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Proceedings of the Chemical Society, Vol. 29, No. 412 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 412,
1913,
Page 65-80
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摘要:
[Issued 39/3/13 Y R 0 C E E D 11 N C3 S OF TRR C H I3 M I C A L S 0 C I E T Y. Vol. 29 No.412. Thursday, March 6th, 1913, at 8.30 p.m., Professor PERCYF. FRANKLAND,LLD., F.R.S., President, in the Chair. The President referred to the loss sustained by the Society through death on February 19th of Prof. William Tate, of Sibpur, who was elecbed a Fellow of the Society on May 15th, 1890. Certificates were read for the first time in favour of Messrs.: Alfred Gilbert Dix, B.Sc., 110, Tufnell Park Road, Rolloway, N. Percy Wolmer Hill, 42, Holyliead Road, Wednesbury. Thomas Arthur Ilolroyd, B.Sc., Carnbuck Club, Perambur Barracks, Madras. John Francis McCann, 2, Prince of Wales Terrace, Sandymouiit Avenue, Ballsbridge, Co. Dublin. Harry Bertram Maynard, The Park, Kingswood, Bristol.'Kali Prosonuo Rai, M.A., 147, Bamnoshee Ghose Street, Calcutta. Tlie following Certificates have been authorised by the Council €or presentation to ballot under Bye-law 1(3) in favour of Messrs.: Herbert Garland, Helouan, Cairo. Julien Pierre Frhderic Pougnet, Natal Estates, Ltd., Mt. Edge- combe, Natal. Thomas Watson, 1156, Davie Street, Vancouver, B.C. 66 Of the following papers, those marked * were read: *56. ‘‘Quinonoid salts of nitroanilines.” By Arthur George Green and Frederick Maurice Rowe. With the object of isolating quinonoid salts oi nitroarnines (com- pare T., 1912, 101, 2452), the authors have subjected solutions of various nitroamines in dry benzene to the action of sodium ethoxide. Deep orange to red precipitates were obtained with the following compounds : o-nitroaniline, p-nitroaniline, p-nitroethylaniline, 2 : 4/-dinitroaniline, 2 : 4 : 6-trinitroaniline (picramide), 2-nitro-p-toluidine, 6-nitro-m-toluidine, 4-nitro-m-toluidinc, 4-chloro-2-nitro- aniline, 3-chloro-2-nitroaniline, 3-chloro-4-nitroaniline, 2-nitro-p-phenylenediamine, 2-nitro-4-acetyl-p-phenylenediamine.The f 01-lowing nitroamines gave no precipitates, and exhibited no change of colour : m-nitroaniline, 5-nitro-o-toluidineY 3-nitro-o-toluidine, 5-nitro-o-4-xylidineY and also the 0-, m-, and p-nitro-derivatives of dimethylaailine.It would therefore appear that all primary and secondary ortho- and para-nitroamines give rise to deeply coloured quinoncid salts under the conditions employed, but that no such reaction occurs in the meta-series.Analysis of the products supports the general NHformula X<NO,Sa. In the case of p-nitroaniline, two “chromo- isomeric ” salts were obtained, namely, a red labile form and an: orange stable form. The tendency of nitroamines to form quinonoid salts is further exemplified by the properties of nitro-p-phenylenediamine. This compound crystallises from water in bluish-red needles, with a dark green reflex, but dissolves in non-ionising solvents with a yellow colour. In the solid ttate and in its aqueous and alcoholic solutions, which are red, it probably possesses the constitution of NHan internal quinonoid salt, NH,* C,H,<No2. I DIsccss ION.Dr. J. T. UEWITTwelcomed the sharp distinction between the 0-and p-nitroanilines on the one hand, and m-nitroaniline on the other, since rm-nitrophenol was not so different from 0-and p-nitro- phenols in its chemical nature as might be expected; thus the tw0 latter compounds were not reduced to azoxyphenols by sodium methoside, neither, however, was m-nitrophenol. 67 *57. The existence of racemic compounds in the liquid state.” By Alec Duncan Mitchell and Clarence Smith. The method of determining the molecular weight of a pure liquid by the change of its molecular surface energy with temperature has been applied to the problem of the existence of racemic com- pounds in the liquid state. Since experience has shown that liquid hydrocarbons and esters usually are unassociated, the substances examined are the active and the inactive modifications of pinene and of limonene, and the dimethyl esters of d-tartaric and racemic acids.The apparatus described by Hewitt and Winmill (T., 1907, 91, 441) has been used, and