisation also occurs, the optically active hydrochlorides being only separable with difficulty from the mixed salts; the enantio-morphously-related hydrochlorides gave in aqueous solution [a], = + 71.9' and -69.7' respectively, The optical inversion seems to occur during the liberation of the base by soda. d-Tetrahydro-naphthylamine d-camphorsulphonate and its enantiomorphously-re-lated isomeride are more easily purified than the corresponding hydro- chlorides; these salt's crystallise with half a molecule of water, and, after drying, give in aqueous solution [.ID = +47.7" and -47.4".The purest specimen of d-tetrahydronaphthylamine, obtained by treating the bromocarnphorsulphonate with soda and distilling under reduced pressure, gave [a], = + 37-24" in a 100 mm. tube ; this still contained about 30 per cent. of the lzevo-rotatory base, so that the pure dextro-base would have given [.ID = + 96' approximately. Optical inversion attending the liberation of a base from its salts has not been previously observed, but E. Fischer has shown that leucine and glutaminic acid undergo partial racemisation on benzoylation ;R,,>C<EH-and the partial these substances all contain the group R' optical inversion is probably due to part of the base being moment- 207 arily converted into a substance containing a group of the type ;:,>C:NK, during conversion of an addition compound into one con-taining triad nitrogen, *158.‘‘ The alkaloids of LHyoscyamus muticus7 and of ‘DaturaStramo-nium ’ grown in Egypt.” By Wyndham R.Dunstan and Harold Brown.” In a previous paper (Trans., 1899, 75, 72), the authors showed that Hyoscyamus muticus grown in India contained 0.1 per cent. of hyoscy-amine which is readily isolated in a pure state. Subsequently Gadamer (A~chivdei. Pharmaxie, 236, 9, 704) in a brief note recorded the fact that the same plant grown in Egypt contains more than ten times this quantity.Through the kindness of Mr. E. A. Floyer, the authors have been enabled to examine a specimen of the plant from Egypt. They find it to be much richer in hyoscyamine than the sample of Indian growth previously examined. The seeds furnished 0.87 per cent. and the sterns and leaves 0.59 per cent. It remains to be determined whether the Indian plant is always poorer in alkaloid or whether it was a peculiarity of the sample examined. The authors call attention to the Egyptian plant as an important source of the alkaloid hyoscyamine. Datura Xtmmonium grown in the Egyptian desert also contains hyoscyamine, unaccompanied by other atropaceous alkaloids, to the extent of 0.35 per cent. An abundant supply of either plant could be obtained from Egypt.159. “ Interaction of urethanes and primary benzenoid amines.” By Augustus Edward Dixon, M.D. Manuelli and Oomanducci have described (Gctxx., 1899, 29, ii, 142) as phenylparatolylcarbamide, PhNH*CO*NHTo,a substance they ob-tained by heating phenylurethane with paratoluidine ; they give its melting point as 259-260°, and confirm the formula by a complete analysis. These chemists have apparently overlooked the descriptions of phenylparatolylcarbamide given by Huhn (Ber., 1886, 19,2408), Uoldschmidt and Meissler (Bey., 1890, 23, 273) and the author (Trans., 1895, 67,562), who record the melting point as 211°, 211°, and 212-213O respectively; Paal and Vanvolxem (Ber,,1894, 2’7, 2426) give its melting point as 212’. It occurred to the author as just possible that Manuelli and Coman- ducci’s compound might be a ‘ labile ’ form of the symmetrical carb- amide, for instance, PhN:C(OH)*NHTo; in order to find out if the 208 discrepancy noted above might be thus explained, the interaction of certain urethanes and aromatic bases was investigated.Phenylurethane and paratoluidine, when heated together, yielded aniline and a crystalline solid ; the latter consisted of a main portion melting at 260-261", which was proved to be, not phanylparatolyl-, but diparatolyl-carbamide, along with a small quantity of phenylpara-tolylcarbamide melting at 213-214'. It is suggested that the pro-duction of diparatolylcarbamide is due to the expuision of aniline by toluidine from the phenyltolylcarbamide initially formed, the actions occurring as follows : (I)PhNH*CO*OEt+ ToNH, = EtOH + PhNH*CO*NHTo.