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Proceedings of the Chemical Society, Vol. 23, No. 329 |
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Proceedings of the Chemical Society, London,
Volume 23,
Issue 329,
1907,
Page 191-202
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摘要:
Issued 13/7/07 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 23. No.329. Thursday, July 4th, 1907, at 8.30 p.m., Sir ALEXANDERPEDLER, C.I.E., F.R.S., Vice-President’, in the Chair. Messrs M.D. Cowsp, H. ILIcCombie, 0. A. Elias, and S. F. Stefl were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Benjamin Omen Jones, Boksburg, Transvaal. Thomas Callan, B.Sc., 22, Church Street, Egremont, Cheshire. Robert Harry Smith, Apsley House, Priory Road, Sheffield. Of the following papers, those marked * were read : *149. (‘isoNitroso-and nitro-dimethyldihydroresorcin.” By Paul Haas. When an ice-cold aqueous solution of the potassium salt of dimethyl-dihydroresorcin mixed with potassium nitrite is acidified, a pale yellow precipitate of isonitrosodimethyIdi~~ydroresorci.iL(I): is obtained.That this substance is in reality an isonitroso-derivative and not a nitroso-derivative is shown by the fact that it does not give 192 Liebermann's reaction, but on the contrary yields coloured potassium, ammonium, and firyous salts after the manner of a-oximino-ketones. Whenisonitrosodimethyldihydroresorcinsuspended in ether is saturated with oxides of nitrogen, prepared from nitric acid and arsenious oxide, it is converted into nitrodimethyldihydroresorcin(11); this substance may also be prepared in a similar manner from dimethyldihydro-resorcin itself. The base (III), obtained by the action of ammonia on dimethyl-dihydroresorcin (Trans., 1906, 89, 191) : when suspended in water and treated with nitrous acid at Oo, yields an isonitroso-derivative of the formula (IV), which gives a crimson potassium salt and a blueferrous salt.Both isonitroso- (I) and nitro- dimethyldihydroresorcin (11) on reduction yield an amine which is converted by nitrous acid into a substance of the formula CsH,,O,N2. That nitrous acid in acting on the base (111) really attacks the carbon atom in the para-position relative to the two methyl groups, and not the imino-group, is shown by the fact that this isonitroso-derivative (IV) yields on reduction and subsequent treatment with nitrous acid the setme substance, C,H,,ON,, as is obtained by a similar series of reactions from the mono-oxinae of isonitrosodimethyldihydro-resorcin (V) : in which the nitrogen atoms arc clearly attached to different carbon atoms.*150. '' The structure of carbonium salts." By Frank Baker. The author has examined the absorption spectra of the sulphates of several derivatives of benzylideneacetone, and also of triphenyl- and trianisyl-carbinol sulphates. These carbonium salts gave rise to two characteristic types of absorption. p-Rosaniline base, as well as the mono-hydrochloride, shows the first type of curve, whilst in presence of more concentrated acid the second of these types of spectra is observed. From these results, the author concluded that the magentas are carbonium salts, similar to triphenyl- carbinol sulphate. 193 Since Gomberg (Ber., 1907, 40, 1847) has shown that the latter compound posse4ees the structure (I): (1.) (11.) the constitution (IT) was ascribed by the author to the salts of p-rosaniline with one equivalent of acid.The second of the above-mentioned types of curve is similar to those of the hydrochlorides of certain members of the hydroxyazo-group (Tuck, Tmm., 1907,91, 449), kind the author suggested that these salts are also carbonium compounds. The absorption spectrum of triphenylmethane was found to differ from that previously described by Harlley (T2*ccns.,1887, 51, 152). DISCUSSION. Dr. CAINmentioned that Gomberg himself, in the paper quoted by the author, adopted Nietzki’s formu!a (NH,-C,H,),C:<~>NH,X for the salts of p-rosaniiine.In view of the work of Hantzsct and Osswald and other chemists, which was generally considered