all measurements of length have been made with a vernier microscope reading directly to 0.01 mm., and by means of a micrometer eye-piece to 0.001 mm. The values of L for 6-, I-, and i-pinene (the last being obtained in two different ways) are 2.36, 2.32, 2.36, and 2.33 respectively, the figures in each case being the mean of four values obtained over a range of about 80°. The values of k for d-and I-limonene and dipentene (the last obtained in two ways) are 2.34, 2.23, 2.29, and 2-26 respectively.Dimethyl d-tartrate and racemate respec-tively give the values 1.99 and 2-03 for k. The results indicate that the substances examined do not, in the optically inactive form, exist as liquid racemates. DIscussION. Mr. F. B. THOLEpointed out that there was considerable evidence for the existence of liquid dimethyl racemate to a certain extent. The viscosities of the active and inactive esters were undoubtedly slightly different, whilst Bruni by cryoscopic measurements in ethylene dibromide solution had found indications of the formation of a racemic complex. The authors appeared to lay particular stress on the absence of variation of R with increasing temperature as indicating the absence of association, for A-altered considerably with temperature in the case of associated liquids, such as water, acetic acid, and alcohol.It wa.s questionable, however, whether the molecular complexes present in these liquids were really comparable with racemic com- pounds. The component molecules of the latter were probably much more firmly united than those forming the complexes- in the ordinary “ associated” liquids, and the variation of K with tem- perature would naturally be much smaller when the complexes were comparatively stable. “58. “The vapour pressures of the lower alcohols and their azeotropic mixtures with water. Part I. Ethyl alcohol.” By Richard William Merriman. Quick lime made from marble was found to be the moet efficient drying agent for ethyl alcohol. The density of dry alcohol, deter- mined by the method recently described (Wade and Merriman, T., 1912, 101, 2429) was found to be 0.80628 Oo/4O.The alcohol, at 100°, has the power of partly dehydrating calcium hydroxide, so that the last fraction in the preparation of dry alcohol should be rejected . The vapour pressures above 14O were determined by distilling the dry alcohol through an eight-section Young evaporator column, keeping the pressure1 constant by means of a manostat (Wade and Merriman, T., 1911, 99,984). Below 14O another method was used, but the distillation method is the best method for determining vapour pressures if a cold room is available for the lower tempera- tures.The view was expressed that experimental results should be smoothed by the method of differences, and not by the use of an empirical formula. The results obtained agree closely with those of Schmidt (Zeitsch. physikal. Chem., 1891, 8,620). The boiling point is 78*30°/760mm., agreeing with Young’s value. Ramsay and Young’s values (Phil. Trans., 1886, 177,i, 155) for the vapour pressures below 30° were shown to be somewhat inaccurate, but on being smoothed became almost identical with the results obtained by the author. The vapour-pressure curves of ethyl acetate (Wade and Merri- man, T., 1912, 101, 2438) and ethyl alcohol cut each other at a point corresponding with a pressure of 948.1 mm. and a tempera- ture of 84.01O. The boiling points of the azeotropic mixtures with water were determined, and compared with the boiling points of the pure alcohol.The differences between the two series of boiling points increases with the pressure, as also does the percentage of water. “59. “The action of chlorine on thymol and on m-cresol.” By Horace Leslie Crowther and Hamilton McCombie. The authors have investigated the action of chlorine under different conditions and in the presence of various catalysts on thymol and on ?n-cresol. When solid thymol was chlorinated the products obtained were 2 :6-dichlorothymol (I) and 2 :4 :4-trichrZoro-3-methyZ-6-isopropgZ-hexadienone (11). The former compound has been described by Blum (Zeitsch. p7iysioZ. Chem., 1893, 16,518) and tbe latter by 69 Lallemande (,4niz.Chim. Phys., 1857, [iii], 49, 148), but this