(11)PhNH*CO*NHTo+ToNH, = PhNH, + CO(NHTo),. Aniline heated with paratolylurethane, gave a solid product which consisted mainly of phenylparatolylcarbamide, m. p. 21 3-214', with only a small quantity of a substance melting at about 256-2557', probably diparatolylcarbamide. From orthotoluidine and phenylurethane, aniline always was liberated, the solid product being a mixture, from which were separated (1)vitreous prisms, melting at 249-2250" (diorthotolylcarbamide), and (2) woolly-looking clumps of needles melting at 203-204'; these mere nearly pure phenylorthotolylcarbamide. The latter compound, when prepared by acting with silver nitrate on the corresponding thiocarbamide, or from phenyl isocyanate and orthotoluidine, melted at 207-208".It seemed, therefore, not improbable that the s-phenyl-a-naphthyl- carbamide prepared by Manuelli and Comanducci from phenyl-urethane and a-naphthylamine, and stated to melt at about 277-278', might prove to be really di-a-naphthylcarbamide ;this interaction was therefore re-examined. Phenyl-a-naphthylcarbamide was prepared in two distinct ways and found to melt at 222-2223'. Immediately after melting it resolidifies, remelting about 20' higher; the cause of this behaviour has not yet been investigated. When phenylurethane was heated with a-naphthylamine as described, much aniline was formed, together with a solid mixture, which, when boiled with alcohol, left di-a-naphthylcarbamide, which is nearly in- soluble, and melts rather indistinctly at 286-287' ; from the extract a small quantity of a substance was deposited which crystallised from alcohol in woolly-looking needles.This melted at about 221°, resolidi- fying immediately, as described above, and evidently consisted of yhenyl-a- naphthylcarbamide. Manuelli and Comanducci also obtained from normal amylamine and phenylurethane a colourless solid, iiielting at 23S0, which they regard as nb-amylphenylcarbamide, but which the author thinks is probably carbanilide. 209 160. The decomposition of chlorates. Part 111. Calcium chlorate and silver chlorate.” By William H.Sodeau, B.Sc. When calcium chlorate is decomposed slowly, about 0.6 per cent. of its total chlorine is evolved, whether the pressure be 760 mm. or 4 mm., but the proportion exceeds 2 per cent. when the decomposition under atmospheric pressure is rendered violent. As the proportion of free chlorine is independent of the pressure of the gaseous products, the calcium chloride in the residue is not produced by the action of chlorine upon oxide first formed. When silver chlorate is heated to about 350’ it explodes with a yellow flash, about 7 per cent. of its chlorine accompanying the oxygen, When slowly decomposed the influence of pressure is even greater than in the case of lead chlorate (T~ans.,1900, 77, 718). At atmospheric pressure only 0.2 per cent.of its chlorine remains free, but 22-6 per cent. is obtained at 2& mm. pressure, and more than 36 per cent. should be obtained if the action between chlorine and silver oxide could be completely eliminated. It is concluded that oxygen and chlorine are produced during the slow decomposition of either chlorate by two simultaneous independent reactions represented by the equations 2M(C10,), = 2MC1, + 60, and 2M(C10,), =2M0 + 2C1, + 50, (where MI =Ca or Ag,). With calcium chlorate the ‘‘chloride ” decomposition proceeds at about 180 times the rate of the “oxide” decomposition, whilst with silver chlorate the ratio is less than 1.8:1. The probability of the “oxide ” decomposition being endothermic suggests an explanation of the increase of chlorine in rapid decom- position at high temperature.Silver chlorate differs from the chlorates of potassium, barium and calcium in its highly-explosive nature and in the occurrence of an extremely strong secondary action between chlorine and the oxide, but resembles the chlorates of potassium, barium, calcium and lead, in that no free chlorine is produced by displacement from the chloride. 