to establish the correctne-s of Nietzki’s formula, it was not likely that Mr. Baker’s suggestion would be accept.ed by colour chemists, par- ticularly as it seemed so improbable that the acidic group X should be attached to the carbon and not to the nitrogen atom. Dr. HEW~TTsaw no necessity to ascribe a carbonium formula to the salts of hydroxyazo-compounds with mineral acids. Chemical reactions pointed to their substances having a quinonoid structure, but it was the phenolic nucleus which apparently becomes altered. In reply, Mr. BAKERpointed out that Gomberg had suggested that in tbe formation of magenta from p-rosaniline base a carbinol cor-re*ponding to the salt of the structure shown by (It) was first formed, and that this compound passed into the iminoquinone, but no proof of the latter change had been presented.“151. “Studies of dynamic isomerism. Part VI. The influence of impurities on the mutarotation of nitrocamphor.” By Thomas Martin Lowry and Egbert Hochey Magson. The velocity of mutarotation of nitrocamphor has been measured in a number of different solvents and in presence of a variety of added impurities. In the experiments on glucose described in the first paper of this 194 series (Trans., 1903, 83,1314), it was found that the mutarotation in aqueous solutions could not be retarded by the addition of either acid or alkali, and appeared to be due to a direct interaction between the sugar and the solvent.In the case of nitrocamphor dissolved in chloro- form, however, it has been found possible to retard the isomeric change by the addition of small quantities of acid, thus confirming the view already arrived at (T~ans.,1899, 75, 221) that the mntarotation of the nitrocamphor in solvents such as chloroform and benzene is con-ditioned by the presence of alkaline impurities. Sodium ethoxide added to an alcoholic solution of nitrocamphor was found to produce an acceleration very similar to that which results from the addition of potassium hydroxide to an aqueous solution of glucose. Extraordinary effects were produced, however, by the addition of piperidine to solutions of nitrocamphor in benzene or chloroform.In presence of N/lOOO piperidine no mutarotation could be detected ; with N/lO,OOO piperidine the mutarotation mas complete in five minutes, with N/lOO,OOO in an hour, and with N/l,OOO,OOO in about ten tiours; with N/10,000,000 piperidine the acceleration was of the same order of magnitude as that due to the trace of impurity normally present in the purified materials. DISCUSSION. Mr. W. A. DAVIS,replying to the question raised by Dr. Lowry as to the origin of the peculiar odour noticed in the chloroform solutions used, suggested that it was due to carbonyl chloride formed by the action of the air on the chloroform. It would appear that this change was accelerated by the presence of an aeid, in this case trichloro-acetic acid ; it was already well known that it could be prevented by hxilg322.s&.u&!!ipw%sPd.,ul.cb a!!kmQ "152.'' The relation between absorption spectra and chemical con-stitution. Part VIII. The phenylhydrazones and osazones of a diketones." By Edward Charles Cyril Baly, William Bradshaw Tuck,Effie Gwendoline Marsden, and [in part] lKaud Gazdar. From a consideration of their absorption spectra it was shown that the phenylhydrazones and osazones of the a-diketones in neutral solution possess the ketonic constitution, and that in alkaline solution the former tend to favour the enolic configuration, thus : Roy:N NH C6H, R*fl-N:N*C,;H, R-CO R*C*OH Nentral solution. Alkaline solution. 195 In the phenylhydrazones of hydroxy-ketones in which the hydroxyl group is adjacent to the :C:N* linking, direct evidence is found of the mutual influence of the hydroxyl group and the C:N linking.This influence is best shown in the great retardation of the change of the hydrazone to the am-form in light; moreover, it is this mutual influence which renders possible the oxidation of the hy droxyl group by excess of phenylhydrazine. Inasmuch as the change to the azo-form removes this influence upon the hydroxyl group, this change tends to restrain the oxidation of the hydroxyl group by phenyl-hydrazine, and as, further, acetic acid retards the change to the azo- form, so the presence of acetic acid aids the formation of the osazones with excess of phenylhydrazine. 