author describes it as t,richlorothymol. The constitution assigned to it is justified by its liberating iodine from potassium iodide with the formation of 2 :6-dichlorothymol and the non-formation of acyl co OH '\ OH MP! ,--\/ ---\,/ C1 CCJ, c1 (1.1 (11.) (111.) derivatives. M7ith sulphuric acid at looo this compound yields 2 :4:6-tric~iloro-m-cresol(111). When thymol is chlorinated in caxbon tetrachloride in the presence of iodine there is formed a small quantity of 2 :4:4 :5-tetra-chloro-3-methyl-6-B-chloroisoiprop~~h~exadieno,?e (IV), This consti-tution is assigned to the substance because it liberates iodine from potassium iodide, does not form acyl derivatives, and with sulphuric acid yields t.et,rachloro-~~z-cresol(V). It was, however, very difficult CO cu (IV.) (\.'*) (Ti.) to arrest the chlorination at this stage, and the main products of the reaction were tetrachlorern-cresol (V) and 2 :4:4:5 :6-pentn-c7~loro-3-~1~eth~l7~cxadic.lzone In addition there was formed a (VI).small quantity of 2 :4 :5-trichlorotoluquinone. Chlorination of thymol in the presence of reduced iron gave rise to 2 :4:6-trichloro-m-cresol (111), tefrachloro-m-cresol (V), and a small quantity of trichlorotoluquinone. Very similar results were obtained when aluminium-mercury was employed as the catalyst. m-Cresol when chlorinated yielded 2 :4 :6-trichloro-m-cresol, tetra- chloro-m-cresol, and 2 :4 :4:5 :6-pentachloro-3-methylheriadienone. 60.'*The nomenclature of sugar derivatives." By James Colquhoun Irvine. At presmt the position occupied by substituting groups in sugars is indicatsd by the use of Greek letters, the carbon atom nest to thO reducing group being termed the a-atom. Attention is now drawn to the fact that confusion arises when, in addition to the position of the substituents, t'he stereochemical form (a or P) of the 70 parent sugar has also to be included in the nomenclature. Several examples were quoted of cases in which, owing to this difficulty, the names at present in use a10 either misleading or incomplete. It is now proposed to restrict the use of the expressions a and p, as a.pplied to sugar derivatives, solely to the indication of the con- figuration of the mutarotatory forms of sugars and of derivatives, such as glucosides, which exist in two stereoisomeric modifications. It is further suggested that the carbon atoms in sugars and their derivatives should be indexed by numbers, the reducing group being termed the No.(1) position in the case of an aldose and No. (2) in the case of a ketose. The numerical system may also be applied to polyhydric alcohols, the numeration in such cases being com-menced at the terminal primary alcohol group which normally oxidises to give an aldose. The application of the method is illus- trat ed by reference to synthetical aminoglucosides, aminoglucoses, methylated sugars, and a series of mixed ethers derived from manni- tol. Examples of the proposed nomenclature are shown below : 707C)H*CH,*CH(OF1)*CH*CH(On~e)*C7H(OI1Ie)*C'H*OH 2 :3-Dimcthyl u-or -B glacose.070MwCH,. H *CH(OR)a CH(0H ) c'(OH) 42 11,SOH 6-Jlonometli~.la-or -8-fructose. 07OH~CH2*CH(OH)*~H*CH(OH).CH(N LI,)*CH*OJle 2-Amino-a-or -8-met~Iylglricoside. 0&X e*CH, C 13(031e) CH( 0Me) CH(0H) C€I,*0H 3 : 4 :5 : 6-l'etraniethyl mannitol. 61. ''Partly methylated glucoses. Part I. <-Monomethyl glucose and yt[ triniethyl glucose." By James Colquhoun Irvine and James Patterson Scott. Glucosediacetone, when methylated by the silver oxide reaction, is converted into <-monomethyl glucosrdiacetoize (b. p. 139-140°/ 12 mm., [aID-32.2O in alcohol), and, on hydrolysis, <-monomethyl glucose is obtained.Both the a-and B-forms of the alkylated sugar were isolated, and the mutarotation of each isomeride deter- mined in various solvents. ~-:-,UononzethyZa-glucose crystallises in rectangular plates melting at 157-158O, and shows the optical change [a]=+ 98.6O -+ + 6S.Oo in methyl alcohol, whilst [-mono-methyl fl-glucose forms prismatic needles (m. p. 130-132O), which show raID + 29.6O -+ + 68.0° in the same solvent. These optical values agree only approximately with those calculated according to Hudson's method (J. A me?.. Chrm. Soc., 1909, 31,SS), but, at 71 the same time, the activity here