161. ‘6 On iron nitride.” By G. J. Fowler, M.Sc. Nitride of iron was prepared by three different methods : by the action of ammonia on (a)finely divided iron, (b) ferrous chloride and bromide, (c) iron amalgam. Of these methods (a) is the most con. venient. The substance was found to correspond to the formula Fe,N. The temperatures of the formation of iron nitride in ammonia and of its decomposition in hydrogen are identical.These results confirm the conclusions of Stahlschmidt, Heated in a current of 210 nitrogen, iron nitride begins to decompose at about 600O; it is slightly magnetic ; its specific gravity is 6.35. When oxidised in air or oxygen, only traces of oxides of nitrogen are produced; heated in a current of air, the substance begins to be converted into ferric oxide and nitrogen at about 200O. It takes fire in chlorine either spontaneously, or when slightly warmed, ferric chloride and nitrogen being formed, but no trace of nitrogen chloride. It is only slowly attacked by bromine, the action probably being due to the presence of hydrobromic acid in the bromine as an impurity.An ethereal solution of iodine has no action on it. Dilute hydrochloric and sulphuric acids yield the corresponding ferrous and ammonium salts, hydrogen being liberated, according to the following equation : 2Fe2N+ 6H,SO, = 4FeS0, + 2NH,HS04 + H,. The simultaneous action of hydrogen peroxide and sulphuric acid is not distinguishable from that of the acid alone. Nitric acid acts only slowly on the nitride even when strong; the products formed vary with the concentration of the acid. Gaseous hydrochloric acid begins to attack the nitride at about ZZO", and at 350" the reaction becomes rapid, the substance being completely converted into ferrous chloride and ammonium chloride. Gaseous hydrogen sulphide has a precisely similar action at 200'.Nitric oxide acts similarly to oxygen, and converts the nitride into oxide, the reaction beginning at about 120° and becoming rapid at 170". Carbon dioxide oxidises the nitride at about 530". On heating the nitride in steam at looo, ammonia is very slowly formed. The nitride heated with sodium and carbon yields sodium cyanide. It was thought that phenol might act on nitride of iron in the same way as dilute acids, but the two substances do not react. On heating with ethyl iodide in a sealed tube to 200-23O0, gas is produced consisting chiefly of olefines, with a trace of paraffins, but no amines. The reaction may probably be thus represented: Fe,N +5C,H,I = NH,I + 5C,H, + ZFeI,. 162. '' The heat of formation and constitution of iron nitride." ByGilbert John Fowler, M.Sc,, and Philip J.Hartog, B.Sc. To determine the heat of formation of iron nitride, the substance was dissolved in dilute sulphuric acid (containing 49 grams to the liDre) as represented by the equation Fe,N +3H2S0,,Aq=2FeSO,,Aq -i-NH,HSO,,Aq +H. A current of nitrogen was passed through,:the solution to avoid oxidation of the ferrous salt, as the reaction is a slow one, though it eventually becomes complete. The mean of ,three de- terminations gave as the thermal value of the reaction +8156 cals. From this value the heat of formation of iron nitride is calculated to-be 211 +3.04 cals. It is suggested that the constitution of iron nitride is 163. Infracampholenic acid : an isomeride of campholytic and isolauronolic acids." By M.0. Forster. By hydrolysing the unsaturated nitrile formed when the anhydride of bromonitrocamphane is treated with hot, aqueous sodium hydroxide (Trans,, 1899, 75, 114l), infiacampholenic acid, C9H1402,is obtained as a viscous oil boiling at 145" and 239", under pressures of 24 mm. and 758 mm. respectively ; it is optically inactive, and is trans-formed into isolauronolic acid by hot, dilute, sulphuric acid. The dibromide, C,H,,O,Br,, produced when a cold solution of bromine (1 mol.) is added to the acid dissolved in chloroform and surrounded by a freezing mixture, crystallises from warm petroleum in minute, white needles, which melt at 125" to a colourless liquid which evolves