153.Permanganic acid.” By Matthew Moncrieff Pattison Huir. By adding the equivalent quantity of dilute sulphuric acid to a solution of barium permanganate, filtering through glass wool, and evaporating over sulphuric acid in n vacuum, solutions of permanganic acid, HMnO,, containing about 17 per cent. of the acid, can be obtained. A small quantity of a fairly concentrated solution of this acid, when left in an open vessel, deposits brown oxides of manganese (zMn02, yMnO, where x=20 and y varies from 6 to lo), mixed with violet-blue crystals of the acid. The latter could not be obtained as a solid except mixed with oxides of manganese. 9very dilute solution of permanganic acid can be boiled without decomposition ;a solution containing about 4 per cent.of the acid deposits a brown film on glass ou keeping for half an hour. More concentrated solutions decompose gradually with evolution of ozonised oxygen ;when evaporated to dryness over sulphuric acid in a vacuum, they give black, almost pure, manganese dioxide. 154. Methyl dicarboxyaconitate.” By Siegfried Ruhemann. The author has found that the esters of dicarboxyaconitic acid are not produced in a manner similar to the formation of ethyl dicarboxy- glutaconate, namely, by the action of the esters of trichloroacetic acid on ethyl sodiomalonate, -but methyl dicarboxyaconitate, C0,Me.C :C(CO,Me),*CH(CO,Me),, was prepared according to the directions of Auschutz and Deschauer (Annakm, 1906, 347,3). Phenylhydrazine reacts with the ester at the ordinary temperature to yield the additive product C0,BIe*C(NH*NH*C,H,)[CH(C0,Me),]2 (colourless prisms, m.p. 135’). This is fairly stable, but is decom-posed when it is digested with dilute caustic potash or boiled with 196 sodium carbonate with formation of malonic acid and monomethyl phenylpyraxolonedicarboxylate (colourless prisms which melt and decom-pose at 201--202'). The author considers that the formula of this N=Y*CO,Hester is C,H,*N< CO CH*CO,Me' On boiling with concentrated, aqueous potassium hydroxide, it furnishes potassium 1-phenyl-5-pyrazol- one-3-carboxylate, C,H,*N< N=y* CO,K CO CH, ' At 1OOO, phenylhydrazine and methyl dicarboxyaconitate form, besides methyl malonate, the compound C2,H,,0,N6. This, with dilute hydrochloric acid, yields phenylhydrazine hydrochloride and the pl~n&draxide of monomethyl phelzylpyl.uxolonedicas.boxyklte, N=y*CO*NH*NH*C,H, C6H5'N<C0 CH*CO,Me (colourless needles which decompose on heating).The compound C,,H,,O,N, therefore is the phem~Zhydvnzineeal t of this substance. Methyl dicarboxyaconitate, on being heated with aniline at loo", is decomposed, and furnishes carboxymetlryZa.nilinosnethylelzemaZonccni1, C0,Me*C(NH*C,H5):C<CO>N*C,H5(canary-yellow- prisms, m. p.CO 194"). 155. (( The action of heat on a,hydroxycarboxylic acids. Part 111. aa'-Dihydroxysebacic acid and its diacetgl derivative." By Henry Rondel Le Sueur. The author has now extended his investigation of the action of heat on a-hydroxy-acids to the hydroxy-derivatives of di basic acids.When aa'-dihydroxysebacic acid or its diacetyl derivative is heated at 250--270°, it decomposes with evolution of carbon monoxide and formation of the dialdehyde of suberic acid : CO,H-CH(OH )*[CH,],*CH(OH)~CO,H -+ CHO-[CH,],*CHO. 156. ('Dihydroxyadipic acids. (Preliminary note.)" By Henry Rondel Le Suenr. When the bromine atoms in aa'-dibromoadipic acid are replaced by hydroxyl groups, two dihydroxyadipic acids are obtained, one melting at 146O and the other at 174'. Both form insoluble, crystalline silver 197 salts, and when the acid melting at 146O is heated, it loses water with foi-mation of a dilactone which sublimes in well-defined plates.As aa’-dihytroxyadipic acid contains two asymmetric carbon atoins, it is probable that the above acids are stereoisomerides. 