ascribed to the &form may not be strictly accurate. Exact agreement with Hudson’s figurea would demand the alteration of the initial specific rotation of the &-form from +29*6O to +15.l0.The sugar gives a monomethyl mefhylglucoside, and is converted into the same monomethyl glucosephenylosazor,s previously obtained from monomethyl fructose. The alkylation of glucosemonoacetone yielded yik-trimethyl glucosemonoacetone as the main product (b. p. 138-139°/12 mm.), from which, on hydrolysis, yik-frimetlzgl glucose was isolated as a colourless syrup. Contrary to expectation, the equilibrium mixture of the a-and &forms of this sugar is laevorotatory ([aID -8*3O iq water), and so also is the a-isomeride. These optical results are quite abnormal, and are being further investigated. 62. ‘-Partly methylated glucoses. Part 11. py-Dimethyl a-glucose and &dimethyl ,3 glucose.” By James Colquhoun Irvine and James Patterson Scott.The introduction of the benzylidene group into methylglucoside enables three of the hydroxyl groups of the parent sugar to be protected from methylation. The application of the silver oxide reaction to benzylidenemethylglucoside therefore gave E[-henzyli- dene-/3y-diniethyl a-methylglitcoside (m. p. 122-123O) [aIDA 97O in water). Cautious hydrolysis removed one molecule of benz-aldehyde, with the production of /3y-rFimetlbyl a-nietliylglucoside (m. p. 80-82”, [a], +142.6O in acetone), from which, on complete hydrolysis, By-dirriethyr! glucose was obtained. Both stereoisomeric forms of the sugar were isola,ted. /3y-B)imetliyl a-glucose melts at 8S-8T0, and shows downward mutarotation in acetone solution ([01ID+ 81.9*-+ + 48.3O), whilst Py-dirrLethzJ P-g!ucose (m.p. 108--110”) exhibits mutarotation in the reverse direction (“a], -t. S.gC-+ + 50.9O in acetone). These values are in good agreement with those calculated by Hudson’s method. This geiiera.lisation seems, however, to be inapplicable to complexes of the type of benzylidenemethylglucoside. In connexion with the constitution of dimethyl glucose, the influence of configuration in controlling the formation of condensa-tion derivatives of sugars was discussed, and the conclusion waa drawn that, in benzylidenemethylglucoside the aromatic residue occupies positions (e) and (y). In the course of the work, a second isomeric form of benzylidene-a-methylglucoside was isolated. The new isomeride, for which the name d-E5-6enzylidene-a-methyl-d-glricoside was suggested, melts at 148--149O, and shows [aID +98O in water.72 63. (‘Perezone.” By Frederic George Percy Remfry. The hydroxy-quinone perezone (pipitzahoic acid), C,,H,,O,, is converted by the action of heat into a colourless isomeride melting at 140-141° (corr.), and having [uJD +13*l0, which has been termed perezol. This substance is phenolic, and yields a monoacetyl derivative, acetylperezol, melting at 114-115O (corr.), a.nd having [uID +6*2O. The latter is identical with the colourless compound obtained by Anschiitz and Leather (Annulen, 1887, 237, 90) by the actmionof acetic anhydride on perezone.Perezol and acetylperezol are, further, doubtless identical with the substances prepared by Sanders (P., 1906, 22, 134), to which, however, diflerent formula: were assigned. Perezone yields ulky7p.uinoZe.s when treated with magnesium alkyl iodides. By-products produced in the preparation of hydroxyperezone and perezinone have also been studied. 64. Polybromides in nitrobenzene solution.” By Alfred Francis Joseph. The solubility of potassium bromide in nitrobenzene solutions of bromine has been measured, and from the results the existence of a polybromide, I<Br2n+1, may be inferred, for which n is about 1. The rate of molecular conci&~tration of bromine to molecular solubility of bromide increases frpm 1.87 to 3.11 as the former increases from 0.075 to 1.5, but it was shown that this does not indicate the presence of polybromides, for which n is greater than 1.The’ colorimetric study of the solutions leads to the same con-clusion. 