gas.Tribronzodihydroinf~aca~zp~~oZenicacid, C,H,,O,Br,, obtained when infracampholenic acid is submitted to the action of bromine under the conditions which lead to the conversion of campholyticacid into its dibromide, crystallises from ethyl acetate, and melts at 182' to a colourless liquid which evolves gas. Aminoinfyacampholene, C,H,,*NH,, prepared from the amide of infracampholenic acid by the action of sodium hypobromite, is a colourless oil which boils at 155-160' under 754 mm. pressure, and has a sp. gr. 0,8770 at 14". The hydrochloride melts at 213', the platinichloride at 238-240°, and the picrate at 213'; the benxoyl, carbamide, and phenylcarbamide derivatives melt at 105O, 182", and 180' respectively. 164. ''Tutu. Part I." By Thomas Hill Easterfield and Bernard Cracroft Aston.The authorshaveexamined three varieties of tutu-Coriaria ruscifolia, C. thymifolia;, C. ccngustissima-which cause serious loss of stock in New Zealand, and have isolated from them a glucoside, tutin, C17H20011, along with acetic, gallic, succinic and other acids. From-C. thymi-folk yuercitin or an isomeric compound was obtained; and from C. mgurtissima a volatile acid, CsH804,which has not been identified. Tutin was obtained in colourless crystals melting at 208--209° (uncorr.), and is perceptibly volatile at 120-130". Its solubility is 1.9 grams in 100 grams water at 10"; 1.5 grams in 100 grams ether at 10"; 8.2 grams in 100 grams alcohol at 16". It is very soluble in acetone, sparingly soluble in chloroform, insoluble in benzene and 212 carbon disulphide.Its optical rotation was determined, and givescU]g+ = + 9.25’. The authors also discussed the formula for coriamyrtin, and con- clude that the formula, CI5HlSO5,which is half that usually accepted, harmonises better with the facts. A comparison of the chemical and physical characters of tutin and coriamyrtin proved that these sub- stances are not identical. A note by Professor Marshall on the pharmacology of tutin states that its action is similar to that of coriamyrtin, but is more slowly produced, and it is much less toxic. Its action is exerted mainly on the medulla oblongata and the basal ganglia of the brain. 165. (‘Experiments on the production of optically active compounds from inactive substances. Preliminary notice.” By J.B. Cohen and C. E. Whiteley. E. Fischer has shown (Annulen, 1892, 270, 64) that in the synthesis of one sugar from another by the addition of hydrocyanic acid to the lower member, a new asymmetric carbon atom is introduced, which may give rise to two stereoisomeric compounds. This may be repre- sented as follows : 0 7 B -CqH + HCN = -?-OH and HO-7-CN CN Although the two new groups are optical antipodes, the two isomer- ides are not necessarily so as a whole, and consequently they are not always produced in equal quantities. Pischer has found, for example, that glucose forms two cyanhydrins in very unequal quantities, whilst in the case of dextro-mannose only one of the two possible cyanhydrins is produced (Hartmann, Annalen, 1892, 272, 190).It is clear, there- fore, that the asymmetric molecule as a whole exerts its influence on the space configuration of the newly added asymmetric carbon group. In these examples, it is impossible to determine exactly the influence Qf the active part of the original molecule on the activity of the new group, seeing that the latter cannot be detached from the molecule. As the formation of active substances in living organisms is probably closely connected with their production from other active substances from which they are afterwards removed, the idea occurred to us to attempt to produce a new asymmetric carbon atom in an already active compound from which the originally active group could be subse- quently detached. A number of reactions readily presented themselves, such as the 213 reduction, bromination or hydroxylation of esters composed of an un-saturated acid and an active alcohol, or the reduction OF a ketonic ester of an active alcohol, the alcohol being afterwards removed by hydrolysis.These reactions may be represented as follows : (X stands for an atom or group not being hydrogen, A indicates the active alkyl or aryl group, and C, the new asymmetric carbon atorn) : 1. (a) *CH:CX*CO,A (b) *CH,*CHX*CO,A (c) *CH,*CHX*CO,H. 2. (a)*CH:CH.CO,A (b) *CHX-CHX*CO,A(c)*CHX*CHX*CO,H. 3. (u)*CO*CO,A (6) *CHOH*CO,A (c) *CHOH*CO,H. Under (1) we have studied the reduction of the menthyl esters of mesaconic and phenylcrotonic acids.