157. The relation between absorption spectra and optical rotatory 64 power. Part 11. The tartaric acids.’’ By Alfred Walter Stewart. The absorption spectra of the two active forms of tartaric acid are identical, and show only slight general absorption. When an equi-molecular mixture of the two antipodes containing the same weight of acid as in the previous cases is used, a greater general absorptioii is found, proving that racemic acid has a greater power of absorption than either active form. When the racemic acid solution is diluted, however, its absorptive power gradually approximates to that of the active acids, with which it eventually becomes identical.This shows that in dilute solution the racemic acid is broken down into the two active forms, as has already been suspected from results obtained in freezing point, boiling point, and vapour density determinations. These spectroscopic results were corroborated by somewhat $irnilar ones obtained with the active limonenes and dipentene. As a double salt above and below it -temperature of transition furnishes the closest parallel to a solution which may contain either a mixture of two antipodes or a racernic compound, the spectrum of astrakanite above and below 22’ was examined. It was found that above this temperature an absorptive power was shown differing from that observed below 22O, so that the two cases itre evidently analogous. This also furnish(s a new method of determining transition temperatures. It was found that i-tartaric acid had the strongest absorptive power of all, being much more absorbent than racemic acid.No absorption bands were found in any of the spectra. Applications of this work to various questions, such as the determination of existence limits in the case of racemic compounds, the proof of the actual formation of a,liquid racemic corupouncl (as distinct from an inactive equimolecular mixture), and the existence of pseudo-racemic compounds were discussed. 158. “Experiments on the synthesis of the terpenes. Part XI. Synthesis of 4-isopropylidenecyclohexanoneand its derivatives.” By William Henry Perkin, jun., and 3oh Lionel Simonsen.The sodium derivative of ethyl a-acetylglutarate, CO,E t CHNa(COMe)CH2*CH,*CO,Et, reacts readily with ethyl /I-iodopropionate with the formation of ethyl y-acetylpentane-ayets.icurboxyZate, C0,Et*C(COMe)(CH2*CH2*C02Et),, which dist,ils at 217" (15 mm.), and on hydrolysis with hydrochloric acid is converted into y-acetylpimelic acid, COMe*C'H(CH,*CH,*CO,H),. This acid is a colourless syrup which yields a semicarbaxone melting at 177". When ethyl y-acetylpimelate is treated with magnesium methyl iodide, it is converted into the lactone of ethyl hydrogen at 200" (22 mm.), and yields, with hpdrobromic acid, ethyl ?hydrogen y-(bronzoisopropyE)pimeZate, Me,CBr CH(CH2*CH,*C02Et)C€€,* CH,=CO,H. EtliyZ y-(bronzoisopropyl)pimelute, Me,C Br CH(CH, CH, C0,E t)2, obtained by the esterification of the latter compound, is decom-posed by pyridine with formation of ethyl y-isopropylidenepimelate, Me,C':C(CH,*CH,*CO,Et), (b.p. 168' under 13 mm.), and, on hydro-lysis, yields y-isopropyZidenepirrzeEic acid, which cry stallises in prisms and melts at 97". Ethyl 4-isopropyliderrecyclohexanone-2-cn~~boxyZc~te, CH,*CH, Me,C:C/ >CO , is obtained when the solution of ethyl \CH, CH*CO,Et y-isopropylidenepimelate in toluene is treated with sodium ;it decom-poses on distillation, combines with hydrogen bromide to form ethyl 4-/3-bromoisoprop~Zcyclo?~exanone-2-carboxylate, is hgdrolysed byand alcoholic potash with formation of 4-isopropyEidenecyclohexanone, This ketone distils at 219-221O and yields a semicurbaxone which melts at 201"; hydrobromic acid converts it into 4-/3-bromoisopropyZ- cyclohexanone, Me,CBr CH<CH,.CH2CH2*CH2>co, The object of this research was to endeavour to synthesise nopinone, CH2*CH2 CH/CM% \GO, from the above bromo-ketone by the elimina- \\ CH,--CH/ tion of hydrogen bromide, but the experiments which were made in this direction have so far been unsuccessful.159. 