65. (‘The action of ay-dibromobutane on the sodium derivatives of ethyl acetoacetate and benzoylacetate.” By Robert George Fargher and William Henry Perkin, jun. ay-Dibromobutane reacts readily with the sodium derivative of ethyl acetoacetate with the formation of ethyl 2 :6-dintethyl-2 :3-dihydro-l :4-pyrau-5-carbolrylate, C&Ie C(C0,Et)O-&l\fe---r:I[,>CH2. which melts at 35O and distils at 325--226’/750 mm. The corre- sponding acid melts at 126O, and is decomposed on distillation into 2 :6-dimethyl-2 :3-c?aAydro-1 :4-ppyrm7, a mobile oil distilling at 1200.When the acid is boiled with water it loses carbon dioxide, and the dihydropyrane ring suffers hydrolysis with formation of heptan-l-oZ-B-one, CH3*CO*C'R,*CH,*CH,*CH(OR)*C~3, viscid sp'up,a which distils at 117O/20 mm., and is converted by oxidation with chromic acid into heptnne-B[-dione, CH,*@OCH,*CB,*CH,*CO'CH3, which melts at about 31°, and distils at 202O/754 mm. Reduction with sodium amalgam converts heptan-[-ol-P-one into heptane-Bc-diol, which distils at 140°/50 mm., and, when heated under the ordinary pressure, is gradually decomposed with the formation of 2 :6-dimethyl-3:3 :5 :6-tetrahydro-l :4-pyran, CH Me-CH O<CHbfe*CH,2>CH,, a mobile oil distilling at 118O/756 mm. P[-Dibromoheptane, C'H3*CHBr*[CH2]3*CHBr*CH3(b.p. looo/ 12 mm.), is obtained when heptane-Pf-diol is digested with phm- phorus tribromide. t-Bromoheptan-P-one, CE3*CO*[CH,],*CHBr~CI13,produced by the action of concentrated hydrobromic acid on ethyl dimethyl- dihydropyrancarboxylate, distils at 130°/50 mm. When the sodium derivative of ethyl benzoylacetate is digested with ay-dibromobutane, ethyl 6-phen yl-2-methyl-2 :3-dihydro-l :4-pyran-5 carbozylate is obtained as a colourless, crystalline mass, melting at 58O. 6-Phenyl-2-methyl-2 :3-dihydro-l :4-pyran-5-carb-orry7ic acid, meits at 147O, and is decomposed on heating with elimin+tion of carbon dioxide and formation of 6-phenyl-2-me t?Ayl-2 :3-dikydro-py~m(b. p. 251°/758 mm.), and, when boiled with water, the acid yields a-pheTI y111 exan-E-ol-a-one, C,H,*CO CH,*CH,*CH,*CH(OH) *C'H3, which melts at 34O, and is reduced by sodium amalgam to phenyl-hexnne-a~-dioZ,which is a syrup.Careful oxidation with chromic acid converts phenylhexanol into a-ph enylhexane-a~-dion e, C,H,*CO*IICH,]3*CO*C~3, a crystalline siibst,aiice, which melts at 65O. Plzenyl ebronzo-a-plz enyllzexan-a-one, C,H,*CO*~CH,],*CTHBr.C'H3,is obtained, when ethyl phenylmethyldihydropyrancarboxylate*is left in contact with concentrated hydrobromic acid, as a syrup which distils with much decomposition at about 188O/21 mm. 66. “The action of aydibromobutane on the sodium derivative of ethyl malonate.” By Qibbs Blackstock and William Henry Perkin, jun, This interaction leads tothe formation of a number of substances, one of which is ethyl 1-methylcyclobutane-2 :2-dicarboxylate.This ester, on hydrolysis, yields 1-methylcyclobutane-2:2-dicarboxylic acid (I),which crystallises from dilute hydrochloric acid in prisms, CHRlecH,e7$>c (c0$3) 2 CH,<-(q_>CH* C0,K 2 (1.1 (11.1 and melts at 160---162°. This dibasic acid is decompmed on distil- lation, with elimination of carbon dioxide and formatim of 1-met hylcyclob utane-2-carboxylic acid (11) , which is an unpleasant smelling oil distilling at 19S0/755 mm. The authors are engaged on the resolution of this acid into its active constituents, and also on the examination of the other substances produced in the above inter action.67. ‘(Studies on cyclic ketones. Part 111.” By Siegfried Ruhemann and Stanley Isaac Levy. The constitution of the red condensation product, previously obtained by the action of heat on 2-hydroxymethylene-1-hydrindoiie (‘I?., 1912, 101, 2549) has been verified by the study of its behaviour towards bromine. Experiments have now been made with the object of preparing similar substances from diphenyl- cyclopentenoiie and from /3-hydrindone, but these attempts were unsuccessful, as no hydroxymethylene derivatives of these ketones could be obtained. These experiments, in turn, led to the investigation of the action of aromatic aldehydes on the two ketones. It was found that, under the influence of hydrogen chloride, condensation readily occurs with two molecules of the aldehyde.With o-hydroxyaldehydes the reaction prxeeds one stage further, polycyclic spiropyran com-pounds being formed. Substances of this nature have been obtained from both ketones by the actbn of salicylaldehyde and of 