(a) CH,*C(CC~,C,,H,,):CH*C02C,oH19 (b)CH,*CH(CO,C, ~Hl9)*CH,*CO,C,,H,, (c) CH,*CH( CO,H)CH,*CO,H* (u) C,H,* CH:C(CH,) * C0,C,oH,9 (b) C&€,CH,*CH(CH,) *CO,C,,H,, (c) C6H,CH,*CH(CH,)*C02H. Under (2) we have prepared the bromine derivatives of the amyl and menthyl esters of cinnamic acid and of dicinnamyl tartrate, and examined the action of various reagents on the dibromo-compounds, also the action of sodium ethylate on rrienthyl fumarate. (a) C,H,CH: CH* CO,C,H,, (b) C6H,CHBr*CHBr*C0,C,H1,. (a) C,H,CH:CH*C0,C,oH19 (b) C,H,CHBr CHBr*CO,Cl0Hlg. C6H,CH: CH*CO,*yH*CO (') C6H,CH: C€€*CO,*C€€*CO>o @) C,H,CHBr* CHBr*CH- C0,H' fiH*C02*C10H19 (a) CH*CO,* C,,H,,' Under (3) me have investigated the reduction of menthyl pyruvate.(a)Me*CO*CO,C,,Hlg (b) Me*CHOH*CO,C,,H,g (c) Me*CHOH*CO,H. The results in all cases have been of a negative character, in spite of every care to avoid possible racemisation by conducting the reac-tions as far as possible at the ordinary temperature. The experiments, which were commenced in 1S9S, have been delayed in consequence of unforeseen difficulties. All the experiments under (2), after a considerable loss of time, had to be abandoned. Although the dibromo-derivatives of amyl and menthyl cinnamate and of dicinnamyl tartrate could be readily obtained in a state of purity, they could not be directly hydrolysed without removing bromine, and all attempts to replace the bromine by hydroxyl failed.Menthyl fumarate, which was readily prepared from silver fumarate and menthyl chloride, gave 214 no ethoxy-derivative by means of Purdie's reaction. Reactions (1)and (3) were, however, ultimately brought to a satisfactory conclusion. Menthyl mesconate and menthyl phenylcrotonate were prepared by heating together menthol and the acid chloride, whilst menthyl pyru- vate was obtained by heating menthol and pyruvic acid under dimin- ished pressure. The reduction of the first two esters mas effected by means of the aluminium-mercury couple in aqueous alcoholic solntion, whilst menthyl pyruvate was reduced with zinc dust and acetic acid. The esters were then hydrolysed with alcoholic potash and the menthol removed with ether. The acid, after careful purification by crystal-lisation or precipitation of its salt, was finally examined in the polari- meter.Pyrotartaric acid, phenylmethylacetic acid, and lactic acid, obtained in this way, were all optically inactive. We propose to extend these experiments to the acid amides of optically active bases- 166. (( Synthesis of isocamphoronic acid." By W.H.Perkin, jun. When the anhydride of CO,H*CMe,*CH,*CH,*CO,H, aa-dimethyl- glutaric acid, is treated with phosphorus pentachloride and bromine and the product poured into alcohol, CO,Et*CMe,*CH,*CHBr*CO,Et,ethyl 6rornodimetl~yZgZuturateis obtained as a colourless oil boiling at 165-170" (35 mm.). This on trearuent with alcoholic potash yields ~i~~-~et7~yZgZutacon~c acid, C02H*CMe,*CH:CH*C0,H, which crystallises from water in plates melting at 172' and is possibly a stereoisomeride of the aa-di- methylglutaconic acid lately prepared by M.Conrad (Bw., 1900, 33, 1920) which melts at 150'. That the acid of melting point 172' has the constitution assigned to it is proved by the fact that when oxidised with permanganat#e at O3 it is quantitatively converted into dirnethylmalonic acid and oxnlic acid, CO,H*CMe,*CH:CH.CO,H +30 =CO,H*CL\Ie,-CO,H +CO,H*CO,H. Dimethylglutaconic acid is readily esterified by means of alcohol and sulphuric acid :theethyZdimet~~~ZyZu~aco?zate,C0,Et*CAIe,*CH:CH*CO,E t, thus produced, is a colourless oil boiling at 200" (200 mm.). When this ester is digested in alcoholic solution with the sodium compound of cyanacetic ester, condensation takes place, and the pro- duct, on heating with dilute sulphuric acid, is almost quantitatively converted into an acid melting at 166', and which on examination has been proved to be isocamphoroizic acid.