'I The purification of acetic ester." By John Kenneth Harold Inglis and Lottie Emily Knight. Great difficulty has always been experienced in preparing pure acetic ester, and although several methods have been suggested, no 199 one of them is satisfactory since the yield of pure eater is small arid the process of preparing it laborious.For the preparation of aceto-acetic ester, very nearly pure acetic ester is required, and the presence of a moderate quantity of alcohol-the most likely impurity-is fatal to success. A series of experiments has shown that the separation can be most easily carried out by first converting the alcohol into an ester of high boiling point and then distilling. If the crude ester, as obtained in the ordinary continuous process, is dried over potassium carbonate (which also removes any acetic acid) and treated with phosphoric oxide, a slow action takes place with the formation of phosphoric esters which are neither volatile nor decomposed at the boiling point of ethyl acetate (77*20° corr.).In this way a yield of 160 grams of ester boiling within one degree was obtained in an experiment in which the theoretical yield was 264 grams, that is, 60 per cent. of ester was obtained pure. This process, however, is slow, and requires several days for completion at the ordinary temperature. On the other hand, the removal of the alcohol takes place more rapidly at the boiling point. Thus a mixture of 100 grams of ester (b. p. 76.65-77.15') with 8 grams of absolute alcohol distilled continuously between 73' and 77', only 21 grams passing oiler above 76.3'. When, however, the fractions had been mixed together and heated for half an hour with 10 grams of phosphoric oxide, using a reflux condenser, a single distillation gave 72 grams of distillate between 76.7' and 77*2O,that is, 72 per cent.of an approximately pure substance. This result shows that it is easy to obtain by this method a good yield of acetic ester boiling within 0.5'; and it was found that an ester of this purity gave' a good yield of acetoacetic ester. 160. Solubility of lead sulphate in concentrated solutions of ammonium acetate (Preliminary note)." By John Jacob Fox. Solubility experiments were carried out with the view of determining the course of the reaction occurring between ammonium acetate and lead sulphate. The solid phases were examined to ascertain whether they changed during the solution. The following are some of the results obtained from the analysis of the solutions saturated at 24.9', the concentration of the ammonium acetate varying from about normal upwards : Molecules of salt per 1000 molecules of water.Density Ainnioniuni Ammonium of solution. acetate. sulpliate. Lead acetate. 1.0197 20‘0 0.54 0’52 1‘0320 31 ‘2 093 0 ’92 1*04.57 44 5 1’29 1‘46 1-0578 55 ‘6 2’11 2 ‘05 1’0694 63 ‘5 2.7’7 2.74 1‘I094 94 .1 2’ii 631 1.1251 133 .:3 2.50 8.10 The curve obtained does not agree with the formula developed by Nojes (Amer. Chem. Soc., 1905, 27, 7473, the solubility beiDg greater than that given by the formula. The solid phase consisted of lead sulphate and was unaltered with concentrations of amrnonium acetate up to rather more than 3N, but with more concentrated ammonium acetate, well-defined crystals of lead ammonium sulphate, mere obtained.The solubility of the lead sulphate increased considerably with ammonium acetate of greater concentrations than above, and the solid phases consisted of mixtures of lead sulphate and lead ammonium siilphate. The lead is probably present in solution as lead acetate, since the amount of siilphate in solution gradually became less than the equivalent of the lead present as the concentration of the arnmoriirrni acetate was increased beyond 3K. 161. ‘‘ Researches on morphine.” Part 111. By Frederic Herbert Lees. In continuation of previous work (Schryvet. and Lees, Trans., 1900, 77, 1024 ; 1901, 79, 563, and Lees and Tutin, Proc., 1906, 22, 253), the author has shown that chloromorphide and brornomorphide yield chlorocodeide and brornocodeide respectively