1-alde- hydo-2-naphthol; they are characterised by the deep colour and strong fluorescence of their solutions in concentrated sulphuric acid. The action of p-nitrosodiethylaniline on diphenylcyclopentenone is found to be exactly parallel to the reaction with nitrosodimethyl- 75 aniline already investigated (T., 1912, 101, 42), with the remark- able difference that the compound which is formed from the product by the action of hydrochloric acid, does not possess the property of forming colloidal solutions, which characterises the analogous derivative obtained from p-nitrosodimethy ladine.68. “The interaction of chlorine and hydrogen. The influence of mass.” By David Leonard Chapman and Leo Kingsley Underhill. The authors have determined the sensitiveness to light of mixtures containing chlorine, oxygen, and hydrogen, the object having been to find the variation in the rate of formation of hydrogen chloride when the concentration of the chlorine and oxygen were kept constant and that of the hydrogen varied. The concentration of tlie oxygen was small in comparison with that of the chlorine. It was found that as the concentration of the hydrogen was increased from zero, the sensitiveness increased at first very rapidly, attained a maximum value, and then gradually fell.Thus, a mixture which contained 50 per cent. of hydrogen was only twice as sensitive as one which contained only 3 per cent., whilst the sensitiveness of a mixture containing 100 per cent. of hydrogen was less than that of a mixture containing 50 per cent., in the ratio of 7 to 10. The above results ’demonstrate conclusively that the rate of formation of hydrogen chloride is not under ordinary conditions proportional to the number of impacts per second between pairs of molecules of hydrogen and chlorine. Accordingly the conclusion of Wilderman (I’/i~l.Ti-om., 1902, 199, 337), that the rate of interaction of chlorine and carbon monoxide is proportional to the concentration of the colourless constituent is not true for the closely analogous chemical actioii between Chlorine and hydrogen.Even if true therefore for tlie special case investigated by Wilder- man, his conclusion cannot be regarded as generally applicable to photochemical changes. The results of the authors are in agreement with the view that by the action of light a comparatively unstable form of chlorine is produced, and that this, in the presence of a sufficient quantity of hydrogen, is almost entirely converted into hydrogen chloride, whereas in the presence of a deficiency of hydrogen it reverts largely to Grdinary chlorine. 76 69. ‘*The behaviour of calcium and magnesium salts with soap solutions, and the determination of hardness of water.” By Helen Masters and Henry Lhwellyn Smith. It is well known that in the titration of hard waters with soap solution equivalent amounts of calcium and magnesium salts use up different quantities of soap, magnesium salts using up more than calcium salts.It is the unsaturated acids that cause this difference, saturated fatty acids giving soap solutions, which give accurate results with calcium salts aiid magnesium salts or with mixture of the two. Potassium myristate makes a convenient stable solution for this purpose. The solubility of calcium oleate decreases, whilst the solubility of magnesium oleate increases with rise of temperature: With magnesium salts and sodium oleate a precipitate soon forms after titrat,ion at 15O, and this carries down or adsorbs some sodium oleate, and so more soap is required.With calcium salts and sodium oleate at 15O no precipitate forins under the usual condi- tions, the liquid remaining translucent. With soaps mads from the saturated fatty acids precipitates form with both calcium and magnesium salts. 