(Found C =49.7 ;H =6.5 ;C,H,,O, requires C =49.5 ;H =6.4.) Professor von Baeyer was kind enough to send the author a sample of isocamphoronic acid which had been prepared from pinene, and on mixing equal quantities of this and the synthetical acid, no altera- 215 tion in the melting point could be observed. Again, when heated with sulphuric acid at looo, the synthetical acid is converted into terpenylic acid, a change which Tiemann (Ber., 1896, 29, 2613) has shown to be characteristic of isocamphoronic acid.There can thus be no doubt that the synthetical acid is in reality isocamphoronic acid, and its synthesis solves the vexed question of the constitution of this important acid. The condensation of ethyl dimethylglutaconate with the sodium corn- pound of ethyl cyanacetate may be represented thus : CO,Et*CMe,*CH:CH* C0,Et + CN* CHNa*CO,Et -CO,E t*CMe,*QH*CHNa. CO,Et, -CN*CH* C0,Et and the cyanester thus produced yields, on hydrolysis and elimination of carbon dioxide, isocamphoronic acid, which, therefore, must have the constitution, CO,H* CMe,* CH(CH,* CO,II)*CH,*CO,H, first proposed €or this acid by Tiemann (Ber., 1896, 29, 2614). 167. (‘On some a-alkyl substitution products of glutaric, adipic, and pimelic acids.” By J.W.Mellor. The author describes the known methods of general application for the preparation of the above acids, and gives an account of some new methods which he has employed in synthesising such acids. He finds that adipic acid itself may be readily prepared in quantity by the action of chloropopylcyanide, Cl*CH,*CH,* CH,* CN, on the sodium compound of ethyl malonate, and subsequent hydrolysis of the ethyl cyanpropylmalonate, CN*CH,*CH,*CH,* CH(CO,Et), (b. p. 17O-175O at 40 mm.), by boiling with dilute sulphuric acid. a-Alkyl substitution products of adipic acid may be obtained by employing the corresponding ethyl a-alkylmalonates in this synthesis in the place of ethyl malonate. The author has prepared several of the known a-alkyl substitution products of glutaric, adipic, and pimelic acids in n state of purity, and determined their dissociation constants.He has also prepared a-p~opyl adipic acid, CO,H* CHPr*CH,* CH,* CH,* CO,H, which melts at 59O and does not appear to have been previously described. 168. (‘On the nature of polyiodides and their dissociation in aqueous solutions.” By H. M. Dawson. From experiments on the ratio of distribution of iodine between solutions of potassium iodide and carbon bisulphide and the simplicity of the dissociation isotherm for the equilibrium in the aqueous solu- tion, which accords with the experimental data, it is concluded that 216 potassium triiodide is a normal salt of potassium, which at correspond- ing concentrations is dissociated electrolytically to the same extent as other binary salts.Experiments with solutions of hydriodic acid lead to the conclusion that hydrogen triiodide is electrolytically dissociated to the same extent as hydriodic acid, and belongs, therefore, to the group of strong acids. These results are in harmony with Abegg and Bodlander’s theory of complex compounds. From their analogy with potassium triiodide, the recently discovered trihaloid derivatives of cwium and rubidium must be placed in the same category. ADDITIONS TO THE LIBRARY. I. Donations. Galt, Hugh. The microscopy of the more commonly occurring starches. Ill. London. 1900. From the Publishers. Hollard, Auguste. La thhorie des ions et l’dectrolyse.Paris. 1900. From the Publishers. Lewes, Vivian B. Acetylene, a handbook for the student aad manufacturer. Ill. Westminster. 1900. From the Author. Mendola, Raphael. Inorganic chemistry, non-metallic and metallic elements, with sections of inorganic analysis, laws of chemistry, chemical action, &c. Revised to date by J. Castell Evans. Fifth edition. Ill. London, 1900. From the Editor, Moissan, Henri. Le fluor et ses composds. Paris. 