on methylation the two latter bases previously obtained by other methods being simply the codeine analogues of the two former bises.By the hj drolysis of chloromorphide, the author has isolated, besides P-isomorphine, an hitherto undeecribed isonieride of morphine previously indicated by the hydrochloride ([.ID -92.5’) obtained hy Srhrjver and Lees. On methylation, this new base gives the so-called ‘‘ $-codeine ” (compare Merck, Arch. Pharm , 1891, 229, I6 1 ; Vongerichten, Ber., 1903, 36,1591, and Knorr and Horlein, Ber., 1906, 39,4409). As the name $-morphine belongs to a well knowu oxidation product of morphine of which Merck’s ‘‘ $-codeine ” is not the methyl ether or codeine analogue, the author has termed the new isomeride of morphine, neoisomoiphine and its methyl ether, neoisocodeine.201 ~Veoisonzorphine, C17H,,0,N, cryetallises from alcohol in brilliant, prismatic needles containing one molecule of the solvent (tn. p. 278') ; its hydrocTdoride, C17Hl,0,N,HCI, forms an hydrous crystals from alcohol ([aID -79.1" in water) ; its naethiodide, C,7H,,0,N,MeI, forms glistening crystals from alcohol (m. p. 297' ; [aID -54.5' in water). Neoisocodeine, C,,H,,O,N, forms large colourless prisms from ethyl acetate (m. p. 181-182° ; [a],, -96.6" in alcohol). P-isoMorphine on met.hylation furnishes P-isocodeine, C,,H2,0,N, which did not crystallise. The methiodide, ClsH2~03N,MeI, forms tabular crystals from water (m.p. 215-216'; [aID-145.5' in water), and on boiling with sodium hydroxide readily yields a met,hine base. It was also shown that the '' A-Bccse" (m. p. 147-147.5' ; [aID-205.5" in chloroform) previously obtained by Lees and Tutin (Zoc. cit.)together with isocodeine (m. p. 171-178'; [aID-155°inchloroform) by the hydrolysis of bromocodeide as a definite substance, not resolv-able by recrystallisation, is in reality a molecular combination of isocodeine and /3-isocodeine. ADDITIONS TO THE LIBRARY. I. Donations. British Guiana. Report of the Commission appointed to enquire into and report upon the general and infantile mortality ; together with minutes of the sittings, evidence of witnesses, &c. pp. viii + 154. Georgetown, Demerara.1906. (Recd. 1/7/7.) From His Excellency the Governor of the Colony of British Guiana. Geneva, L7niversityof, Seance solennelle de distribution des prix de Concours, 28 Janvier, 1907. Rapports du Recteur et des Jurys pi*ecGddsd'une notice biographique sur Humphry Davy [par Philippe A. Guye]. pp. 96. Genhve 1907. (Recd. 10/6/6.) From Professor Philippe A. Guye. Neumann, Bernhcwd. Elektrometallurgie des Eisens. pp. x + 176. ill. Hall a 8. 1907. (Recd. 21/6/7.) From Dr. F. M. Perkin. Zeitschrift fur anorganische Chemie. Edited by G. Kruss. Vol. I. Hamburg 1892. (Recd. 26/6/7.) From Professor J. W. Mallet. 202 THE LIBRARY. ‘l’he Library will be closed throughout the month of Augusk, when the Society’s Rooms will be redecorated, and the annual revision of the volumes will take place.Fellow3 are particularly requested to return all Library Rooks in their possession not late?*thnit TVed?Lesday,July 31st. LIST OF FELLOWS, 1907. The List of Fellows for 1907 is now in active preparation, and ,changes of address received after 31st July cannot be imluded in it. In order that the new list may be as complete as possible, those Fellows whose degrees and Christian names do not appear in full are requested to communicate them to the Assistant Secretary. CORRECTION. 1907. Page 144, lines 1 and 2 from top : Dr. Divers finds himself to have been in error when he assumed that Messrs. Barlow and Pope had allowed no valency to the oxygen in hydroxyl. He had read literally their expression 2Mg(F)(OH) (I’rccns.,1906, 89, 1686), instead of as 2Mg with 1F and l(OH), as was intended by the authors it should be read. The next Ordinary Meeting will be held on Thursday, October 24th, $907,at 8-80 p.m. R. CLAY AND SONS, LTD., BREAD ST. HlLL, E.C., AND BUNOAT, SUYFOLK
ISSN:0369-8718
DOI:10.1039/PL9072300191
出版商:RSC
年代:1907
数据来源: RSC
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