70. ‘(Organic deiivatives of bismuth.” (Preliminary note.) By Frederick Challenger. With the object of preparing organic compounds of bismuth possessing an asymmetric structure, and the resolution of which into optically active components might, under suitable conditions, conceivably be accomplished, the preparation and properties of certain organic derivatives of bismuth are being studied. . Pfeiffer and Pietmh (Ber., 1904, 37,4620) showed that bismuth chloride reacts with an ethereal solution of magnesium phenyl bromide with the formation of triphenylbismuthine in a 25 per cent.yield. This compound was first prepared by Michaelis and Polis (Ber., 1887, 20,54). During the course of the present research triphenylbismuthine has been prepared in an analogous manner from bismuth bromide in a yield of about 50 per cent. Diphenylbromobismuthine, Ph,BiBr (m. p. ISSO), was simultaneonsly produced. Michaelis and Ma.rquard (L4?bn<11e72, 1889, 251, 327) first prepared this substance by the interaction of bismuth bromine and triphenylbismuthine in ethereal solution, and gave the melting point as 157-158O. Pfeiffer and Pietscli do not mention the formation of diphenyl-chlorobismuthine in their experiments.When treated with magnesium a-naphthyl bromide in ethereal solution, diphenylbromobismuthine dissolves and a solid is precipi-tated. Diphenyl-a-naphthylbismuthine has, however, not yet been isolated from the reaction mixture. Tri-a-naphthylbismuthine: which does not seem to have been previously described, has been prepared from bismuth bromide and magnesium a-naphthyl bromide. It crystallises in almost colourless, glistening needles, melting at 235O (uncorr.). When tri-a-naphthylbismuthine (2 mols.) is treated with bismuth bromide (1 mol.) in ether-chl orof orm solution a golden-yellow, crystalline substance separates. This crystallises well f rom benzene (m. p. 211O uncorr.), and has not yet been analysed, but from its properties and method of forniation it would appear to be di-a- naphthylbromobismuthine.The interaction of bismuth bromide and magnesium benzyl chloride under conditions in which a good yield of triphenyl-bismuthine is obtained, does not seem to lead to the formation of tribenzylbismuthine, Bi(CH,Ph),. A yellow substance containing bismuth, bromine, and organic matter, which decomposes without melting and is insoluble in most solvents except glacial acetic acid, is the principal product. The action of the Grignard reagent on derivatives of quinque-valent bismuth, such as triphenylbismuthine dibromide, Ph,BaBr, is being investigated. 71. (‘The estimation of mercury as metal by the dry method.” By Alexander Charles Cumming and John Macleod, The estimation of mercury as metal by the dry method as ordin- arily applied is very troublesome, although it gives accurate result,s. It is found that the process is simplified, and that equally good results are obtained if the mercury compound is heated in a small Penfield tube with a mixture of lime, iron filings, and lead chromate.The modified method was applied to the determination of mercury in mercuric chloride, mercuric sulphide, cinnabar, and mercuric iodide; the results were in all cases satisfactory. 72. “Studies in the diphengl series. Part IV. The absorption spectra of the two isomeric o-dinitrobenzidines.” By John Cannell Cain, Alexander Killen Macbeth, and Alfred Walter Stewart. A comparison between the absorption spectra of the two isomeric o-dinitrobenzidines (Cain, Coulthard, and Micklethwait, T., 1912, 78 101,2298) and that of o-nitroaniline shows that there is a general resemblance between the spectrum of the latter and that of 3:3’-di-nitrobenzidine, whilst the spectrum of 3 :5’-dinitrobenzidine differs distinctly from them.The authors regard o-nitroaniline as having the quinonoid consti- tution : NH,*O ()=N:O I ,“ 1.H and, applying this conception to the case of the o-dinitrobenzidinss, it was shown that their constitutions are satisfactorily explained by the formulze: NH“ I1 l=N:O ()=7:0Y IN H,*o iH,-o 3 :3’-Dinitrobenzidine.* 3 :5’-Dinitrobenzidine.* The constitutions of the isomeric o-dinitrodiphenyls and the acetyl derivatives of the isomeric o-dinitrobenzidines may be explained in an analogous manner.73. ‘‘ A novel method for resolving externally compensated amines : derivatives of d-and I-oxymethylenecamphor.” By William Jackson Pope and John Read. The condeiisation products which d-and I-oxymethylenecamphor form with externally compensated hydroxyhydrindamine and a-phenylethylamine can be conveniently employed in the resolution of these bases into their optically active components. It was also shown that a-camphylamine is a pure optically active base with the aid of the same oxymethylene derivatives. 