1900. From Sir John Evans. The climates and baths of Great Britain, being the report of a committee of the Royal Medical and Chirurgical Society of London. Vol. I. The climates of the Sout’hof England, and the chief medicinal springs of Great Britain. London, 1895. From the Publishers. 11. By Pus.chase.von Richter, V. Chemie der Kohlenstoff verbindungen oder organische Chemie. Ninth edition, edited by R. Anschutz. Vol. I. Die Chemie der Fettkorper. Bonn 1900. Rufe, Hans. Die Chemie der naturlichen Farbstoffe. Brann-schweig 1900. Vallery-Radot, R. La vie de Pasteur. Paris 1900. 217 Dalton, John. A new system of chemical philosophy. Part I. (Second edition), London 1842. Part 11. Manchester 1810. Vol. 11. Part I. Manchester 1827. Smith, R. Angus. Memoir of John Dalton and history of the atomic theory up to his time. London 1856. Roscoe, Sir H. E. Lecture on John Dalton and his atomic theory. Manchester 1874. Mills, E. J. Destructive distillation, a manualette on the par- affin, coal tar, rosin oil, petroleum and kindred industries.Fourth edition. London 1892. Janus, Lacinius. Pretiosa Margarita, de philosophorum lapide. Venice 1546. Jorgensen, Alfred. Micro-organisms and fermentation. Third edition, translated by A. K. Miller and A. E. Lennholm. London 1900. Filhol, Edouard. Recherches sur les eaux minBrales des PyrBdes. muvre posthume publike par Leon Joulin. Paris 1888. Garrigou, Fdlix. Etude chimique et mddicale des eaux sulfureuses d’Ax (Aridge). Paris 1862. Lecoq, Henri. Les eaux mindrales du massif central de la France considkrhes dans leurs rapports avec la chimie et la geologie. 2 vols . Paris 1865. Marchand, Eugkne. ktude sur la force chimique contenue dans la lumikre da soleil. Paris [1S76]. 111. Pamphlets. Beitter, Albert. Pharmacognostisch-chemische Untersuchung der Cathu edulis.Strassburg, 1900- Brough, B. H. Cantor lectures on the nature and yield of metalliferous deposits. (Read before the Society of Arts, 1900.) Bresler, J. Dionine. (From the Psychiatrische TtTochenschrift, No. 39, 1899. Burnett, T. R. Ueber die Bestimmung der Halogensalze neben- einander. Inaugural dissertation. Base1 1900. Dixon, W. E. A note on the physiological action of Poehl’s spermine. (From the Jourizccl of Physiology, xxv., 1900.) Greshoff, M. Echinopsine, a new crystalline vegetable base. (From the Proceedings of the Akademie van Wetenscha2pen te Amsterdam, 1900.) Vernon-Harcourt, L. F. Experimental investigations on the action of sea water in accelerating the deposit of river silt and formation of deltas.(From the Proceedings of the Institution of Civil Engineers, cxlii., 19 00.) 218 Hartley, W. N. The action of heat on the absorption spectra and chemical constitution of saline solutions. Ill. 1900. (From Trans. Royal Dub. Soc., ser. ii, Vol. vii.) Hesse, Ludwig. Bromipin. (From the AlZgemeine Medicinische Cents-al-Zeitung. No. 21, 1900.) . Iodipin. (From the Pharmaceutische Centmlhalle, No. 1, 1900.) Jones, Francis. The air of rooms. Manchester, 1900. Long, J. H. On the relation of the reducing power of normal urine to the amount of certain nitrogen compounds present. (From the Journal of the American Chemical Society. No. 6, 1900.) -. On certain peculiarities in the urine of vegetarians. (From the Journal of the American Chemical Societp, No.9, 1900.) power, F. B., and Shedden, Frank. The composition and deter- mination of cerium oxalate. (From the J.S.C.I., xix., 1900.) Spring, W. Sur la floculation des milieux troubl8s. (From the &ll. de Z’Acad. roy. de Belgique, 1900.) -, Propri6t6s des solides sous pression, diffusion de la matiere solide, mouvements internes de la matiere solide. Paris 1900. RAMMELSBERG MEMORIAL LECTURE. The Rammelsberg Memorial Lecture will be delivered by Professor H. A. Miers, D.Sc., F.R.S., on Thursday, December 13th, 1900, at 8.30 p.m. At the next meeting, on Thursday, December 20th, the following paper mill be communicated. ‘‘ On the union of hydrogen and chlorine.” By J.W. Mellor, B.Sc. HICIIARD CLAY \X.DSOKS, LIBUTED, LOh‘DOX AXD BUXGAY

ISSN:0369-8718    

DOI:10.1039/PL9001600203

出版商:RSC    

年代:1900

数据来源: RSC