6-Oxymethylenecamphor can be used to effect a ready separation of d-bornylamine from the d-neohornylamine which accompanies it.* These names are retaiiied for convenience of reference. 74. ‘(A new iron bacterium.” By Ernest Moore Mumford. A new bacillus has been isolated from the Bridgewater Canal tunnels at Worsley, Lancashire. The bacillus designated by the laboratory number, M7, exerts a specific action on solutions containing iron. The organism is a facultative aerobe, and the action on iron solutions varies as the conditions are zerobic or anzrobic. Under zerobic conditions the iron in solution, whether ferrous or ferric, is precipitated as ferric hydroxide. Under anzerobic condi- tions neither ferrous nor ferric solutions are precipitated, but ferric hydroxide already precipitated biologically or chemically is dehydrated and reduced to bog-ore.In Nature these two actions are symbiotic, and are probably the cause of the deposits of bog-ore hitherto attributed to higher bacteria alone. An enzyme has been separated from the organism by the usual methods, and all the chemical reactions of the living organism have been reproduced by the enzyme. The optimum of the enzyme is 70°. Neither the specific action of the organism on iron solutions nor the enzyme are produced in the absence of nitrogen in the medium. The enzyme is a complex substance containing amino-groups, but the basicity of the enzyme to acids bears no relation to the precipi- tating power. The orgmism is a short, round-ended bacillus, 2 microns by 0.4 micron in size. It exhibits a varying motility, and forms endospores and involution forms.It grows well on ordinary media, the growth on potato of greenish-brown nodules being characteristic. 75. ‘(The presence of neon in hydrogen after the passage of the electric discharge through the latter at low pressures.” ByJohn Norman Collie and Hubert Sutton Patterson. A detailed account of an investigation of which a preliminary note has already appeared (this vol., p. 22). 76. (‘The double platinic and cupric iodides of substituted ammonium bases.” By Rasik La1 Datta. The author has prepared the platini-iodides of rubidium, CiEsium, methyl-, ethyl-, allyl-, dimethyl-, diethyl-, trimethyl-, triethyl-, tetra- methyl-, and tetraethyl-ammonium, anilinium, and pyridinium. 80 The cupri-iodides of tetraethyl- and tetraphenyl-ammonium, pyri- dinium, and quinolinium were also described.ADDITIONS TO THE LIBRARY. Berry, Arthur John. The atmosphere. Cambridge 1913. pp. x + 146. ill. 1s. Od. net. (Red 18/2/12.) From the Author.. Canada, Depccrtmsnt of Mines. Report on the utilization of peat fuel for the production of power. By 6.3’. Haanel. Ottawa 1912. pp. xii + 145. ill. (Red.6/2/13.) Mica: its occurrence, exploitation, arid uses. By Hugh S. de Schmid. Ottawa 1912. pp. xiv+411. ill. (Red 6/2/13). From the Department. Plimmer, Robeyt Iienry Adws. The chemical constitution of the proteins. 2nd edition. Part 11. Lgndou 1913. pp. xii + 107. 3s. 6d. net. (Red 11/2/13.} FIoui the Publishers : i\lessr*s.Lougrwns, Green & Co.At the next Ordinary Scientific Meeting on Thursday, April 3rd, 1913, at 8.30p.m., the following papers will be communicated : ‘’ Studies in the camphane series. Part XXXIV. Configuraiion of the eight oximino-derivatives of camphorquinone.” By 31. 0. Forster. ‘‘ Synthesis of a methyl tetrose.” (Preliminary note.) By R. Gilmour. *‘ Experiments on the Walden Inversion. Part IX. The inter- conversion of the optic a 1Iy active phe n y 1met11y1c ar bi n o1s.’ ’ By A. McKenzie and G. W. Clough. “The vapour density of ammonium nitrate.” By P. C. R&yand S. C. Jana. Externally compensated hydroxyliydrindenehydrazine, its de-rivatives, and resolution into optically active components.” By D. H. Peacock. ‘‘ Studies in substituted quaternary azonium compounds contain- ing an asymmetric nitrogen atom. Part I. Resolution of phenyl-ethylmethylazonium iodide into optically active components.” By B. I<. Singh. 11. CLlY AlVD SOSS, LTD., BRUSS\YLCH ST., STAHFORD ST., S.E., AND BUNGAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9132900065
出版商:RSC
年代:1913
数据来源: RSC
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